KR101712687B1 - Hydrazide compound, process for production of same, and curing agent, resin composition and cured article each comprising same - Google Patents

Abstract

A hydrazide compound which can be used as a curing agent which reacts stably with high activity to a resin having an unsaturated bond, a process for producing the same, and a thermosetting agent, a resin composition and a cured product. That is, it is a hydrazide compound comprising a crystalline hydrazide compound having at least one hydrazide group in the molecule and a metal element capable of forming a complex with the crystalline hydrazide compound. And is a resin curing agent containing the hydrazide compound. A resin having at least one unsaturated bond in one molecule, and an epoxy resin. Is a cured product obtained by curing the resin composition. Further, there is also provided a method for producing a crystalline hydrazide compound, which comprises heating a crystalline hydrazide compound having at least one hydrazide group in a molecule and a metal element capable of forming a complex with the crystalline hydrazide compound to obtain a mixture, Thereby obtaining a solidified product. The present invention also provides a method for producing a hydrazide compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a hydrazide compound, a method for preparing the same, a curing agent, a resin composition and a cured product using the same,

The present invention relates to a hydrazide compound which can be used as a curing agent for a resin composition, a process for producing the same, and a curing agent, a resin composition and a cured product using the hydrazide compound.

BACKGROUND ART [0002] In the production of electronic parts and the like, a photo-thermal curing type (e.g., a photo-curing type) type in which after temporary fixation by primary curing by light irradiation of ultraviolet Is known.

As the photo-curable resin composition, a composition in which a resin having a (meth) acryl group as a photo-curable component and a resin having an epoxy group as a heat curing component are blended in an arbitrary ratio is used.

Such a photo-curable resin composition is used, for example, in a dropping method of a liquid crystal panel. This method is applied as a method of manufacturing a liquid crystal display cell, in which a liquid crystal is dropped on the inside of a bank made of a liquid crystal seal formed on one substrate, and the other substrate is bonded to manufacture a liquid crystal display cell Method.

When the photo-curable resin composition is applied to a dropping method of a liquid crystal panel, insufficient curing occurs in the light shielding portion where the irradiated light is not wound, thereby causing sealing pass, panel peeling, liquid crystal contamination due to resin component elution, and the like.

In recent years, electronic parts and the like tend to be increased in light-shielding portions which are less likely to be irradiated with ultraviolet light or the like due to wiring, layout, etc., A hardening agent that does not cause shortage of hardening is required.

(1) a method of scattering light transmitted through a resin composition by adding a filler having a constant specific surface area (for example, Patent Document 1), ( (2) a method of adding a photo-sensitizer and a photosensitizer to a resin composition, (3) a method of adding a thermosetting agent of an acrylic resin to a resin composition and improving the lack of primary curing by a secondary curing by heat (4) a method of adding a thermosetting agent of an epoxy resin to the resin composition to improve the lack of primary curing in the light-shielding portion by secondary curing by heat.

However, (1) In the method by the light scattering of the filler, the curing distance depends on the gap, and there is a problem that the design is restricted because hardening of the light shielding portion of 0.3 mm or more from the opening becomes difficult.

(2) In the method of adding a photosensitizer or photosensitizer with high sensitivity, the liquid crystal is contaminated by a by-produced component in the curing reaction.

(3) In the method of adding a thermosetting agent for an acrylic resin, organic peroxides are used as a thermosetting agent. Since these peroxides are liquid, elution into liquid crystals tends to occur, which is a cause of contamination and causes bleeding have. Further, since the organic peroxide is inhibited from being cured by oxygen, there is a problem that the curing is defective in an atmospheric environment. As the organic peroxide-based thermosetting agent, for example, ketone peroxide, peroxyketal, hydroperoxide, dialkylperoxide, diacylperoxide, peroxyester, peroxycarbonate and the like are used.

(4) In the method of adding the epoxy resin thermosetting agent, an amine compound, an acid anhydride, a hydrazide compound and the like are used as a thermosetting agent.

Among these curing agents, amine compounds have low-temperature curability and are therefore widely used in fields requiring fast curability. However, the amine compound has a problem that moisture resistance and electric characteristics are deteriorated and the usable time is short. The acid anhydride has an advantage of high transparency, but has a problem that the moisture resistance is slightly lowered.

Examples of the amine compound include fatty acid polyamines such as diethyl triamine and triethylene tetramine, modified polyamines obtained by adding an epoxy resin, acrylonitrile, ethylene oxide or the like to an aliphatic polyamine, metaphenylene diamine, diamino di Aromatic polyamines such as phenylmethane and diaminodiphenylsulfone, and the like.

As the acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride and the like are used. As the hydrazide compound, dibasic acid hydrazide such as adipic acid dihydrazide, dodecanedioic acid dihydrazide, and sebacic acid dihydrazide is used.

Among hydrazide compounds of epoxy resins, hydrazide compounds, especially dibasic dihydrazide compounds, are superior in storage stability to amine compounds and acid anhydrides, have a relatively low curing temperature and a relatively short curing time, Has been widely used.

In addition, for example, a dibasic acid dihydrazide compound (adipic acid hydrazide; ADH) having an average particle size of 1 to 5 m as a heat curing agent is added to a photo-setting resin composition, and the curing agent is uniformly dispersed in the matrix And the resolution of the defective hardening in the light shielding portion is improved.

However, since the thermosetting agent including a hydrazide compound typified by a dibasic hydrazide compound is a single crystal of an organic compound, it rapidly dissolves in the vicinity of the melting point, causing a viscosity drop and causing the adherend to be contaminated. In order to avoid such a problem, the use of a hydrazide compound having low-temperature curability results in poor solution stability, resulting in a problem in the available time. On the contrary, a hydrazide compound having a good usable time lacks low-temperature curability.

Patent Document 1: Japanese Patent Application Laid-Open No. 2006-58466

Disclosure of the Invention Problems to be Solved by the Invention A hydrazide compound having high activity for a resin having an unsaturated bond and capable of lowering the curing temperature and shortening the curing time and being stable in time and also useful as a thermosetting agent, And a curing agent, a resin composition and a cured product using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that by reacting a crystalline hydrazide compound having at least one hydrazide group in a molecule with a metal element capable of forming a complex with the crystalline hydrazide compound, A hydrazide compound useful as a curing agent which is capable of reacting uniformly and reacting uniformly with a resin having a low curing temperature and shortening a curing time and being stable in pot life can be obtained .

That is, the present invention is as follows.

[1] A hydrazide compound comprising a crystalline hydrazide compound having at least one hydrazide group in a molecule and a metal element capable of forming a complex with the crystalline hydrazide compound.

[2] The hydrazide compound according to [1], which has a peak in the range of 5.5 to 7.5 ° of Bragg angle 2θ (error 2θ ± 0.2 °) in the X-ray diffraction spectrum of CuKα line (wavelength 1.541 Å) .

[3] Hydrazide compound according to [1] or [2], wherein the hydrazide compound has a melting point of 60 to 240 ° C.

