JP2544686B2 - Epoxy resin powder composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an epoxy resin powder composition and a method for producing the same.

[0002]

BACKGROUND ART There are three known methods for producing an epoxy resin powder composition: a dry blending method, a melt blending method and a pressure-bonding blending method.
The dry blending method is a method in which an epoxy resin as a blending component and a curing agent are mixed in powder form. Although the mixing operation is easy in this method, since the bonding strength between the epoxy resin and the curing agent is weak, the obtained powder composition has a resin and curing agent during transportation, handling, or powder coating. Including the problem of easy separation. The melt blending method is a method in which the blended components are held in a molten state, mixed or kneaded, cooled and solidified, and pulverized. In this method, since the bonding force between the resin and the curing agent is strong, there is no problem of separating the resin and the curing agent. However, in this method, since the compounding ingredients are once melted, when a crystalline compound is used as the compounding ingredient, the crystallinity is lost. The pressure-bonding blending method is a method in which the components are mixed by a dry-blending method, then high pressure is applied to the components to bond them, and the resulting pressure-bonded product is pulverized (JP-A-61-55123). . In this method, since the compounding ingredients are not melted during the operation, there is no problem of losing the crystallinity even if crystalline ingredients are used as the compounding ingredients. However, the powder composition obtained by this method still has a problem of separation between the resin and the curing agent during transportation or handling because the bonding force between the resin and the curing agent is still insufficient. Further, in the case of this method, since high pressure is used, there is a problem that the manufacturing apparatus cost becomes high. An epoxy resin powder composition containing a crystalline epoxy resin or a crystalline curing agent as a compounding component has a low viscosity when melted, so that it easily penetrates into a fine gap, and a powder coating for fixing a coil. Etc. are very useful. However, the conventional technique has various problems as described above, and is not yet satisfactory as a technique for producing an epoxy resin powder composition containing a crystalline substance.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an epoxy resin powder composition containing a crystalline substance which solves the above problems found in the prior art and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention.

That is, according to the present invention, it comprises at least one crystalline substance and at least one non-crystalline substance,
At least one of the crystalline substances is present in the form of particles, and at least one of the non-crystalline substances has a glass transition point lower than the melting point of the crystalline substance present in the form of particles and is present in the form of particles. The crystalline substance is bonded to the non-crystalline substance by an adhesive force generated by heating the non-crystalline substance, and the combination of the crystalline substance and the non-crystalline substance is at least one epoxy resin and at least one type. An epoxy resin powder composition is provided, which comprises the curing agent of

According to the present invention, it further comprises at least one crystalline substance and at least one non-crystalline substance, wherein at least one of the non-crystalline substances has a glass transition temperature lower than the melting point of the crystalline substance. The combination of the crystalline substance and the non-crystalline substance having a point is a powder mixture containing at least one epoxy resin and at least one curing agent, and having a melting point of at least one crystalline substance. A method for producing an epoxy resin powder composition, which comprises heating at a temperature higher than at least one glass transition point of the amorphous substance, cooling and solidifying, and then pulverizing the obtained solidified product. Will be provided.

The crystalline substance used in the present invention includes a crystalline epoxy resin and a crystalline curing agent. Examples of the crystalline epoxy resin, triglycidyl isocyanurate (“Epicote RXE-15”, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 103, melting point 120 ° C.), epoxy propoxydimethylbenzyl acrylamide (“Kanekaresin AXE”, Kanebuchi Kagaku) Kosei Co., Ltd., epoxy equivalent 270, melting point 100 ° C.), hydroquinone diglycidyl ether (“HQDGE”, Nippon Kayaku Co., Ltd., epoxy equivalent 125, melting point 100 ° C.), bisphenol S diglycidyl ether (Nippon Kayaku Co., "EBPS-200", epoxy equivalent 200, melting point 125 ° C, tetramethylbiphenol diglycidyl ether ("Epicoat YX-4000, manufactured by Yuka Shell Epoxy Co., epoxy equivalent 185, melting point 105 ° C), tetramethylbiphenol diglycidyl ether modified Things (`` YL-6
074C ", manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 190, melting point 93 ° C), 2,5-di-t-butylhydroquinone diglycidyl ether (" DTBHQ-EX ", manufactured by Yuka Shell Epoxy Co., epoxy equivalent 202, And a terephthalic acid diglycidyl ether. Examples of the crystalline curing agent include 5 (2,5-dioxotetrahydrofuryl) -3-methyl-3
-Cyclohexene-1,2-dicarboxylic acid anhydride ("Epiclon
B-4400 ", Dainippon Ink, melting point 167 ° C), tetrahydrophthalic anhydride (THPA) (melting point 100 ° C), bisphenol A
(Melting point 157 ° C.), bisphenol S (melting point 245 ° C.), organic acid hydrazides, dicyandiamide and the like can be mentioned.

