JP6547247B2 - Heat curable composition - Google Patents

Description

  The present invention relates to a heat curable composition.

Conventionally, a composition containing a urethane prepolymer has been used as an adhesive, a sealing material, a coating material, and the like.
Such compositions are generally used as a one-component type or additionally as a two-component type with a polyamine compound, but a one-component composition is usually moisture curable and therefore cures slowly and a two-component composition Although the storage stability is excellent, the workability is poor.
On the other hand, the (A) polyisocyanate compound and the terminal active isocyanate group-containing urethane prepolymer obtained by reacting an excess amount of the polyisocyanate compound with the polyol component for the purpose of coexistence of low temperature curability and storage stability, alone or respectively And a mixture of them; and (B) solid powder having a melting point of 50 ° C. or more and a central particle diameter of 20 μm or less, a fine powder having a central particle diameter of 2 μm or less, and a weight ratio of the solid amine to the fine powder of 1 / 0.001 A heat-curable composition is known which is characterized in that it comprises a fine powder-coated amine coated with an active amino group on the surface so as to be fixed at -0.5 (Patent Document 1).

WO 95/26374

However, the inventors have found that when the coating material used to coat the solid amine is a fine powder, the storage stability may be low.
Then, an object of the present invention is to provide a thermosetting composition which is excellent in storage stability.

As a result of intensive research to solve the above problems, the present inventor
At least one terminal isocyanate-containing urethane prepolymer obtained by reacting a polyisocyanate compound and a polyol compound,
Containing a solid amine having a melting point of 50 ° C. or more and a coated amine coated with a filler,
When the value of the ratio of the major axis of the filler to the particle thickness of the filler (major axis / particle thickness) is 4 or more and 100 or less and the particle thickness is 0.01 μm or more and 1 μm or less, heat curability excellent in storage stability We found that a composition was obtained and completed the present invention.
That is, the present invention provides the following heat-curable composition.

[1] At least one terminal isocyanate-containing urethane prepolymer obtained by reacting a polyisocyanate compound and a polyol compound,
Containing a solid amine with a melting point of 50 ° C. or higher and coated with a filler;
The heat-curable composition, wherein the value of the ratio of the major axis of the filler to the particle thickness of the filler (major axis / particle thickness) is 4 to 100, and the particle thickness is 0.01 μm to 1 μm.
[2] The thermosetting composition according to [1], wherein the average particle diameter of the coated amine is 100 μm or less.
[3] The heat-curable composition according to [1] or [2], wherein the solid amine is pulverized.
[4] The heat-curable composition according to any one of [1] to [3], wherein at least a part or all of the surface of the coated amine is hydrophobized by a silane coupling agent and / or a silicone oil. .
[5] The heat curable composition according to any one of [1] to [4], wherein the average particle size of the solid amine is 75 μm or less.
[6] The heat-curable composition according to any one of [1] to [5], wherein the shape of the filler is plate-like or non-plate-like.

  The thermosetting composition of the present invention is excellent in storage stability.

FIG. 1 is a photograph of the comparative coated amine 1 produced in the Example of the present application observed with an electron microscope (2000 × magnification). FIG. 2 is a photograph of the coated amine 1 produced in the Example of the present application observed with an electron microscope (2000 × magnification). FIG. 3: is an (a) top view and (b) front view which represents typically an example of a plate-shaped filler. FIG. 4: is (a) top view and (b) II sectional drawing which represents typically an example of a spindle-shaped filler.

The present invention will be described in detail below.
The thermosetting composition of the present invention (hereinafter also referred to as "the composition of the present invention") is
At least one terminal isocyanate-containing urethane prepolymer obtained by reacting a polyisocyanate compound and a polyol compound,
Containing a solid amine with a melting point of 50 ° C. or higher and coated with a filler;
It is a heat-curable composition, wherein the value of the ratio of the major axis of the filler to the particle thickness of the filler (major axis / particle thickness) is 4 to 100, and the particle thickness is 0.01 to 1 μm. .