[4] The method according to any one of [1] to [4], wherein the metal element is selected from the group consisting of aluminum, titanium, tin, zirconium, zinc, iron, magnesium, cobalt, nickel, bismuth, molybdenum, copper, antimony, barium, boron, manganese, indium, cesium, The hydrazide compound according to any one of the above [1] to [3], wherein the hydrazide compound is at least one selected from the group consisting of germanium and gold.

[5] The hydrazide compound according to any one of [1] to [4], wherein the content of the metal element is 0.1 to 20.0% by mass relative to the total amount of the crystalline hydrazide compound and the metal element.

[6] The hydrazide compound according to any one of [1] to [5], which comprises at least two kinds of crystalline hydrazide compounds.

[7] The hydrazide compound according to any one of [1] to [6], which comprises a dibasic acid hydrazide compound.

[8] The hydrazide compound according to the above [6], wherein at least two kinds of crystalline hydrazide compounds are all dibasic acid hydrazides.

[9] The hydrazide compound according to any one of the above [6] or [8], wherein the content of one kind of crystalline hydrazide compound is 1 to 99% by mass based on the total of two or more kinds of crystalline hydrazide compounds. .

[10] The hydrazide compound according to any one of [1] to [9], wherein the average particle diameter is 0.5 to 20.0 μm.

[11] A curing agent for a resin comprising the hydrazide compound according to the above [1] to [10].

[12] A resin composition comprising the curing agent according to the above [11] and a resin having at least one unsaturated bond in the molecule and / or an epoxy resin.

[13] The resin composition according to the above [12], wherein the resin having an unsaturated bond is a resin having at least one (meth) acryloyl group in the molecule.

[14] A cured product obtained by curing the resin composition according to the above [12] or [13].

[15] A method for producing a crystalline hydrazide compound, comprising the steps of: heating a crystalline hydrazide compound having at least one hydrazide group in a molecule and a metal element capable of forming a complex with the crystalline hydrazide compound to obtain a mixture; And then cooling the mixture to obtain a solidified product.

[16] The production method according to the above-mentioned [15], which comprises a step of pulverizing solid matter into particles having an average particle diameter of 0.5 to 20.0 탆.

The hydrazide compound of the present invention includes a crystalline hydrazide compound having at least one hydrazide group in the molecule and a metal element capable of forming a complex with the crystalline hydrazide compound to form at least a part of the crystalline hydrazide compound and the metal It is assumed that the element forms a complex. As a result, the hydrazide compound of the present invention has an increased activity with respect to the unsaturated bond.

Further, the hydrazide compound of the present invention tends to have a lower melting point than that of the crystalline hydrazide compound as a raw material and has a smaller heat of fusion. Therefore, the hydrazide compound of the present invention can be produced at a relatively low temperature with an unsaturated bond (e.g., And the curing time can be shortened by uniformly curing without decreasing the viscosity and causing contamination of the adherend. As described above, the hydrazide compound of the present invention can be preferably used as a curing agent such as a resin having an unsaturated bond and / or an epoxy resin, because the curing temperature can be lowered and the curing time can be shortened. The resin composition using the hydrazide compound of the present invention as a curing agent is stable over time and has good productivity.

1 is an X-ray diffraction spectrum of a hydrazide compound (Example 1: T1-2h) of the present invention.
2 is an X-ray diffraction spectrum of a hydrazide compound (Example 2: T1-5h) of the present invention.
3 is an X-ray diffraction spectrum of a hydrazide compound (Example 3: C3-2h) of the present invention.
4 is an X-ray diffraction spectrum of a hydrazide compound (Example 4: C3-2h-5Hold) of the present invention.
5 is an X-ray diffraction spectrum of the hydrazide compound (Example 5: E3-2h) of the present invention.
6 is an X-ray diffraction spectrum of the hydrazide compound (Example 6: F3-2h) of the present invention.
7 is an X-ray diffraction spectrum of the hydrazide compound (Example 7: G3-2h) of the present invention.
8 is an X-ray diffraction spectrum of a hydrazide compound (Example 8: hX3-2h) of the present invention.
9 is an X-ray diffraction spectrum of the hydrazide compound (Example 9: hY3-2h) of the present invention.
10 is an X-ray diffraction spectrum of a hydrazide compound (Example 10: hZ3-2h) of the present invention.
11 is an X-ray diffraction spectrum of the hydrazide compound (Example 11: S-C3-2h) of the present invention.
12 is an X-ray diffraction spectrum of the hydrazide compound (Example 12: DSI-111C3-2h) of the present invention.
13 is an X-ray diffraction spectrum of a crystalline hydrazide compound of Comparative Example (Comparative Example 1: SDH).
FIG. 14 is an X-ray diffraction spectrum of a crystalline hydrazide compound (Comparative Example 2: DDH) of Comparative Example; FIG.
15 is an X-ray diffraction spectrum of a crystalline hydrazide compound (Comparative Example 4: N-2h-5Hold) of Comparative Example;
16 is a view showing the DSC curve of the hydrazide compound (Example 1: T1-2h) of the present invention.
17 is a DSC curve of the hydrazide compound (Example 2: T1-5h) of the present invention.
18 is a diagram showing the DSC curve of the hydrazide compound (Example 3: C3-2h) of the present invention.
19 is a view showing the DSC curve of the hydrazide compound (Example 4: C3-2h-5Hold) of the present invention.
20 is a view showing the DSC curve of the hydrazide compound (Example 5: E3-2h) of the present invention.
21 is a view showing a DSC curve of the hydrazide compound (Example 6: F3-2h) of the present invention.
22 is a view showing a DSC curve of the hydrazide compound (Example 7: G3-2h) of the present invention.
23 is a view showing the DSC curve of the hydrazide compound (Example 8: hX3-2h) of the present invention.
24 is a diagram showing the DSC curve of the hydrazide compound (Example 9: hY3-2h) of the present invention.
25 is a view showing a DSC curve of the hydrazide compound of the present invention (Example 10: hZ3-2h);
26 is a view showing a DSC curve of the hydrazide compound (Example 11: S-C3-2h) of the present invention.
27 is a view showing a DSC curve of the hydrazide compound of the present invention (Example 12: DSI-111C3-2h).
28 is a view showing a DSC curve of a crystalline hydrazide compound of Comparative Example (Comparative Example 1: SDH);
29 is a view showing a DSC curve of a crystalline hydrazide compound (Comparative Example 2: DDH) of Comparative Example.
30 is a view showing the DSC curve of the crystalline hydrazide compound of Comparative Example (Comparative Example 3: SD55).
31 is an X-ray diffraction spectrum of the hydrazide compound (Example 13-1: C3-b12-0h) of the present invention.
32 is an X-ray diffraction spectrum of the hydrazide compound (Example 13-2: C3-b12-1h) of the present invention.
33 is an X-ray diffraction spectrum of the hydrazide compound (Example 13-3: C3-b12-2h) of the present invention.
34 is an X-ray diffraction spectrum of the hydrazide compound (Example 13-4: C3-b12-3h) of the present invention.
35 is a view showing FT-IR of the hydrazide compound (raw material mixture, T1-b5-0h, T1-b5-1h, T1-b5-2h, T1-b5-4h, T1-b5-5h) .
36 is a diagram showing ¹ H-NMR of a gas released at the time of preparing the hydrazide compound (Example 1: T1-2h) of the present invention.
37 is a view showing the DSC curve of the resin composition of the present invention (Example 15: curing agent T1-2h).
38 is a view showing a DSC curve of the resin composition of the present invention (Example 16: curing agent T1-5h).
39 is a view showing a DSC curve of the resin composition of Comparative Example (Comparative Example 4: curing agent SD55).
40 is a view showing a DSC curve of the resin composition of the present invention (Example 17: curing agent T1-2h).
41 is a view showing a DSC curve of the resin composition of the present invention (Example 18: curing agent T1-5h).
42 is a diagram showing the DSC curve of the resin composition of the comparative example (Comparative Example 5: curing agent SD55).
43 is a view showing the DSC curve of the resin composition of the present invention (Example 19: curing agent T1-2h);
44 is a view showing a DSC curve of the resin composition of the present invention (Example 20: curing agent T1-5h);
Fig. 45 is a diagram showing the DSC curve of the resin composition of Comparative Example (Comparative Example 6: curing agent SD55). Fig.