The amorphous substance used in the present invention includes an amorphous epoxy resin and an amorphous hardener. As the non-crystalline epoxy resin, various conventionally known resins are used, and bisphenol A diglycidyl ether (“Epicoat 1001”, epoxy equivalent 475, Tg (glass transition point) 29 ° C., Durance softening point (abbreviated as SP hereinafter) : 68 ° C, "Epicoat 1002", epoxy equivalent 6
50, Tg: 42 ° C., SP: 83 ° C., “Epicoat 10
04 ", epoxy equivalent 950, Tg: 53 ° C, SP: 9
8 ° C. Yuka Shell Epoxy Co., o-cresol novolac type epoxy resin (“Epicoat E180S65” epoxy equivalent: 200, Tg: 18 ° C., SP: 65 ° C.,
"Epicoat E180S90" epoxy equivalent: 220,
Tg: 43 ° C. SP: 90 ° C.) and the like. As the non-crystalline epoxy resin, a liquid one can be used as long as it is used in an amount within a range in which the powder characteristics of the crystalline substance and the non-crystalline substance are not impaired. As the non-crystalline curing agent, various conventionally known ones are used, for example, phenol novolac type resin (“Tamanol # 754” Tg: 49 ° C.,
SP: 100 ° C., manufactured by Arakawa Chemical Co., Ltd., o-cresol novolac type resin (“OCN90” Tg: 40 ° C., SP: 9)
0 ° C, "OCN120" Tg: 70 ° C, SP: 120
C., manufactured by Nippon Kayaku Co., Ltd.) and the like. The melting point of the crystalline substance used in the present invention is preferably 90 ° C. or higher,
The glass transition point of the amorphous component is 15 to 75 ° C.,
Moreover, the Durance softening point (hereinafter, simply softening point or S
(Abbreviated as P) is preferably 50 ° C. or higher.

In the present invention, in addition to the above-mentioned epoxy resin and curing agent, a curing accelerator and a commonly used auxiliary component such as a reactive solid organic substance, a colorant, a flame retardant, a flow conditioner and a filler are further added. Can be used together. These may be crystalline or amorphous. Examples of the curing accelerator include imidazole (“Curazole 2MZ”).
Melting point: 147 ° C., manufactured by Shikoku Kasei Co., Ltd., or modified imidazole (Curezol 2MZ-AZINE ”melting point: 248
C., manufactured by Shikoku Kasei Co., Ltd., pre-reacted product of epoxy resin and imidazole (“Epicure P-200”, manufactured by Yuka Shell Epoxy Co., Ltd., Tg: 95 ° C.), triphenylphosphine, diazabicycloundecene phenol. Novolak resin salts (“U-Cat831” manufactured by San-Apro) and the like can be mentioned. Reactive solid organic substances are reactive with epoxy resins and exhibit various effects. Examples of such substances include, for example, improving the heat resistance of the cured product and improving the binder effect of the compounding ingredients. In addition, bismaleimide triazine resin (BT resin) (“BT-2170”, manufactured by Mitsubishi Gas Chemical Co., Inc., Tg: 42 ° C.), to improve the heat resistance of the cured product and to reduce the viscosity during melting, bismaleimide Resin (`` MB-300
0 ", manufactured by Mitsubishi Yuka Co., Ltd., melting point 156 ° C), butyral resin (" ESREC BLS ", manufactured by Sekisui Chemical Co., Ltd., Tg: 120 ° C) for improving the adhesiveness of the cured product. In order to improve the flexibility, solid polyols such as tris (2-hydroxyethyl) isocyanurate (“THEIC”, manufactured by Shikoku Kasei Co., melting point: 135 ° C.) and the like can be mentioned. The flow regulator is added to prevent craters from being generated in the cured product, and examples thereof include acrylic acid ester oligomers (“Nikalite XK-21”, manufactured by Nippon Carbide Co.).

In the epoxy resin composition of the present invention, the mixing ratio of the crystalline substance and the non-crystalline substance is the total crystalline substance.
The amount is 15 to 70 parts by weight, preferably 20 to 60 parts by weight, based on 100 parts by weight. If the blending ratio of the non-crystalline substance is less than the above range, the bonding force between the crystalline substance and the non-crystalline substance will be weakened, while if it is more than the above range, disadvantages such as an increase in viscosity upon melting occur. The mixing ratio of the curing agent to the epoxy resin is 0.5 to 1.5 equivalents, preferably 0.7 to 1.2 equivalents, as the equivalent of functional groups, per epoxy equivalent of all epoxy resins. The amount of the curing accelerator is 0.1 to 5.0 parts by weight, preferably 0.3 to 3.0 parts by weight, based on 100 parts by weight of the total epoxy resin. The proportion of the reactive solid organic compound is appropriately selected as desired, but generally 10 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.
The proportion is 0 parts by weight, preferably 20 to 40 parts by weight.