Although the reason why the composition of the present invention is excellent in storage stability is not clear, the present inventor speculates the reason as follows.
As in the prior art, when solid amine is coated with fine powder, fine powder is an aggregate of fine powder and / or particles and is often spherical, so the coverage of solid amine surface with fine powder is It is considered low.
In addition, in the case of simply using a material having a large particle size as a spherical material for coating a solid amine in order to increase the coverage, although the solid amine can be coated more, the amine after coating also becomes larger. In a composition containing such a large coated amine, it is considered that the coated amine becomes a lump and the composition does not become uniform.
On the other hand, when the ratio of the major axis of the filler to the particle thickness of the filler used in the production of the coated amine (major axis / particle thickness) is 4 or more and 100 or less and the particle thickness of the filler is 0.01 μm or more and 1 μm or less It is considered that the surface of the solid amine can be efficiently covered (including the case of complete coating), and the generation of the filler particles is suppressed at the time of coating, and excellent storage stability is realized.

The terminal isocyanate-containing urethane prepolymer is described below.
The terminal isocyanate-containing urethane prepolymer (hereinafter referred to simply as "urethane prepolymer") contained in the composition of the present invention is a terminal isocyanate obtained by reacting a polyisocyanate compound with a polyol compound. It is a urethane prepolymer having a group.
The urethane prepolymer preferably has a plurality of isocyanate groups.

  The polyisocyanate compound used in the production of the urethane prepolymer is not particularly limited. For example, aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate can be mentioned. Among them, aromatic polyisocyanate is preferable, and diphenylmethane diisocyanate (hereinafter sometimes referred to as “MDI”) is more preferable, from the viewpoint of being excellent in storage stability and excellent in thermosetting property.

  The polyol compound used in the production of the urethane prepolymer is not particularly limited as long as it has two or more hydroxy groups. For example, polyether polyol, polyester polyol, polymer polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, acrylic polyol, and mixtures thereof can be mentioned.

  The polyether polyol includes, for example, polyoxyethylene diol, polyoxyethylene triol, polyoxypropylene diol, polyoxypropylene triol, diol or triol of a copolymer of oxyethylene and oxypropylene.

Examples of polyester polyols include at least one low molecular weight polyol selected from the group consisting of ethylene glycol, propylene glycol, butanediol pentanediol, hexanediol, glycerin and 1,1,1-trimethylolpropane, and glutaric acid, Condensation polymers with at least one member selected from the group consisting of adipic acid, pimelic acid, suberic acid, sebacic acid, dimer acid, low molecular weight aliphatic carboxylic acid and oligomeric acid; ring-opening weights such as propionolactone and valerolactone Coalescence is mentioned.
The polyol compound is mentioned as one of the preferred embodiments of polyoxypropylene diol (PPG).

  The amount of the polyisocyanate compound and the polyol compound to be used when producing the urethane prepolymer is preferably such that NCO group / OH group (molar ratio) is 1.2 to 2.5, and 1.5 to 2 It is more preferable to be .2. When the ratio is in such a range, the viscosity of the resulting urethane prepolymer becomes appropriate, and the composition can be made difficult to foam.

The urethane prepolymer is not particularly limited for its production. For example, it can carry out by heating and stirring a polyisocyanate compound and a polyol compound at 50 to 100 ° C. In addition, if necessary, urethanization catalysts such as organic tin compounds, organic bismuth, amines and the like can be used.
The urethane prepolymers can be used alone or in combination of two or more.

The coated amine is described below.
The coated amine contained in the composition of the present invention is a solid amine having a melting point of 50 ° C. or higher coated with a filler,
The ratio of the major axis of the filler to the particle thickness of the filler (major axis / particle thickness) is 4 or more and 100 or less, and the particle thickness of the filler is 0.01 μm or more and 1 μm or less.

The solid amine is described below. The solid amine used for producing the coated amine contained in the composition of the present invention has a melting point of 50 ° C. or higher.
Here, the melting point is a value measured at a temperature rising rate of 10 ° C./min by differential scanning calorimetry (DSC-Differential Scanning Calorimetry).
The melting point of the solid amine is preferably 50 to 100 ° C. from the viewpoint of excellent storage stability and excellent thermosetting.
The solid amine is mentioned as one of the preferred embodiments as a polyamine having two or more amino groups or imino groups (-NH-) in one molecule.