The hydrazide compound of the present invention includes a crystalline hydrazide compound having at least one hydrazide group in the molecule and a metal element capable of forming a complex with the crystalline hydrazide compound.

The crystalline hydrazide compound is not particularly limited as long as it has crystallinity and has at least one hydrazide group in the molecule, and includes monobasic acid hydrazide having one hydrazide group in the molecule, dibasic acid having two hydrazide groups in the molecule Hydrazide, a tribasic acid hydrazide having three hydrazide groups in the molecule, and a multifunctional hydrazide having at least four hydrazide groups in the molecule. Among them, it is preferable to use a polyfunctional hydrazide compound from the viewpoint of heat resistance.

The crystalline hydrazide compound may use one kind of crystalline hydrazide compound alone or two or more kinds of crystalline hydrazide compounds in any combination.

As the optional combination of the crystalline hydrazide compound, for example, one kind of monobasic acid hydrazide compound may be used alone, or two or more monobasic acid hydrazide compounds may be used in combination, The hydrazide compound may be used alone, or a combination of a monobasic acid hydrazide compound and a dibasic acid hydrazide compound may be used, or two or more dibasic acid hydrazide compounds may be used in combination or a monobasic acid hydrazide And a dibasic acid hydrazide compound and a tribasic acid hydrazide compound may be used in combination. Among them, when two or more kinds of crystalline hydrazide compounds are used in combination, the melting point is lowered, so that temperature control of the constant temperature treatment can be easily performed as compared with the case of the single use.

When two or more kinds of crystalline hydrazide compounds are used, the content of one kind of crystalline hydrazide compound relative to the total amount of two or more kinds of crystalline hydrazide compounds is preferably 1 to 99% by mass, more preferably 10 To 90% by mass, and more preferably from 30% to 70% by mass.

Examples of the crystalline hydrazide compound include monobasic acid monohydrazides represented by the formula (1).

≪ Formula (1) >

(Wherein R represents a hydrogen atom, an alkyl group, or a substituted or unsubstituted aryl group)

Examples of the alkyl group represented by R include straight chain alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl groups, and cycloalkyl groups having 3 to 12 carbon atoms such as cyclohexane . Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. Examples of the substituent include a halogen atom such as a hydroxyl group, fluorine, chlorine and bromine, a halogen atom such as methyl group, ethyl group, n-propyl group, isopropyl group, n- Or a straight chain or branched chain alkyl group of 1 to 4 carbon atoms.

Specific examples of the monobasic acid hydrazide represented by the formula (1) include acetohydrazide, propionic acid hydrazide, pentanoic acid hydrazide, lauric acid hydrazide, cyclohexanecarbohydrazide, salicylic acid hydrazide, p- Hydroxybenzoic acid hydrazide, and naphthoic acid hydrazide. Specific examples of the monobasic acid hydrazide include benzenesulfono hydrazide.

As the crystalline hydrazide compound, there may be mentioned, for example, a dibasic acid dihydrazide represented by the formula (2).

≪ Formula (2) >

(Wherein A represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group or an oxo group, and n represents an integer of 0 to 18)

Examples of the alkylene group represented by A include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonanemethylene group, And straight chain alkylene groups having 1 to 12 carbon atoms such as a methylene group. The substituent of the alkylene group includes, for example, a hydroxyl group. Examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group. Examples of the substituent of the arylene group include the same substituents as those of the aryl group.

Specific examples of the dibasic acid hydrazide represented by the formula (2) include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, pimelic acid dihydrazide, Azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, hexadecanedioic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, and the like. Specific examples of the dibasic acid hydrazide include carbhydrazide, maleic dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, 2,6-naphthoic acid Dihydrazide, 1,4-naphthoic acid dihydrazide, 4,4'-bisbenzene dihydrazide, hydroquinone diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, catechol diglycolic acid dihydrazide, 4,4'-ethylidene bisphenol-diglycolic acid dihydrazide, 4,4'-vinylidene bisphenol-diglycolic acid dihydrazide, and the like.

Examples of the tribasic acid hydrazide include 1,3,5-tris (2-hydrazinocarbonylalkyl) iso-propyl isocyanurate such as 1,3,5-tris (2-hydrazinocarbonylethyl) And the like.

As the polyfunctional hydrazide, for example, poly (acrylic acid hydrazide) and the like can be given.

Examples of the metal element include aluminum, titanium, tin, zirconium, zinc, iron, magnesium, cobalt, nickel, bismuth, molybdenum, copper, antimony, barium, boron, manganese, indium, cesium, holmium, yttrium, , Silver, germanium, and gold. As the metal element, at least one element selected from the group consisting of aluminum, titanium, tin, zirconium, zinc, iron, magnesium, cobalt, nickel, bismuth, molybdenum, copper, antimony, barium and boron is preferably used . The metal elements may be used alone or in combination of two or more. The metal element may be in the form of a metal oxide or a metal hydroxide.

The content of the metal element is preferably 0.1 to 20.0 mass%, more preferably 1.0 to 10.0 mass% with respect to the total amount of the crystalline hydrazide compound and the metal element.

If the content of the metal element is 0.1 to 20.0 mass% with respect to the total amount of the crystalline hydrazide compound and the metal element, it is assumed that the metal element and the crystalline hydrazide compound form a good complex.

The kind, number and ratio of the crystalline hydrazide compound and the kind, number and ratio of the elements capable of forming a complex are appropriately selected depending on various conditions such as the type and use of the resin composition to be cured, the required curing time, You can decide.

Next, the physical properties of the hydrazide compound of the present invention will be described.