To produce the composition of the present invention, first, the respective components are mixed in powder form by the dry blending method.
In this case, at least one of the amorphous substances to be mixed is selected so that the glass transition point is lower than the melting point of the crystalline substance. The glass transition point of the non-crystalline substance may be specified to be 10 ° C. or more, preferably 30 ° C. or more lower than the melting point of the crystalline substance. The average particle size of the crystalline substance is 10 to 150 μm, preferably 20 to 100 μm.
The average particle size of the amorphous substance is 10 to 150 μm, preferably 2
0 to 100 μm. As a specific combination of the crystalline substance and the non-crystalline substance, for example, the combinations shown in the following table can be shown.

[0012]

[Table 1]

In powder mixing the crystalline substance and the non-crystalline substance, when the non-crystalline substance is composed of two or more kinds,
These non-crystalline substances are melt-mixed in advance by the melt blending method, cooled and solidified, and finely pulverized.
It is preferable to use an amorphous substance and powder-mix it with the crystalline substance. Moreover, if the crystalline material consists of more than two, leaving at least one, melt mixing other things the non-crystalline material, was cooled and solidified, and pulverized, non-crystalline the pulverized product This was a sex materials can be mixed remaining crystalline material and a powder. In this case, the crystalline substance to be melt-mixed with the non-crystalline substance is selected so that the glass transition point of the molten mixture with the non-crystalline substance is lower than the melting points of the remaining crystalline substances. As described above, when an amorphous substance composed of a molten mixture of each compounding component is used as the amorphous substance to be mixed with the crystalline substance, the dispersion uniformity is further improved and the physical properties of the cured product are improved. . In addition to the epoxy resin and the curing agent, the powder mixture may contain an auxiliary additive such as a crystalline or non-crystalline curing accelerator and an active hydrogen-containing solid organic substance. The powder mixture of the crystalline substance and the non-crystalline substance is formed into an arbitrary shape such as a block shape or a layer shape so that it can be easily heat-treated, but is preferably formed into a layer shape. When forming into a layer, the thickness of the powder layer is 0.1 to 30 mm, preferably 1 to 5 mm.

The powder mixture obtained as described above is heated. Stir the powder mixture when heating
Absent. The heating temperature is below the melting point of the crystalline material present in particulate form in the mixture and above the glass transition temperature of at least one component of the amorphous material. The glass transition point is the softening start temperature of the polymer substance, and when heated above this temperature, the non-crystalline substance begins to generate thermal adhesiveness. Therefore, the crystalline substance and the non-crystalline substance can be adhered to each other by heating to a temperature higher than this temperature. In order to perform this mutual adhesion by heating under atmospheric pressure in a short time, it is preferable to heat to a temperature higher by 15 ° C. or more than the glass transition point of the component having the lowest glass transition point in the amorphous substance. This is because when heated under atmospheric pressure, adhesion occurs at the glass transition point of non-crystalline materials, but the adhesive strength at temperatures slightly higher than the glass transition point is small, and it is difficult to bond them to each other to the desired degree. Is because it takes a long time. The heating temperature is preferably lower than the melting point of the substance having the lowest melting point in the crystalline substance and lower than the softening point of the substance having the lowest softening point in the non-crystalline component. . The crystalline substance loses its crystallinity by compatibilizing with other components, and when heated above the melting point of the crystalline substance, it becomes a cause of blocking when it becomes a powder coating material . Further, when heated above the softening point of the non-crystalline substance, the viscosity of the non-crystalline substance becomes low, and a phenomenon of fluidizing downward in the mixture occurs, resulting in a uniform dispersion of the non-crystalline substance and the non-crystalline substance. You will be told.

As a heating method, there are a heating method using a heating medium such as air and nitrogen gas, and a heating method using a heating plate. In this heating, an appropriate pressurizing condition can be adopted before heating, during heating, or during cooling after the powder mixture is heated. It is sufficient that the pressure is 2 kg / cm ² or more. In order to preferably heat the powder mixture, it is advisable to place the mixture in layers on a moving conveyor and pass it through a heating furnace. By heating the powder mixture as described above, the non-crystalline substance is softened to give adhesiveness, and the non-crystalline substance not only joins the crystalline substance particles having a high melting point and the non-crystalline substance particles to each other. , Easily bond with other component particles. In the present invention, the mixture in such a heated state is cooled and solidified to about room temperature to obtain a mixture in which the whole is integrally bonded. A time of 1 minute or more, particularly 2 to 15 minutes, is sufficient for heating the mixture to bond them to each other, and a cooling time after the bonding is 1 minute or more, particularly 10 to 15 minutes.
If the heating time is too long, the epoxy resin and the curing agent will not cure.
It causes a response and is not preferable.

In the present invention, the above-mentioned mixture in which the whole is integrally bonded is pulverized. This mixture has excellent pulverizability and can be easily pulverized by an ordinary pulverizer. The particles produced by this pulverization have a structure in which a crystalline substance existing in the form of particles is bonded to an amorphous substance, and each crystalline substance particle is bonded to each other through the amorphous substance. ing. The ground product is classified into a desired particle size to obtain a product. The average particle size of the particles constituting the powder composition of the present invention is usually 1000 to 50 μm, preferably 800 to 60 μm. The apparent density of the powder composition of the present invention depends on its particle size, but is generally 1 g.
/ Cm ³ or less, usually 0.35 to 0.6 g / cm ³ .