As the solid amine, for example, o-phenylenediamine, m-phenylenediamine, 2,3-tolylenediamine, 2,4-tolylenediamine, 2,5-tolylenediamine, 2,6-tolylenediamine, 3 Aromatic polyamines such as 2,4-tolylenediamine; 1,12-dodecanediamine, 1,10-decanediamine, 1,8-octanediamine, 1,14-tetradecanediamine, 1,16-hexadecanediamine, etc. Such aliphatic polyamines can be mentioned.
Among them, aliphatic polyamines are preferable, aliphatic diamines are more preferable, and 1,12-dodecanediamines are more preferable, from the viewpoint of being excellent in storage stability and thermosetting.

  A solid amine is mentioned as one of the desirable modes that it is ground from a viewpoint that it is excellent in storage stability and is excellent in the homogeneity of a composition, and thermosetting.

The average particle size of the solid amine is preferably 75 μm or less, and more preferably 2 to 20 μm, from the viewpoint of being excellent in storage stability, and excellent in uniformity of the composition and thermosetting property.
In the present invention, the average particle size is measured by dispersing particles in methanol and using a particle size distribution measuring apparatus (Microtrac MT 3000 II (laser diffraction / scattering type particle size distribution measuring apparatus, manufactured by Nikkiso Co., Ltd.)) by laser diffraction. Volume average particle diameter.

The maximum particle diameter of the solid amine is preferably 300 μm or less from the viewpoint of being excellent in storage stability and excellent in uniformity of the composition and thermosetting property.
The maximum particle size refers to the maximum value of the volume particle size obtained by the measurement of the average particle size.

  The filler is described below. In the present invention, the ratio of the major axis of the filler to the particle thickness of the filler used in the production of the coated amine (major axis / particle thickness) is 4 or more and 100 or less, and the particle thickness of the filler is 0.01 μm or more and 1 μm It is below.

  In the present invention, the major axis of the filler is the length of the longest side of the square circumscribing the filler and in which all the corners are at right angles.

When the long diameter / particle thickness of the filler is 4 or more and 100 or less, the storage stability, the thermosetting property, and the appearance of the heat-curable composition obtained are excellent (for example, lumps and particles of coated amine are generated in the composition) It is difficult to do so.
In addition, the long diameter / particle thickness of the filler is preferably 4 to 95, and more preferably 4 to 75 from the viewpoint of being excellent in storage stability and excellent in curability.

When the particle thickness of the filler is 0.01 μm or more and 1 μm or less, the storage stability, the curability, and the appearance of the heat-curable composition obtained are excellent.
The particle thickness of the filler is preferably 0.01 to 0.9 μm, and more preferably 0.02 to 0.8 μm from the viewpoint of being excellent in storage stability and excellent in thermosetting property.

The long diameter of the filler is preferably 0.1 to 15 μm, and more preferably 0.3 to 5 μm, from the viewpoint of being excellent in storage stability and excellent in thermosetting property.
In the present invention, the major axis of the filler is an average value of major axes obtained by measuring 20 fillers optionally extracted by magnifying them with an electron microscope. The particle thickness of the filler is also the same.

  In the present invention, the filler used for producing the coated amine does not include those having a major axis / particle thickness of less than 4. As a thing of long diameter / particle | grain thickness being less than 4, a spherical filler (The thing of about 1 long diameter / particle | grain thickness) is mentioned, for example.

The shape of the filler that can be used for producing the coated amine is not particularly limited as long as the major axis / particle thickness is 4 or more and 100 or less. For example, plate-like or non plate-like can be mentioned.
The plate-like filler is not particularly limited as long as it has a plate-like shape.
Examples of the shape of the plate-like filler include a disk-like, square plate-like, strip-like and other irregularly shaped plate-like. The periphery of the plate-like filler may be distorted.