[X-ray diffraction spectrum]

It is presumed that the hydrazide compound of the present invention is a compound in which the crystalline hydrazide compound becomes a ligand and is coordinatively bonded to a metal ion, and at least a part of the crystalline hydrazide compound forms a complex with the metal element.

It is not clear whether or not the crystalline hydrazide compound and the metal element form a strict complex. However, when the hydrazide compound of the present invention is compared with the crystalline hydrazide compound which is one of the raw materials, the X- A range in which the maximum intensity peak of 10 DEG or less of the Bragg angle 2 &thetas; (error 2 &thetas; +/- 0.2 DEG) appears with respect to the diffraction spectrum is different. The crystalline hydrazide compound which is one kind of raw material has a peak in the range of 4.0 to 5.0 of Bragg angle 2? (Error 2? ± 0.2 °) with respect to the X-ray diffraction spectrum with respect to the CuK? Ray.

On the other hand, in the hydrazide compound of the present invention, a peak appears in the range of 5.5 to 7.5 ° of Bragg angle 2? (Error 2? ± 0.2 °) with respect to the X-ray diffraction spectrum with respect to the CuK? The hydrazide compound of the present invention is shifted in the direction in which the inter-lattice distance becomes shorter as compared with the crystalline hydrazide compound, which is one of the raw materials, at a maximum intensity peak of 10 degrees or less of the Bragg angle 2 ?. From this, it is presumed that at least a part of the crystalline hydrazide compound and the metal element form a complex.

The hydrazide compound of the present invention is a compound having a crystal transformation in which a peak appears in the range of 5.5 to 7.5 degrees of Bragg angle 2? (Error 2? ± 0.2 degrees) with respect to the X-ray diffraction spectrum of CuK? Ray (wavelength 1.541 angstroms).

The X-ray diffraction spectrum is measured using, for example, an X-ray diffraction apparatus (product name: XRD-6100, manufactured by Shimadzu Corporation).

The crystalline hydrazide compound not containing a metal element also contains two or more crystalline hydrazide compounds in comparison with the peak of one kind of crystalline hydrazide compound at a Bragg angle 2? Of the maximum intensity peak of 10 degrees or less tends to shift in the direction of 5.5 degrees of the Bragg angle.

The hydrazide compound of the present invention is obtained by reacting a crystalline hydrazide compound which is one kind of raw material in a range of 20.0 to 25.0 ° of Bragg angle 2θ (error 2θ ± 0.2 °) with respect to the X-ray diffraction spectrum of CuKα line (wavelength 1.541 Å) A broad peak is observed. From these results, it is considered that the hydrazide compound of the present invention is a partial crystal compound in which a part of the metal element and the crystalline hydrazide compound forms a complex and the amorphous state and the crystal state are mixed.

[Melting point]

The hydrazide compound of the present invention preferably has a melting point in the range of 60 to 260 캜, more preferably 60 to 230 캜, and still more preferably 60 to 220 캜.

The melting point of the hydrazide compound is determined, for example, by using a differential scanning calorimeter (Pyris6DSC, manufactured by Perkin Elmas Inc., hereinafter referred to as " DSC ") as the melting point of the maximum peak temperature of endothermic melting.

The hydrazide compound of the present invention tends to have a lower melting point than a crystalline hydrazide compound which is a raw material not containing a metal element.

[Heat of fusion]

In addition, the hydrazide compound of the present invention has a heat of fusion of 15% or less as compared with a crystalline hydrazide compound which is a raw material containing no metal element.

Since the hydrazide compound of the present invention becomes smaller than the crystalline hydrazide compound which is the raw material of the heat of fusion, the hydrazide compound is used as a thermosetting agent such as a resin having an unsaturated bond (for example, a (meth) acrylic resin) or an epoxy resin , The curing temperature can be lowered and the curing time can be shortened.

The heat of fusion is obtained by using the same apparatus as the apparatus for measuring the melting point, and the peak area of the endothermic peak due to melting is determined as the heat of fusion (J / g).

[Form of hydrazide compound]

The hydrazide compound of the present invention is preferably in the form of a ground particle. For example, when the hydrazide compound is pulverized into a particulate form, when the hydrazide compound is used as a heat curing agent, the reactivity with the resin can be further increased and the curing time can be further shortened.

The average particle size of the hydrazide compound is not particularly limited. When the hydrazide compound of the present invention is used as a curing agent for a resin, the average particle size is preferably 0.5 to 20.0 mu m, more preferably 1.0 to 10.0 mu m, to be.

If the average particle diameter of the hydrazide compound is less than 0.5 mu m, there is a possibility that the storage stability is lowered, and the viscosity of the resin composition containing the hydrazide compound as a heat curing agent is increased, which is not preferable. On the other hand, when the average particle diameter exceeds 20.0 탆, the reactivity is lowered, and when used as a heat curing agent, the cured state becomes uneven, and the heat resistance and moisture resistance of the cured product are lowered.

The average particle size can be obtained by a particle size distribution measuring apparatus using a laser diffraction / scattering method. The average particle size is a mass average value D ₅₀ (D ₅₀ is a cumulative mass of 50% or less) in the particle size distribution measurement by laser diffraction / , That is, the median diameter).

<Curing agent>

The hydrazide compound of the present invention has high activity for a resin having an unsaturated bond, since it is presumed that at least a part of the crystalline hydrazide compound forms a complex with the metal element. Therefore, the hydrazide compound of the present invention preferentially reacts with a resin having an unsaturated bond. Further, the hydrazide compound of the present invention tends to lower the melting point as compared with the crystalline hydrazide compound as a raw material, and since the heat of fusion becomes smaller, it also reacts with a resin having an unsaturated bond and an epoxy resin at a relatively low temperature, It can be uniformly cured in a short curing time without causing deterioration, contamination to the adherend, bleeding phenomenon, and the like. As described above, the hydrazide compound of the present invention can be preferably used as a thermosetting agent such as a resin having an unsaturated bond, an epoxy resin and the like, and can lower the curing temperature and shorten the curing time, and has a high liquid stability. Stable and productive.

When the hydrazide compound of the present invention is used as a curing agent for a resin, one kind or two or more kinds of them may be mixed and used.

When the hydrazide compound of the present invention is used as a resin curing agent, it is not particularly limited, but it is preferably 0.1 to 80 parts by mass, more preferably 1 to 50 parts by mass, based on 100 parts by mass of the resin (depending on purpose).

<Resin composition>

The resin composition comprises a curing agent containing the hydrazide compound of the present invention and a resin having at least one unsaturated bond in the molecule and / or an epoxy resin, and examples thereof include a resin having at least one unsaturated bond in the molecule or One type of epoxy resin may be used alone, or a plurality of types may be used together, or an unsaturated bond-containing epoxy resin may be used.

Examples of the epoxy resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, Glycidyl ester-based resins, glycidylamine-based epoxy resins, heterocyclic epoxy resins, and urethane-modified epoxy resins. Among them, it is preferable to use bisphenol A type epoxy resin, cresol novolak type epoxy resin or the like. Epoxy (meth) acrylic acid obtained by modifying a resin having a glycidyl group with (meth) acrylic acid may also be used.