[0017]

In the epoxy resin powder composition of the present invention, at least one crystalline substance exists in the form of particles,
Amorphous material is bonded to the crystalline material particles, and
The crystalline substance particles have a structure in which they are bonded to each other through an amorphous substance. In such a powder composition,
Since the bonding between the crystalline particles and the non-crystalline particles is due to the adhesive force generated by the softening of the non-crystalline material by heating, in the case of the powder composition obtained by the conventional dry blending method or the pressure-bonding blending method. Is very strong compared to
The crystalline substance and the non-crystalline substance are not easily separated by an external force during transportation and handling, and the blocking resistance is excellent. Further, the method for producing the epoxy resin powder composition of the present invention includes a heating step of the powder mixture, but by only softening only a part of the powder constituting the powder mixture by heating, the melt blending method Since the mixture is not melt-mixed as a whole as described above, the amount of heat is small and the time required for heating and cooling is short, which is very efficient. Further, as compared with the pressure-bonding blending method, since a high-pressure device is not required, the method of the present invention is very advantageous in terms of manufacturing equipment, and further, the bonding force of each compound particle of the obtained composition is also large. Therefore, it is excellent in terms of transportation and handling, and also in terms of powder coating. Since the epoxy resin powder composition of the present invention contains a crystalline substance and has a very low viscosity when melted, it has an excellent permeability into fine voids. The powder composition of the present invention is suitable as a powder coating material in the fluidized-bed method, electrostatic coating method, spray method and the like. The powder composition of the present invention is also suitable as a raw material for a powder varnish for impregnation.

(Examples) Next, the present invention will be described in more detail with reference to Examples. The melting point (MP) and glass transition point (Tg) shown below are both measured by DSC (differential thermal scanning calorimeter). The softening point (SP) is measured by the Durance method.

Example 1 As a component material, the following crystalline epoxy resin and amorphous hard resin were used.
An agent, a curing accelerator (catalyst), and an additive were used. <Process> Crystalline epoxy resin (YX4000): 57.5 parts by weight Non-crystalline curing agent (OCN90): 23.5 parts by weight Catalyst (Epicure P-200): 0.8 parts by weightAmorphous additive (BT-2170): 18.2 parts by weight  Total: 100.0 parts by weight Each of the above components was pulverized to a particle size of 2 mm or less. Next
, Crystalline epoxy resin (trade name "YX4000", TE
Tramethyl biphenol diglycidyl ether, MP:
105 ° C, manufactured by Yuka Shell Epoxy Co., Ltd.)
Amorphous curing agent (trade name "OCN90", o-cresol
Novolak resin, Tg: 40 ° C, manufactured by Nippon Kayaku Co., Ltd.
Medium (trade name "Epicure P-200", imidazole
Bisphenol A type epoxy adduct, oiled shell epoxy
Manufactured by Shisha Co., Ltd. and an amorphous additive (trade name "BT-217"
0 ", bismaleimide triazine resin, Tg: 42
C., manufactured by Mitsubishi Gas Co., Ltd.) with the above weight ratio
, And mix it with an extruder.
Extruded at a temperature of 100 ° C, melt-blended, then cooled
It was cooled through a roll and formed into a plate. Furthermore this plate
The substance was pulverized with a pulverizer into particles of 2 mm or less. This crush
The product had a Tg of 41 ° C. Next, this crushed product
-Soluble epoxy resin is added and the Henschel mixer is mixed,
This mixture is pulverized with a 100 mesh pass 100%
It was pulverized to the size of. Through the above steps, component materials
A well-dispersed mixture was obtained.

Next, the low temperature semi-melt blending method of the present invention was carried out on the finely pulverized mixture under the following conditions. That is,
First, the finely pulverized mixture obtained above was placed on a stainless plate with a thickness of 2 mm and heated at a surface temperature of 60 ° C. for 10 minutes. In this temperature state, not all of the component materials are melted, but among the component materials, OCN90, Epicure P-200, and BT-21 that have been melt-mixed beforehand are mixed.
The particles consisting of 70 and 70 slightly melt or soften to form a binder, which acts on the crystalline epoxy resin particles having a high melting point (that is, remains solid at 60 ° C.) to form an aggregate. Next, the aggregate was allowed to stand at room temperature for 10 minutes and cooled to 25 ° C. to be solidified. This was further pulverized by a pulverizer to obtain a composition consisting of powder having a size of 20 mesh pass and 100%. In this case, since the agglomerates were excellent in pulverizability, the pulverization could be performed smoothly. In addition, it was confirmed that the obtained powder composition is very easy to use because it is a powder composition in which the components do not easily separate.