A plate-like filler is demonstrated below using attached drawing. The present invention is not limited to the attached drawings.
FIG. 3: is an (a) top view and (b) front view which represents typically an example of a plate-shaped filler.
In FIG. 3, the plate-like filler 30 has (a) a surface 32 of the plate-like filler shown in the plan view and (b) a side face 34 shown in the front view.
The largest diameter of the surface 32 is the major diameter B of the plate-like filler 30. Further, the thickness of the side surface 34 is the particle thickness A of the plate-like filler 30.

The non-plate-like filler is described below.
As a shape which a non-plate-like filler has, rod-shaped is mentioned, for example. Examples of the shape of the rod-like filler include a spindle shape, a cylindrical shape, a prismatic shape, and a needle shape.
The ends of the rod-like filler may be sharp or rounded.
The spherical shape is excluded as the shape of the non-plate-like filler.

When the non-plate-like filler is a rod-like filler, the particle thickness of the rod-like filler may be the same or may vary from the end of the rod-like filler to the other end.
When the rod-like filler is a spindle-shaped filler, the particle thickness of the spindle-shaped filler refers to the maximum diameter of the cross section perpendicular to the major axis of the spindle-shaped filler.

The spindle shaped filler is described below with the aid of the attached drawings. The present invention is not limited to the attached drawings.
FIG. 4: is (a) top view and (b) II sectional drawing which represents typically an example of a spindle-shaped filler.
In FIG. 4A, the spindle-shaped filler 40 has a major axis D, and the position of the I-I cross section is approximately at the center of the major axis D.
FIG. 4 (b) shows a cross section 44 in the I-I cross section of FIG. 4 (a), where the cross section 44 has a particle thickness C.

  Examples of the filler include talc, mica, calcium carbonate and the like. Among them, talc and calcium carbonate are preferable from the viewpoint of easy surface treatment (for example, hydrophobic treatment) and easy coating of solid amine particles (filler is easily adsorbed on the surface of solid amine particles).

  The amount of the filler used in producing the coated amine is preferably 50 to 300 parts by mass with respect to 100 parts by mass of the solid amine, from the viewpoint of being excellent in storage stability and excellent in thermosetting property. It is more preferable that it is 100-250 mass parts.

  The method for producing the coated amine is not particularly limited. For example, it can manufacture by mixing solid amine and a filler using a Henschel mixer etc.

  In the present invention, it is mentioned as one of the preferred embodiments that at least a part or all of the surface of the coated amine is hydrophobized by a silane coupling agent and / or a silicone oil. In an embodiment in which at least part or all of the surface of the coated amine is hydrophobized, for example, at least part or all of the surface of the plate filler, non-plate filler and solid amine possessed by the coated amine is hydrophobized The aspect currently processed is mentioned.

When the filler absorbs moisture, the reaction between the urethane prepolymer and the solid amine may proceed. For this reason, when the filler is hydrophobized with a silane coupling agent and / or silicone oil, it is more preferable for its storage stability.
In addition, when the solid amine is hydrophobized by a silane coupling agent and / or silicone oil, it has a barrier effect that prevents active hydrogen on the particle surface of the solid amine from contacting and reacting with isocyanate groups in the matrix. It is excellent by storage stability.

The silane coupling agent and / or silicone oil as a surface treatment agent used for hydrophobization treatment (surface treatment) is not particularly limited.
Examples of silane coupling agents include isocyanate silanes, alkyl silanes, epoxy silanes, vinyl silanes and the like.
Among them, isocyanate silanes and silicone oils are preferred from the viewpoint of the excellent storage stability and the high hardness of the cured product obtained using the heat-curable composition.

  The isocyanate silane is not particularly limited as long as it is a silane coupling agent having an isocyanate group. For example, at least one poly selected from the group consisting of an adduct of 1,1,1-trimethylolpropane (TMP) and tolylene diisocyanate (TDI) and an adduct of TMP and xylylene diisocyanate (XDI) Isocyanate compound, N, N-bis [(3-trimethoxysilyl) propyl] amine, N, N-bis [(3-triethoxysilyl) propyl] amine, N, N-bis [(3-tripropoxysilyl) 1) selected from the group consisting of (propyl) amine, 3- (n-butylamino) propyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and 3- (n-propylamino) propyltrimethoxysilane Aromatic isocyanate silanes obtained by addition with a silane compound of a kind or more; Trimethoxysilane, include aliphatic isocyanate silanes such as isocyanate propyl triethoxysilane.