The resin composition preferably contains a resin having at least one unsaturated bond in the molecule.

Examples of the resin having at least one unsaturated bond in the molecule include styrene derivatives, ethylene derivatives, maleimide derivatives, (meth) acrylic acid derivatives and the like. Among them, it is preferable to use an acrylic acid derivative having at least one (meth) acryloyl group in the molecule.

Specific examples of the acrylic acid derivatives include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i- ; (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; (Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- Methacrylic acid esters; (Meth) acrylic esters of alicyclic alcohols such as cyclohexyl (meth) acrylate, and the like. Here, (meth) acrylic acid means both of acrylic acid and methacrylic acid.

The blending amount of the epoxy resin and the resin having at least one unsaturated bond in the molecule can be appropriately determined depending on the purpose of the cured product obtained by curing the composition. When the resin having at least one unsaturated bond in the molecule is an acrylic acid derivative having at least one (meth) acryloyl group in the molecule, the (meth) acryloyl group is added in an amount of 0.1 to 9.0 equivalents based on 1 equivalent of the epoxy group (Meth) acryloyl group is more preferably 0.3 to 4.0 equivalents.

The resin composition may contain a silicone resin, a urea resin, an imide resin, glass, and the like, if necessary, in addition to the above resin.

The resin composition may optionally contain various additives such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, drawing modifiers, thermal polymerization inhibitors, leveling agents, surfactants, colorants, preservation stabilizers, plasticizers, lubricants , A filler, an inorganic particle, an antioxidant, a wettability improver, and an antistatic agent.

The resin composition containing the hydrazide compound of the present invention as a curing agent has a good liquid stability of the resin composition and a stable change in viscosity (liquid stability) per one week at 25 DEG C, and is stable in the time available.

As a method of measuring the liquid stability, for example, a 3 占 R7.7 cone rotor was attached to this viscometer using a RE-105U type viscometer (manufactured by Axis KK), and 0.1 ml of the resin composition to be measured The measurement is carried out at 2.5 rpm by setting in a viscometer. After the object to be measured is allowed to stand at 25 占 폚 for one week, the viscosity is measured again, and the rate of change in viscosity before and after the rest for one week is calculated.

&Lt;

The cured product obtained by curing the resin composition of the present invention has good productivity because the curing temperature is low, the curing time is shortened, and the time is stable.

Next, the method for producing the hydrazide compound of the present invention will be described.

A method for producing a hydrazide compound of the present invention comprises the steps of heating a crystalline hydrazide compound having at least one hydrazide group in a molecule and a metal element capable of forming a complex with the crystalline hydrazide compound to obtain a mixture, And a step of cooling the mixture to obtain a solidified product.

As a process for obtaining a molten mixture, first, a crystalline hydrazide compound having at least one hydrazide group in a molecule and a metal element capable of forming a complex with the crystalline hydrazide compound are heated to form a crystalline hydrazide The compound is dissolved to obtain a mixture.

The temperature for heating the crystalline hydrazide compound is not particularly limited, but is preferably a temperature at which the crystalline hydrazide compound is in a substantially liquid state. The temperature at which the crystalline hydrazide compound is in a substantially liquid state may be a temperature near the melting point of the crystalline hydrazide compound, for example, a temperature lower than the melting point of the crystalline hydrazide compound by about 10 ° C, .

Next, as a step of incubating the mixture, the mixture is incubated at a constant temperature for a certain period of time. The term &quot; constant temperature treatment &quot; means maintaining the mixture at a constant temperature (error range +/- 10 DEG C) for a certain period of time.

The temperature for carrying out the incubation treatment is not particularly limited, but is preferably 100 to 280 ° C, more preferably 130 to 250 ° C.

If the temperature for the incubation treatment is excessively high (for example, at a temperature exceeding 280 캜), the complex formation proceeds sharply and becomes difficult to control. On the other hand, if the temperature for the incubation treatment is excessively low (for example, a temperature lower than 100 ° C), the time for the constant temperature treatment becomes long and the production efficiency becomes low.

The time for carrying out the incubation treatment is not particularly limited, but is preferably 0.01 to 10 hours.

The time for carrying out the incubation treatment differs depending on the temperature at which the incubation is carried out. When the temperature is high, the treatment time is short. When the temperature is low, the treatment time is prolonged. Therefore, It is possible.

Thereafter, the mixture is cooled to obtain a solidified product. In the step of obtaining a solidified product, the cooling rate is preferably 0.01 ° C / min to 200 ° C / min, more preferably 0.1 ° C / min to 100 ° C / min. The cooling may be carried out in multiple stages. For example, the mixture may be cooled to about 200 ° C in the first stage and crystals may be grown at this temperature, followed by cooling to room temperature in the second stage.

In addition, the method for producing a hydrazide compound of the present invention preferably includes a step of pulverizing a solid obtained by cooling and pulverizing it into a particle having an average particle diameter of 0.5 to 20.0 占 퐉.

As a method of grinding, it is preferable to grind the solidified material using, for example, a high-pressure grinder. Examples of the high-pressure pulverizer include cross jet mills (manufactured by Gurimotec Corp.), counter jet mills (manufactured by Hosokawa Micron Corporation), and nanojet millers (manufactured by Aisin Nanotechnology Co., Ltd.).

The FT-IR chart of the hydrazide compound prepared by the production method of the present invention is measured by an FT-IR measuring apparatus (for example, Spectrum one, manufactured by Perkin Elmas) The peak derived from NH stretching at a wavelength of about 3300 cm &lt;&quot; ¹ &gt; becomes smaller. On the other hand, the peaks derived from CH stretching in the wavelength range of 2800 to 3000 cm &lt; ^-1 &gt; hardly change.

Further, gas is generated in the production of the hydrazide compound. When the collecting the gas ¹ H-NMR measuring device measuring the ¹ H-NMR in (for example, JNM-ECA600, manufactured by Nippon Denshi), a peak appears in 2.9592ppm. This peak is a peak indicating water (H ₂ O).

In the hydrazide compound of the present invention, the peak derived from NH stretching by FT-IR decreases in size, and water (H ₂ O) is generated in the gas released during the production of the hydrazide compound by ¹ H-NMR , It can be inferred that at least a part of the crystalline hydrazide compound and the metal element form a complex.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

&Lt; Two kinds of crystalline hydrazide compounds and metal elements >

[Example 1]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical), and 500 parts by weight of titanium oxide (AEROXIDE P25, 20 parts by weight (titanium content: 1.2% by mass)) was placed in a separable flask of 5000 ml and heated at 200 캜 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified material, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient), sieved into a sieve having a mesh size of 500 mu m, and finally passed through a high-pressure mill (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) A hydrazide compound having an average particle size of 2.8 mu m (hereinafter, the hydrazide compound of Example 1 was referred to as "T1-2h") was prepared.