Example 2 As a component material, the following crystalline epoxy resin and amorphous hard resin were used.
Agents, catalysts and additives were used. <Process> Crystalline epoxy resin (YX-4000): 60.2 parts by weight Non-crystalline curing agent (OCN 90): 38.0 parts by weight Catalyst (Epicure P-200): 0.9 parts by weight Non-crystalline Additive (Nicalite XK-21): 0.3 parts by weightAmorphous additive (S-REC BLS): 0.6 parts by weight  Total: 100.0 parts by weight Of the above ingredients, ingredients other than epoxy resin are
Were blended by the melt blending method. That is, non-crystalline
Hardening agent coarsely crushed product, catalyst coarsely crushed product, first additive (commodity
Name "Nikalite XK-21", acrylic acid ester oligomer
-, Manufactured by Nippon Carbide Co., Ltd., and a second additive (trade name "S
REC BLS ", butyral resin, Sekisui Chemical Co., Ltd.)
The weight ratio was mixed using a Henschel mixer. next,
This mixture was extruded by an extruder at a temperature of 100 ° C and melted.
After melt-blending, cool through a chill roll and plate
Molded into. Further, this plate-like material is crushed with a crusher of 2 mm or less.
Crushed to size. The Tg of this ground product was 41 ° C.
Coarse crushed product of crystalline epoxy resin (YX-4000)
Add it, mix it with a Henschel mixer, and add 100 with a fine pulverizer.
Finely pulverized to a size of 100% mesh pass. In the above process
Therefore, a mixture in which each of the component materials is well dispersed is obtained.
Was. Next, the finely ground mixture obtained above is
Thus, the low temperature semi-melt blending method of the present invention was applied. Immediately
Then, first, the finely pulverized mixture obtained above was sprayed to a thickness of 2 mm.
Place on a stainless steel plate and heat at a surface temperature of 65 ° C for 10 minutes.
Was. For the reasons stated in Example 1, melt blending
Particles containing OCN-90 as the main component prepared in
Could act to form aggregates. Then
This aggregate is left at room temperature for 10 minutes and cooled to 25 ° C.
It was made to solidify. This is further crushed with a crusher
Then, a powder composition having a size of 20 mesh pass and 100% was obtained.

Example 3 As a component material, the following non-crystalline epoxy resin and crystalline hard resin were used.
Agents, catalysts and additives were used. <Process> Non-crystalline epoxy resin (Epicoat 1002): 29.6 parts by weight Non-crystalline epoxy resin (Epicoat E180S90): 29.6 parts by weight Crystalline curing agent (bisphenol A): 17.2 parts by weight Crystallinity Curing agent (Epiclon B-4400): 4.1 parts by weight Catalyst (Epicure P-200): 0.6 parts by weightAdditive (MB-3000): 18.6 parts by weight  Total: 100.0 parts by weight First, of the above components, the first non-crystalline epoxy resin
(Product name "Epicoat 1002", Tg: 42 ° C, oil
Shell epoxy) and a second non-crystalline
Poxy resin (trade name "Epicoat E180S90", T
g: 43 ° C., manufactured by Yuka Shell Epoxy Co., Ltd.),
The coarsely crushed product of the catalyst (Epicure P-200) and the first binder
Crystalline curing agent (trade name "bisphenol A (BPA)",
MP: 157 ° C., manufactured by Mitsui Toatsu Co., Ltd.) powder and second crystal
Curing agent (Brand name "Epiclone B-4400", MP1
67 ° C., made by Dainippon Ink and Chemicals, Inc.) powder and crystallinity additive
Powder of additive (“MB-3000”, manufactured by Mitsubishi Petrochemical Co., Ltd.)
The Henschel mixer was mixed in the above weight ratio.
This mixture is pulverized with 100 mesh pass 100%
Crushed to size. Next, for this finely ground mixture,
Apply the low temperature semi-melt blending method of the present invention as follows
did. That is, first, the finely pulverized mixture obtained above was mixed with 2 mm.
On a stainless steel plate with a thickness of 10
Heated for minutes. For the reason described in the first embodiment,
The crystalline epoxy resin particles act as a binder and coagulate.
A collection was formed. This agglomerate is further added at room temperature for 10 minutes.
It was left to stand and cooled to 25 ° C. to solidify it. this
Is further crushed with a crusher, and 20 mesh pass 100%
A powder composition having a size was obtained.