  Examples of silicone oils include diorganopolysiloxanes such as dimethyl silicone oil and methyl phenyl silicone oil; organohydrogenpolysiloxanes such as methyl hydrogen silicone oil; various functional groups introduced into side chains and / or ends Silicone oil is mentioned.

  The amount of the surface treatment agent is 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the filler and the solid amine from the viewpoint of being excellent in storage stability and excellent in thermosetting and adhesiveness. Preferably, it is more preferably 0.5 to 2 parts by mass.

  The method of hydrophobization treatment is not particularly limited. For example, when mixing solid amine particles and a filler, a surface treatment agent may be added to carry out a hydrophobization treatment. In addition, the hydrophobic treatment may be applied to the filler and the solid amine in advance. It may be applied to coated amines.

The average particle diameter of the coated amine is preferably 100 μm or less, more preferably 2 to 75 μm, from the viewpoint of being excellent in storage stability and excellent in uniformity and thermosetting properties of the composition.
The coated amines can be used alone or in combination of two or more.

  The amount of coated amine (including the amount of surface treatment agent when coated amine is surface-treated) is more excellent in storage stability and excellent in physical properties of cured product, relative to 100 parts by mass of urethane prepolymer. 0.1 to 50 parts by mass is preferable, and 0.3 to 30 parts by mass is more preferable.

  The composition of the present invention may further contain an additive, in addition to the above components, as needed, as long as the effects thereof are not impaired. The additives are not particularly limited. For example, plasticizers such as diisoninyl phthalate, fillers, catalysts, solvents, adhesion promoters and the like can be mentioned.

  The composition of the present invention is not particularly limited for its production. For example, urethane prepolymers, coated amines, and additives which can be optionally used can be mixed and manufactured.

  Since the composition of the present invention is excellent in storage stability, it can be produced as a one-pack type. For example, the inside of the container containing the composition of the present invention may be replaced by nitrogen gas.

  The composition of the present invention can be cured by heating. The heating is preferably at 60 to 90 ° C. Since the composition can be cured by such low temperature heating, the composition of the present invention is easy to handle and can be cured in a short time.

The substrate to which the composition of the present invention can be applied is not particularly limited. For example, metal, painted plate, glass, rubber, plastic and the like can be mentioned.
The composition of the present invention can be used, for example, as an adhesive for automobile parts and an adhesive for septic tanks.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these.

<Production of coated amine> (coated amines 1 to 8, comparative coated amines 1 to 4)
As a solid amine, 1,12-dodecamethylenediamine (manufactured by Tokyo Kasei Kogyo Co., Ltd., melting point 68 ° C., pulverized material pulverized by a pin mill pulverizer and having passed screen width 300 μm, average particle diameter: 10 μm) was used.
The amount (parts by mass) of the covering material (filler) described in the column of production of coated amine in Table 1 below with respect to 30 parts by mass of the solid amine was used.
When a surface treatment agent is used, the surface treatment agent (silane coupling agent (R-Si treatment agent, NCO-Si treatment agent) or silicone oil) shown in Table 1 with solid amine and a covering material (filler) 1 part by mass was used with respect to a total amount of 100 parts by mass.
And the above-mentioned solid amine, a covering material (filler), and the surface treatment agent used as needed were mixed for 10 minutes-30 minutes under conditions of 50 ° C using a Henschel mixer apparatus, and coated amine was manufactured. . In addition, it is as showing in the following Table 1 about the average particle diameter of the manufactured coated amines 1-8.