[Example 2]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical), and 500 parts by weight of titanium oxide (AEROXIDE P25, 20 parts by weight (titanium content: 1.2% by mass)) was placed in a separable flask of 5000 ml and heated at 200 캜 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 5 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient), and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 2 is referred to as &quot; T1-5h &quot;).

[Example 3]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical), aluminum oxide (AEROXIDE AluC, (Aluminum content: 2.5% by mass) was placed in a 5000 ml separable flask and heated at 200 占 폚 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient) and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 3 is referred to as &quot; C3-2h &quot;).

[Example 4]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical), aluminum oxide (AEROXIDE AluC, (Aluminum content: 2.5% by mass) was placed in a 5000 ml separable flask and heated at 200 占 폚 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled in an oven from 200 to 180 DEG C at a cooling rate of about 1.0 DEG C / min, and crystals were grown at 180 DEG C for 5 hours. Further, the mixture was cooled to room temperature at a cooling rate of 1.0 캜 / min to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient) and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 4 was referred to as &quot; C3-2h-5Hold &quot;).

[Example 5]

(DDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of zinc oxide (ZnO, manufactured by CI Chemical Industries, Ltd.), 500 parts by weight of sodium hexametaphosphate dihydrazide (SDH, manufactured by Otsuka Chemical Co., ) Was placed in a separable flask of 5000 ml and heated at 200 占 폚 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient) and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 5 was referred to as &quot; E3-2h &quot;).

[Example 6]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical), tin oxide (SnO ₂ , (Content of tin: 3.7 mass%) was placed in a 5000 ml separable flask and heated at 200 占 폚 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient) and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 6 is referred to as &quot; F3-2h &quot;).

[Example 7]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical), bismuth oxide (bismuth oxide A, (Bismuth content: 4.3% by mass) was placed in a separable flask of 5000 ml and heated at 200 캜 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient) and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 7 is referred to as &quot; G3-2h &quot;).

[Example 8]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical), 0.5 part by weight of cobalt hydroxide (manufactured by Tanaka Kagaku Kogyo Co., ) Was put into a 5000 ml separable flask and heated at 200 캜 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient) and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 8 was referred to as &quot; hX3-2h &quot;).

[Example 9]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical Co., Ltd.), nickel hydroxide (manufactured by Tanaka Chemical Industry Co., ) Was placed in a 5000 ml separable flask and heated at 200 캜 to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient) and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 9 is referred to as &quot; hY3-2h &quot;).

[Example 10]

500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical Co., Ltd.), zirconium hydroxide (zirconium hydroxide 999- 50 parts by weight (zirconium content: 2.6% by mass)) was placed in a separable flask of 5000 ml and heated at 200 占 폚 to dissolve the two kinds of crystalline hydrazide compounds in a substantially liquid state . This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified material, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient) and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound having an average particle diameter of 2.9 μm The hydrazide compound of Example 10 is referred to as &quot; hZ3-2h &quot;).

<One kind of crystalline hydrazide compound and metal element>

[Example 11]

1000 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical) and 50 parts by weight of aluminum oxide (AEROXIDE AluC, manufactured by Nippon Aerosil Co., Ltd.) (content of aluminum of 2.5% by mass) And the mixture was heated at 200 DEG C in a flask to obtain a mixture in which two kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified product, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient), and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 11 was referred to as &quot; S-C3-2h &quot;).

<Three kinds of crystalline hydrazide compounds and metal elements>

[Example 12]

, 300 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 300 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Otsuka Chemical Co., Ltd.) and 300 parts by weight of isophthalic acid dihydrazide , And 45 parts by weight of aluminum oxide (AEROXIDE AluC, manufactured by Nippon Aerosil Co., Ltd.) (content of aluminum of 2.5 mass%) were placed in a separable flask of 5000 ml, heated at 200 캜, To obtain a mixture in which the three kinds of crystalline hydrazide compounds were dissolved in a substantially liquid state. This mixture was incubated at 200 DEG C for 2 hours.

Thereafter, the mixture was transferred to a Pyrex (registered trademark) glass tray preliminarily heated to 200 占 폚 and set in an oven at 200 占 폚. Then, the molten mixture was cooled to room temperature at a cooling rate of about 1.0 DEG C / min in an oven to obtain a solidified product.

The solidified material, which had been completely cooled to room temperature, was pulverized with a cutter mill (manufactured by Orient), and finally pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnology) to obtain a hydrazide compound The hydrazide compound of Example 12 was referred to as &quot; DSI-111C3-2h &quot;).

[Comparative Example 1]

A commercially available sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical) was used as Comparative Example 1.

[Comparative Example 2]

Commercially available dodecanedioic acid dihydrazide (DDH, manufactured by Otsuka Chemical) was used as Comparative Example 2.

[Comparative Example 3]

(Hereinafter referred to as &quot; SD55 &quot;) obtained by mixing 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical) and 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Otsuka Chemical Co., ) Was used as Comparative Example 3.

[Comparative Example 4]

The mixture of Comparative Example 3 was heated to 200 ° C to melt the mixture in a liquid phase, and then the hydrazide compound of Comparative Example 4 was obtained in the same manner as in Example 4.

The X-ray diffraction spectra of the hydrazide compounds of Examples 1 to 12 and Comparative Examples 1 to 2 and 4, the DSC curves of Examples 1 to 12 and Comparative Examples 1 to 3, and the liquid stability of Examples 1 to 12 were evaluated by the following method . The results of measurement of Examples 1 to 12 and Comparative Examples 1 to 3 are shown in Table 1 as liquid stability, melting point and heat of fusion.

[X-ray diffraction spectrum]

The X-ray output voltage was 40.0 KV, the X-ray output current was 40.0 mA, and the scan step width was 0.02 using an X-ray diffraction apparatus (product name: XRD-6100, manufactured by Shimadzu Corporation).

[Differential Scanning Calorimetry (DSC)]

Using a differential scanning calorimeter (Pyris 6 DSC, manufactured by Perkin Elmer), the hydrazide compound as a measurement sample was enclosed in a container made of aluminum, and the maximum peak temperature of endothermic melting was obtained as a melting point. The peak area of the endotherm was obtained as the heat of fusion.

[Solution stability]

15 parts by weight of the hydrazide compound and 100 parts by weight of bisphenol A type epoxy acrylic resin (KR-850CRP, manufactured by KSM) were mixed using the hydrazide compound of Examples 1 to 12 as a thermosetting agent to prepare a resin composition . The bisphenol A type epoxy acrylic resin had one equivalent of the acryloyl group per one equivalent of the epoxy group. The resin composition was incubated at 25 占 폚, and a 3 占 R7.7 cone rotor was attached to a RE-105U type viscometer (manufactured by Ohkusan Co., Ltd.), and 0.15 ml of the resin composition to be a target was set in a cone rotor. The viscosity of the resin composition at 25 캜 at rpm was measured. The resin composition to be measured was allowed to stand at 25 占 폚 for 1 week, and the viscosity of this resin composition after one week was measured by the above-mentioned method, and the rate of change (% / week) of viscosity after one week from the initial viscosity was calculated. If the measurement range is exceeded, the measurement is not possible. In addition, the standard for the measurement range overflow is 1,200,000 mPa 占 퐏.