Example 4 As a component material, the following crystalline epoxy resin and non-crystalline epoxy resin were used.
Poxy resin, crystalline hardener, non-crystalline hardener, crystalline additive
Additives and catalysts were used. <Prescription> Crystalline epoxy resin (YX-4000): 33.8 parts by weight Non-crystalline epoxy resin (Epicoat E180S90): 11.3 parts by weight Non-crystalline epoxy resin (Epicoat 1002): 11.3 parts by weight Crystallinity Hardener (Epiclone B-4400): 5.6 parts by weight Crystalline hardener (bisphenol A): 11.3 parts by weight Non-crystalline hardener (OCN120): 11.8 parts by weight Crystalline additive (Sake): 14.1 parts by weightCatalyst (Epicure P-200): 0.8 parts by weight  Total: 100.0 parts by weight First of all, crystalline epoxy resin (Epicoat
YX-4000) coarsely pulverized product and a first amorphous epoxide
Si resin (Epicoat 180S90) and second non-crystalline resin
Non-consolidated with coarsely crushed Poxy resin (Epicoat 1002)
Coarsely pulverized crystalline hardener (OCN120) and catalyst (epi
Cure P-200) coarsely pulverized product, and first crystalline curing agent
(Epiclone B-4400) powder and second crystalline hard
Agent (bisphenol A) and crystalline additive (trade name)
"THEIC", Solid Polyol, MP: 1
At 35 ° C, manufactured by Shikoku Kasei Co., Ltd. and Henschel at the above weight ratio.
Mix with a mixer, then pulverize with a fine pulverizer and
A 100% shredded mixture was obtained. Next
For this finely pulverized mixture,
The bright low temperature semi-melt blending method was applied. That is, first
The finely pulverized mixture obtained in the above step was spread to a thickness of about 2 mm.
It was placed on a glass plate and heated at a surface temperature of 60 ° C. for 10 minutes. Real
For the reasons as described in Example 1, particles of non-crystalline component
Acted as a binder to form aggregates. This
The collection is left at room temperature for 10 minutes and cooled to 25 ° C.
It was solidified by letting. This is further crushed with a crusher,
20 mesh pass 100% size powder composition
Was.

Example 5 As a component material, the following crystalline epoxy resin and non-crystalline epoxy resin were used.
Poxy resin, crystalline hardener, non-crystalline hardener, additives
used. <Formulation> Crystalline epoxy resin (Epicoat YX-4000): 39.0 parts by weight Non-crystalline epoxy resin (Epicoat 1002): 13.0 parts by weight Non-crystalline epoxy resin (Epicoat E180S90): 13.0 parts by weight Crystals Hardening agent (bisphenol A): 13.0 parts by weight Crystalline hardening agent (Epiclone B-4400): 6.5 parts by weight Non-crystalline hardening agent (OCN90): 13.6 parts by weight Catalyst (Epicure P-200) : 1.0 parts by weight Additive (Nicalite XK-21): 0.3 parts by weightAdditive (S-Rex BLS): 0.6 parts by weight  Total: 100.0 parts by weight Of the above components, the first crystalline curing agent (bisphenol
A) A coarsely pulverized product and a second crystalline curing agent (Epiclone B-
4400) and an amorphous hardener (OCN9
0) coarse crushed product and catalyst (Epicure P-200)
A pulverized product and a first additive (Nicalite XK-21),
With the second additive (S-Rex BLS: Sekisui Chemical Co., Ltd.)
Were mixed in the above weight ratio using a Henschel mixer.
Then, the mixture is extruded by an extruder at a temperature of 120 ° C.
And melt-blend, then cool through a chill roll
And formed into a plate shape. Furthermore, this plate-shaped material is crushed by 2m
It was crushed to a size of m or less. Crystalline epoxy
Coarsely crushed resin (Epicoat YX-4000)
1 non-crystalline epoxy resin (Epicoat 1002) and
2 non-crystalline epoxy resin (Epicoat E180S9
0) coarsely pulverized product was added and mixed with a Henschel mixer,
This mixture is pulverized with a fine pulverizer and 100 mesh pass 1
A finely ground mixture with a size of 00% was obtained. Then get above
For the finely pulverized mixture,
A warm semi-molten blend was applied. That is, first,
The finely pulverized mixture to a stainless plate with a thickness of about 2 mm.
And heated at a surface temperature of 65 ° C. for 10 minutes. In Example 1
For the reasons mentioned above, the particles of the amorphous epoxy resin component are
Particles made by melt blending with the child
Agglomerates were formed. 10 minutes for this aggregate
It was left to stand for a while and cooled to 25 ° C. to solidify. This
This is further crushed with a crusher and 100% of 20 mesh pass
A powder composition having a size of

Comparative Example 1 As a component material, the following non-crystalline epoxy resin, non-crystalline
Hardeners, catalysts and additives were used. <Process> Non-crystalline epoxy resin (Epicoat 1002): 35.5 parts by weight Non-crystalline epoxy resin (Epicoat E180S65): 35.5 parts by weight Non-crystalline curing agent (OCN-120): 27.0 parts by weight Catalyst (Epicure-200): 1.1 parts by weight Additive (Nicalite XK-21): 0.4 parts by weightAdditive (S-Rex BLS): 0.7 parts by weight  Total: 100.0 parts by weight Of the above ingredients, the ingredients other than epoxy resin are
Mix by weight in a Heschel mixer and extrude this mixture.
After melt-blending at a temperature of 100 ° C with a machine, cooling
It was cooled through a roll and formed into a plate. Furthermore this plate
Was pulverized with a pulverizer to a size of 2 mm or less. This crushed product
Had a Tg of 76 ° C. Coarse powder of each epoxy resin
Add crushed material and mix with a Henschel mixer, then fine powder
Crushed with a crusher to a size of 100 mesh pass 100%
Was. Next, this finely ground mixture was belt-combed with a thickness of 2 mm.
And was heated at a surface temperature of 65 ° C. for 10 minutes. This is
And allow it to stand at room temperature for 10 minutes, then cool to 25 ° C to solidify.
Made into This is further crushed with a crusher, and a 20 mesh
A powder composition having a size of 100% was obtained.