The details of the components (coating material, surface treatment agent) used in the production of the coated amine in Table 1 are as follows.
Fine powder: titanium oxide (trade name: MT-150A, manufactured by Tayca Corporation, shape: cubic, average particle size: 0.015 μm, major axis / particle thickness: 3.4)
-Coating material 1: Talc (trade name: NANO ACE D-600, manufactured by Nippon Talc, shape: plate-like, long diameter / particle thickness: 2.4, particle thickness: 0.25 μm)
・ Covering material 2: Mica (trade name: TM-10, Yamaguchi mica, shape: plate-like, long diameter / particle thickness: 130, particle thickness: 0.08 μm)
-Plate-like talc 1: MICRO ACE P-3 (manufactured by Nippon Talc, shape: plate-like, long diameter / particle thickness: 20, particle thickness: 0.025 μm, no surface treatment)
-Surface treatment agent (R-Si treatment): KBM-3103 (decyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.-Surface treatment agent (NCO-Si treatment): KBE-9007 (isocyanate propyltriethoxysilane), Shin-Etsu Chemical Industry surface treatment agent (silicone oil treatment): KF-99 (methyl hydrogen silicone oil) Shin-Etsu Chemical Co., Ltd. mica 1: A-11 (Yamaguchi Mica company, shape: plate-like, major axis / particle thickness) : 4.8, particle thickness: 0.3 μm, no surface treatment)
· Light calcium carbonate 1: Tama Pearl TP-123 (Okutama Chemical Industry Co., Ltd., Shape: spindle-like, particle thickness: 0.2 μm, long diameter: 1.5 μm, long diameter / particle thickness: 7.5)

A comparative coated amine 1 produced using finely divided titanium oxide as the coating material is described below with the aid of the attached drawings.
FIG. 1 is a photograph of the comparative coated amine 1 produced in the Example of the present application observed with an electron microscope (2000 × magnification).
In FIG. 1, in the comparative coated amine 1 (reference numeral 10), the solid amine 12 was coated with the fine powder 14 of titanium oxide. However, as shown in FIG. 1, in the case of comparative coated amine 1 (symbol 10), solid amine 12 was exposed in the portion of symbol 12 and the like. It is considered that this is because the major axis / particle thickness of titanium oxide used as the covering material is less than 4. The average particle diameter [Phi ₁ of Comparative coating amine 1 (reference numeral 10) was about 12 [mu] m.

FIG. 2 is a photograph of the coated amine 1 produced in the Example of the present application observed with an electron microscope (2000 × magnification).
In FIG. 2, the coated amine 1 (symbol 20) was completely coated with the solid amine (not shown) with the plate-like filler 24. The average particle diameter Φ ₂ of the coated amine 1 (symbol 20) was about 15 μm.

<Production of heat-curable composition>
The components shown in the heat-curable composition of Table 1 below were used in the amounts (parts by mass) shown in the same Table and mixed under the conditions of 20 ° C. to produce a heat-curable composition.

<Evaluation>
Hardness The heat-curable composition produced as described above is applied to a container made of aluminum at a thickness of 5 mm, and the hardness of the cured product after heating for 10 minutes under conditions of 80 ° C. is measured using a JISA hardness tester. , Hardness (Hs) was measured. The results are shown in Table 1.

Storage stability The initial viscosity (Pa · s) of the heat-curable composition produced as described above was measured using a No. 7 rotor of a BS-type viscometer (manufactured by Tokyo Trigger Co., Ltd.) at 23 ° C., 50% relative humidity, rotation The speed was measured at 10 rpm.
In addition, the viscosity (viscosity after storage) of the heat-curable composition prepared as described above after storage for 10 days under the conditions of 40 ° C. and 50 RH% humidity is the same condition as the initial viscosity described above. It measured by.
The viscosity change rate was determined by applying the initial viscosity obtained as described above and the viscosity value after storage to the following equation.
Viscosity change rate (%) = [(viscosity after storage-initial viscosity) / initial viscosity] x 100
When the viscosity change rate was 5% or less, the storage stability was evaluated as “A” as being particularly excellent.
When the viscosity change rate was more than 5% and 15% or less, the storage stability was evaluated as "B".
When the viscosity change rate was more than 15% and 25% or less, the storage stability was evaluated as "C" as being good. The results are shown in Table 1.