As shown in Figs. 1 to 12, the hydrazide compounds of Examples 1 to 12 exhibited an X-ray diffraction spectrum for a CuK? Ray (wavelength 1.541 Å) of 5.5 to 7.5 ° of Bragg angle 2θ (error 2θ ± 0.2 °) Lt; / RTI &gt; On the other hand, as shown in Figs. 13 and 14, the crystalline hydrazide compound, which is one of the raw materials of Comparative Examples 1 and 2, has a maximum intensity peak at 10 degrees or less of the Bragg angle 2? (Error 2? The range of 4.0 to 5.0 degrees of the error 2 &amp;thetas; +/- 0.2 DEG). The hydrazide compounds of Examples 1 to 12 exhibited a maximum intensity peak of 10 DEG or less of Bragg angle 2 &amp;thetas; (error 2 &amp;thetas; +/- 0.2 DEG) as compared with one kind of crystalline hydrazide compound, Lt; / RTI &gt;

In Fig. 10, the peak appearing near 2 deg. Of the Bragg angle 2 [theta] (2 &thetas; +/- 0.2 deg.) Is scattered light and is not a peak derived from X-ray diffraction.

From the results shown in Figs. 1 to 12 and Table 1, it is presumed that at least a part of the hydrazide compound of the hydrazide compounds of Examples 1 to 12 forms a complex with the metal element.

In addition, the hydrazide compounds of Examples 1 to 12 exhibited a peak appearing in the range of 5.5 to 7.5 degrees of Bragg angle 2? (Error 2? +/- 0.2 degrees) as compared with the crystalline hydrazide compound of one of the raw materials of Comparative Examples 1 and 2 And the proportion of the amorphous material as a whole is increased.

In addition, the hydrazide compounds of Examples 1 to 12 had a peak appearing in the range of 20.0 to 25.0 ° of Bragg angle 2? (Error 2? ± 0.2 °) of the crystalline hydrazide compound which is one of the raw materials of Comparative Examples 1 and 2 Compared to peak, it is broad. From these results, it is considered that the hydrazide compounds of Examples 1 to 12 form a complex at least partially and a partial crystal compound in which an amorphous state and a crystalline state are mixed.

Further, as shown in Fig. 15, the two types of crystalline hydrazide compounds of Comparative Example 4 were shifted in the direction of the maximum intensity peak of 10 DEG or less of the Bragg angle 2 &amp;thetas; (error 2 &amp;thetas; Since it does not contain a metal element, it was not a peak derived from the complex formation of a hydrazide compound with a metal element.

The hydrazide compounds of Examples 1, 2, 3, 5 to 7, 9, 10, and 12, as shown in the DSC curves and Table 1 of Figs. 16 to 30, The melting point was low. In addition, the hydrazide compounds of Examples 1 to 12 had a heat of fusion of 45% or less as compared with the hydrazide compounds of Comparative Examples 1 to 3.

From these results, when the hydrazide compounds of Examples 1 to 12 were used as a heat curing agent, the curing temperature could be lowered and the curing time could be shortened.

In addition, the hydrazide compounds of Examples 1 to 12 can change the numerical value of the liquid stability by changing the conditions (time, temperature, etc.) of the constant temperature treatment. In addition, the heat of fusion (J / g) of Comparative Example 4 was not improved more than that of Example 4 in which the same heat treatment was carried out.

When a hydrazide compound is used as a thermosetting agent, it is possible to form a hydrazide compound which can be used as a preferable thermosetting agent by changing the conditions of the thermosetting treatment with a resin to be cured or the like. When the hydrazide compound is used as a thermosetting agent, the hydrazide compound is formed so that the liquid stability is preferably 80% / week or less, more preferably 50% / week or less, and still more preferably 30% / week.

&Lt; Hydrazide compound having a different time for treating at a constant temperature >

[Example 13]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical), aluminum oxide (AEROXIDE AluC, (Aluminum content: 2.5% by mass) was placed in a separable flask of 5000 ml and heated to 200 占 폚. It was confirmed that the two kinds of crystalline hydrazide compounds were completely melted to obtain a molten mixture. This molten mixture was subjected to a constant temperature treatment at 200 占 폚 for 0 to 3 hours, sampled every 0, 1, 2, and 3 hours, and subjected to natural cooling to obtain a hydrazide compound. Each of the hydrazide compounds is referred to as Example 13-1 (C3-b12-0h, Figure 31), Example 13-2 (C3-b12-1h, Figure 32), Example 13-3 33) and Example 13-4 (C3-b12-3h, Fig. 34).

[Example 14]

, 500 parts by weight of sebacic acid dihydrazide (SDH, manufactured by Otsuka Chemical Co., Ltd.), 500 parts by weight of dodecanedioic acid dihydrazide (DDH, manufactured by Ohtsuka Chemical Co., Ltd.) and titanium oxide (AEROXIDE AluC, 20 parts by weight (titanium content: 1.2% by weight) was placed in a separable flask of 5000 ml and heated to 200 占 폚. It was confirmed that the two kinds of crystalline hydrazide compounds were completely melted to obtain a molten mixture. The molten mixture was subjected to a constant temperature treatment at 200 캜 for 0 to 5 hours, sampling at 0, 1, 2, 4, and 5 hours, and naturally cooled to obtain a hydrazide compound. Each hydrazide compound is referred to as "T1-b5S-0h", "T1-b5S-1h", "T1-b5S-2h", "T1-b5S-4h" and "T1-b5S-5h", respectively.

The X-ray diffraction spectrum of each hydrazide compound in Example 13 was measured by the above-mentioned method. The results are shown in Figs. The FT-IR of each hydrazide compound of Example 14 was measured by the following method. The results are shown in Fig. In addition, the gas generated during the incubation treatment was collected in Example 1, and the component of the gas was measured by ¹ H-NMR. The results are shown in Fig. In addition, DSC curves of Examples 13 and 14 were also measured, although the illustration was omitted.

[FT-IR]

FT-IR was measured using Spectrum circle (manufactured by Perkin Elmer).

[ ¹ H-NMR]

¹ H-NMR was measured by dissolving 50 μl of a sample in 500 μl of acetone-d6 (deuteration ratio: 99.9% or more) using JNM-ECA 600 (manufactured by Nippon Denshoku) at 25 ° C.

As shown in Figs. 31 to 34, the peak of the hydrazide compound of Example 13 in the vicinity of 5.0 deg. Of Bragg angle 2 [theta] (error 2 [theta] +/- 0.2 deg.) At 0 hours of the constant temperature treatment, It was confirmed that the surface lattice spacing in the range of 5.5 to 7.5 degrees of 2 [theta] (error 2 [theta] [theta] 0.2 [deg.]) Was shifted to a narrower side. From these results, it is presumed that the hydrazide compound of Example 13 increases in the ratio of the crystalline hydrazide compound and the metal element to form a complex as the time for the constant temperature treatment becomes longer.