Comparative Example 2 As a component material, the following crystalline epoxy resin and amorphous hard resin were used.
Agents, catalysts and additives were used. <Process> (Same as Example 2) Crystalline epoxy resin (Epicoat YX-4000): 60.2 parts by weight Amorphous curing agent (OCN 90): 38.0 parts by weight Catalyst (Epicure P-200): 0.9 parts by weight Additive (Nicalite XK-21): 0.3 parts by weightAdditive (S-Rex BLS): 0.6 parts by weight  Total: 100.0 parts by weight Of the above component materials, resin, curing agent, catalyst
Coarse crushing with shell mixer, 2mm size coarse crushing
A mixture was obtained. Add each additive to this mixture in the above weight ratio.
The obtained mixture was mixed with an extruder at a temperature of 60 to 70 ° C.
After melt blending for 1 minute, chill roll
And cooled to form a plate. This plate is sticky
It could not be crushed at room temperature. This plate with liquid nitrogen
Cool to about minus 70 ℃, crush with a crusher, and
A powder having a size of 100% of Spass was obtained.

Comparative Example 3 The following non-crystalline epoxy resin and crystalline hard resin were used as component materials.
Agents, catalysts and additives were used. <Process> Non-crystalline epoxy resin (Epicoat 1002): 36.0 parts by weight Non-crystalline epoxy resin (Epicoat E180S65): 36.0 parts by weight Crystalline curing agent (bisphenol A): 20.9 parts by weight Crystallinity Curing agent (Epiclon B-4400): 5.0 parts by weight Catalyst (Epicure P-200): 1.1 parts by weight Additive (Nicalite XK-21): 0.4 parts by weightAdditive (S-Rex BLS): 0.7 parts by weight  Total: 100.0 parts by weight The above ingredients are mixed in powder form with a Henschel mixer.
Then, the mixture is heated in an extruder at a temperature of 90 to 100 ° C.,
Melt blend for 1 minute and then pass through a chill roll.
Then, it was cooled and molded into a plate. Furthermore, bring this plate to about 5 ° C
Cool and crush with a crusher, 20 mesh pass 100%
A finely ground mixture was obtained.

Comparative Example 4 The following crystalline epoxy resin and non-crystalline epoxy were used as component materials.
Poxy resin, curing agent, catalyst and additives were used. <Process> (Same as Example 5) Crystalline epoxy resin (Epicoat YX-4000): 39.0 parts by weight Non-crystalline epoxy resin (Epicoat 1002): 13.0 parts by weight Non-crystalline epoxy resin (Epicoat E180S90) ): 13.0 parts by weight non-crystalline curing agent (OCN90): 13.6 parts by weight crystalline curing agent (bisphenol A): 13.0 parts by weight crystalline curing agent (Epiclone B-4400): 6.5 parts by weight Parts Catalyst (Epicure P-200): 1.0 parts by weight Additives (Nicalite XK-21): 0.3 parts by weightAdditive (S-Rex BLS): 0.6 parts by weight  Total: 100.0 parts by weight The above ingredients are mixed in powder form with a Henschel mixer.
Then, this mixture was heated in an extruder at a temperature of 70 ° C. for 1 minute.
After melt blending in time, cool through chill roll
And formed into a plate shape. Furthermore, this plate is about minus 70 ℃
It is cooled to 20% and crushed by a crusher, and 20 mesh pass is 100%.
A pulverized mixture of

Comparative Example 5 In Comparative Example 4, the operating temperature of the extruder was 90 to 100 ° C.
An experiment was conducted in the same manner except that the temperature was changed to 20 to obtain a finely pulverized mixture having a size of 20 mesh and 100%.