The details of the components used for the thermosetting composition of Table 1 are as follows.
Urethane prepolymer: 600 g of polypropylene ether triol having a number average molecular weight of 5,000 (G-5000, trade name "EXCENOL 5030", manufactured by Asahi Glass Co., Ltd.) and 300 g of polypropylene ether diol having a number average molecular weight of 2,000 (D-2000, trade name "EXCENOL 2020" “Asahi Glass Co., Ltd.” was charged into a flask, heated to 100 ° C. to 130 ° C., stirred while degassing, and dewatered until the water content became 0.01% or less. After cooling to 90 ° C. and adding diphenylmethane diisocyanate (MDI, trade name “Sumidur 44S”, Sumitomo Bayer Japan Ltd.) to NCO mol / OH mol = 1.70, nitrogen atmosphere for about 24 hours. The reaction proceeded below to produce a urethane prepolymer.
Plasticizer (DINA): Diisononyl adipate, manufactured by J Plus Co., Ltd. Surface-treated calcium carbonate: trade name Sealets 200, manufactured by Maruo Calcium Co., Ltd. Solid amine: similar to the solid amine used in the production of the coated amine in the table. · Plate-like talc 1: Similar to plate-like talc 1 used in the production of the coated amines of the same table · Comparative coated amines 1 to 3 and coated amines 1 to 8: those produced according to the production of the coated amines of the same table

As is clear from the results of the thermosetting composition of Table 1, Comparative Example 1 in which the solid amine was not coated with the specific filler had poor storage stability (Comparative Example 1).
The storage stability was low in Comparative Examples 2 and 3 which do not contain coated amines but instead contain comparative coated amines 1 and 2 (using a coating material having a major axis / particle thickness of less than 4).
The thing (comparative example 4) using the covering material whose major axis / particle thickness exceeds 100 had low storage stability, and hardness of a hardened material after hardening at 80 ° C for 10 minutes was low.

On the other hand, Examples 1-8 are excellent in storage stability.
When Example 1 is compared with Examples 2, 3 and 4, it can be seen that Examples 2, 3 and 4 are superior to Example 1 in storage stability at high temperature (40 ° C.). From this, a coated amine (coated amine 2, 3, 4), which was prepared by simultaneously adding a surface treatment agent (silane coupling agent or silicone oil) in the step of coating with a solid amine filler, was used in the formulation. It can be said that the storage stability at high temperature is excellent.
Also, in the comparison of Examples 5 and 6 in which mica is used for the covering material and in the comparison of Examples 7 and 8 in which spindle-like light calcium carbonate is used for the covering material, the method using the surface treatment agent (silicone oil) is the same. It became a result excellent in the storage stability in high temperature.

Also, comparing Example 1 with Example 3, Example 3 in which the coated amine is surface-treated with an isocyanate silane is more of a cured product obtained than Example 1 in which the coated amine without surface treatment is used. The hardness was high.
Also, Example 5 and Example 6, Example 6 in which the coated amine was surface-treated had a higher hardness of the obtained cured product than Example 5 in which the coated amine without surface treatment was used. The same applies to Example 7 and Example 8.

  Moreover, when the heat-hardenable composition of Examples 1-8 manufactured as mentioned above was observed visually, there were no dust particles of coating amine in a composition, and the external appearance of the composition was all favorable.

10 Comparative coated amine 1
12 Solid amine 14 Fine powder of titanium oxide _{1 1} Average particle size 20 Coated amine 1
24 plate-like filler _{2 2} average particle diameter 30 plate-like filler 32 surface 34 side A particle thickness B major axis 40 spindle shaped filler 44 cross section C particulate thickness D major axis

Claims (3)

At least one terminal isocyanate-containing urethane prepolymer obtained by reacting a polyisocyanate compound and a polyol compound,
The average particle diameter of melting point 50 ° C. or more solid amine of 2 to 20 [mu] m, the solid amine 100 parts by weight of a plate-like or spindle-shaped filler 100 to 250 parts by weight, an average particle diameter of coated is 2~75μm , a coating amine containing,
The heat-curable composition, wherein the value of the ratio of the major axis of the filler to the particle thickness of the filler (major axis / particle thickness) is 4 to 75 , and the particle thickness is 0.01 μm to 1 μm. The heat curable composition according to claim 1 , wherein the solid amine is ground. The heat-curable composition according to claim 1 or 2 , wherein at least a part or all of the surface of the coated amine is hydrophobized by a silane coupling agent and / or a silicone oil.