Next, with respect to the powder compositions obtained in the above Examples and Comparative Examples, their gel time, flowability, dispersibility, glass transition point, adhesive strength and blocking resistance were measured as follows, and the results were obtained. Is shown in Table 2. Gel time The gel time at 150 ° C. was measured according to JIS C 2104. Flowability The iron plate is preheated to 150 ° C and has an inclination of 10 ° in advance. Next, 0.5 g of a sample is taken, a tablet having a diameter of 13 mm is prepared by a conventional method, and the tablet is placed on an iron plate.
Minute, heated at 150 ℃, tablets before and after heating
The flowability was measured from the length of the melted and flowed. Flowability is judged to be good when it is 20 or more. Dispersibility The degree of difference in reactivity (gel time) due to the difference in particle size distribution was measured based on JISC 2104. <Particle size distribution> (A) 60 mesh pass product (B) 40 to 20 mesh pass product (C) 20 mesh on product The smaller the difference in gel time, the better the dispersibility was judged, and the evaluation was made in three stages. ◯: Almost no difference in A to C Δ: Difference in A to C is within 5 ×: Difference in A to C is within 10 Glass transition temperature (Tg) of cured product Measured with a thermomechanical analyzer (TMA). When the Tg is 140 ° C. or higher, it is judged to be good. Adhesive strength Adhesive strength of 180 kg / cm ² or more is judged to be good. The curing conditions of the cured product used for and were 180 ° C. × 30 minutes. Blocking resistance A powder sample of 50 g was placed in a cup, placed in a constant temperature bath at 40 ° C. for 3 hours and then taken out to examine the blocking situation. ○: No lumps at all △: There is lumps but can be easily loosened with fingers ×: Hard lumps

[0031]

[Table 2]

From the results shown in Table 2, it can be seen that the powder compositions obtained in Examples 1 to 5 according to the present invention have good performance as a powder coating material.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Katsuji Kitagawa 4-11-12 Ginza, Chuo-ku, Tokyo Somer Co., Ltd. (56) References JP-A-55-152761 (JP, A) JP-A-SHO 50-28532 (JP, A) JP-A-56-139563 (JP, A) JP-A-57-164117 (JP, A) JP-B 50-2163 (JP, B1) JP-B 50-5214 (JP, A) B1)

Claims (18)

(57) [Claims] 1. At least one crystalline substance and at least one non-crystalline substance, at least one of the crystalline substances is present in the form of particles, and at least one of the non-crystalline substances is the particles. Having a glass transition point lower than the melting point of the crystalline substance present in the form of particles, the crystalline substance present in the form of particles is bonded to the non-crystalline substance by an adhesive force generated by heating the non-crystalline substance, An epoxy resin powder composition, characterized in that the combination of the crystalline substance and the non-crystalline substance contains at least one epoxy resin and at least one curing agent. 2. The crystalline substance comprises a crystalline epoxy resin, and the amorphous substance comprises an amorphous curing agent.
Composition. 3. The composition according to claim 1, wherein the crystalline substance comprises a crystalline epoxy resin and a crystalline curing agent, and the amorphous substance comprises an amorphous curing agent. 4. The composition of claim 1, wherein the crystalline material comprises a crystalline epoxy resin and the non-crystalline material comprises a non-crystalline epoxy resin and a non-crystalline curing agent. 5. The composition of claim 1, wherein the crystalline material comprises a crystalline epoxy resin and a crystalline curing agent and the non-crystalline material comprises a non-crystalline epoxy resin. 6. The crystalline material comprises a crystalline hardener,
The amorphous material comprises an amorphous epoxy resin.
Composition of 1. 7. The crystalline material comprises a crystalline curing agent,
The composition of claim 1, wherein the non-crystalline material comprises a non-crystalline epoxy resin and a non-crystalline hardener. 8. The composition according to claim 1, wherein the crystalline substance comprises a crystalline epoxy resin and a crystalline curing agent, and the non-crystalline substance comprises a non-crystalline epoxy resin and a non-crystalline curing agent. 9. The composition of claim 1 wherein said non-crystalline material comprises a molten mixture of two or more non-crystalline materials. 10. The composition of claim 1 wherein said amorphous material comprises a molten mixture of crystalline material and amorphous material. 11. The composition according to claim 1, further comprising a curing accelerator. 12. The composition according to claim 1, which contains a reactive crystalline or amorphous solid organic substance. 13. The composition according to claim 1, wherein the ratio of the non-crystalline substance to 100 parts by weight of the crystalline substance is 15 to 70 parts by weight. 14. At least one crystalline material and at least one non-crystalline material, wherein at least one of the non-crystalline materials has a glass transition point below the melting point of the crystalline material, and The combination of the crystalline material and the non-crystalline material is a powder mixture obtained by dry blending at least one epoxy resin and at least one curing agent, and melting point of at least one crystalline material of the crystalline material. Epoxy resin powder characterized in that it is heated at a lower temperature than at least one glass transition point of the non-crystalline substance under non-stirring , cooled and solidified, and then the obtained solidified product is ground. A method for producing a body composition. 15. At least 15 glass transition points below the melting point of the lowest melting point component of the crystalline material and above the glass transition point of the lowest glass transition point component of the amorphous material.
The method for producing an epoxy resin powder composition according to claim 14, which comprises heating at a temperature higher by ° C and at a temperature lower than the Durance softening point, cooling and solidifying, and then pulverizing the obtained solidified product. 16. The method of claim 14 or 15 wherein said non-crystalline material comprises a molten mixture of two or more non-crystalline materials. 17. The method of claim 14 or 15 wherein said amorphous material comprises a molten mixture of crystalline material and amorphous material. 18. The method according to claim 14, wherein the powder mixture is formed into a layer.