Further, as the time of the constant temperature treatment became longer, the peak intensity appearing in the range of 23.0 to 24.0 ° of the Bragg angle 2? (Error 2? ± 0.2 °) decreased.

The DSC curves of the hydrazide compounds of Examples 13 and 14 were measured. However, the heat of fusion of the hydrazide compounds of Examples 13 and 14 was similar to that of the hydrated hydrazide compounds (SDH , DDH, SD55), it was less than 70%. In addition, the heat of fusion of the hydrazide compounds of Examples 13 and 14 tended to decrease as the time for the constant temperature treatment became longer. Further, it is assumed that the curved patterns of the hydrazide compounds of Examples 13 and 14 tend to become broader as the incubation time becomes longer, so that the proportion of amorphous as a whole increases.

As shown in Fig. 35, the hydrazide compound of Example 14 had a smaller peak derived from the NH stretching vibration near the wavelength of 3300 cm &lt; ^-1 &gt; as the time for the constant temperature treatment became longer. On the other hand, almost no change in peak derived from CH stretching vibration in the wavelength range of 2800 to 3000 cm ^-1 was observed.

As shown in Fig. 36, the ¹ H-NMR chart of the gas generated in the production of the hydrazide compound showed a peak at 2.9592 ppm. This peak is a peak indicating water (H ₂ O).

From the results shown in FIG. 35 and FIG. 36, it can be inferred that the hydrazide compound of the Examples forms a complex with at least a part of the crystalline hydrazide compound as a raw material and the metal element.

<Resin composition>

[Example 15]

15 parts by weight of this hydrazide compound and 100 parts by weight of bisphenol A type epoxy acrylic resin (KR-850CRP, manufactured by KSM) were compounded by using the hydrazide compound (T1-2h) of Example 1 as a thermosetting agent, .

[Example 16]

A resin composition was prepared in the same manner as in Example 15 except that the hydrazide compound (T1-5h) of Example 2 was used as a heat curing agent.

[Comparative Example 5]

A resin composition was prepared in the same manner as in Example 15 except that the hydrazide compound (SD55) obtained from the two kinds of crystalline hydrazide compounds of Comparative Example 3 was used as a curing agent.

[Example 17]

30 parts by weight of the hydrazide compound and 100 parts by weight of bisphenol A type epoxy resin (850S, manufactured by DIC) were mixed using the hydrazide compound (T1-2h) of Example 1 as a thermosetting agent to prepare a resin composition .

[Example 18]

A resin composition was prepared in the same manner as in Example 17 except that the hydrazide compound (T1-5h) of Example 2 was used as a heat curing agent.

[Comparative Example 6]

A resin composition was prepared in the same manner as in Example 17 except that hydrazide compound (SD55) obtained from two kinds of crystalline hydrazide compounds of Comparative Example 3 was used as a curing agent.

[Example 19]

Using the hydrazide compound (T1-2h) of Example 1 as a thermosetting agent, 15 parts by weight of this hydrazide compound and 40 parts by weight of an epoxyacrylate having 100% of a bisphenol A type epoxy resin (850S, manufactured by DIC) And 100 parts by weight of a resin were blended to prepare a resin composition.

[Example 20]

A resin composition was prepared in the same manner as in Example 19 except that the hydrazide compound (T1-5h) of Example 2 was used as a heat curing agent.

[Comparative Example 7]

A resin composition was prepared in the same manner as in Example 19 except that the hydrazide compound (SD55) obtained from the two kinds of crystalline hydrazide compounds of Comparative Example 3 was used as a curing agent.

Curing initiation temperatures of the resin compositions of Examples 15 to 20 and Comparative Examples 4 to 6 were measured using a differential scanning calorimeter (Pyris 6 DSC manufactured by Perkin Elmas). The measurement method is the same as described above. The results are shown in Figs.

The curing initiation temperatures of the resin compositions of Examples 15 to 20 and Comparative Examples 5 and 6 were measured using a differential scanning calorimeter (Pyris 6 DSC manufactured by Perkin Elmas Inc.). The measurement method is the same as described above. The results are shown in Figs.

As shown in Fig. 37, the resin composition of Example 15 started to cure from around 105 deg. C, and the resin composition of Example 16 started to cure from around 90 deg. C as shown in Fig. On the other hand, as shown in Fig. 39, the resin composition of Comparative Example 5 started curing at around 150 占 폚.

It was confirmed that the resin compositions of Examples 15 and 16 had a curing temperature lower than that of the resin composition of Comparative Example 5 by 30 占 폚 or more to improve the reactivity.

As shown in Fig. 40, the resin composition of Example 17 started curing at around 120 占 폚. Further, as shown in Fig. 41, the resin composition of Example 18 started curing at around 108 占 폚. On the other hand, as shown in Fig. 42, the resin composition of Comparative Example 5 started curing at around 160 占 폚.

It was confirmed that the resin compositions of Examples 17 and 18 had a curing temperature lower than that of the resin composition of Comparative Example 6 by 30 占 폚 or more to improve the reactivity.

As shown in Fig. 43, the resin composition of Example 19 starts curing from around 80 deg. C, and the resin composition of Example 20 starts curing from around 80 deg. C as shown in Fig. 44, In the resin composition of Comparative Example 7, curing was started from about 110 占 폚.

It was confirmed that the resin compositions of Examples 19 and 20 had a curing temperature lower than that of the resin composition of Comparative Example 7 by 30 占 폚 or more to improve the reactivity.

The hydrazide compound of the present invention can be used as a curing agent exhibiting preferable liquid stability depending on the purpose by changing the time of the constant temperature treatment. The effects of different liquid stability due to the constant temperature treatment time were confirmed as follows.

[Comparative Example 8]

The mixture of Comparative Example 3 was heated to 200 占 폚 to melt the mixture into a liquid phase and then cooled to room temperature at a cooling rate of about 1.0 占 폚 / minute in an oven without being subjected to a constant temperature treatment to obtain a solidified product.

This hydrated compound was used in the same manner as in Example 1 to obtain the hydrazide compound of Comparative Example 7.

(J / g) of each hydrazide compound of Examples 1 to 4 and Comparative Examples 4 and 8 and the heat of fusion of each hydrazide compound to the heat of fusion of the hydrazide compound of Comparative Example 3 (SD55: Table 2 shows the rate of decrease.

As shown in Table 2, the hydrazide compounds of Examples 1 to 4 exhibited a decrease in the heat of fusion and a rate of decrease in the heat of fusion, respectively, as the incubation time was longer regardless of the kind of the metal element.

On the other hand, the hydrazide compound of the comparative example did not increase the rate of decrease of the heat of fusion as long as the constant temperature treatment time was longer than that of the hydrazide compound of the Examples.

That is, in the hydrazide compounds of Examples 1 to 4, the decrease rate of the heat of fusion was as large as 57.3 to 83.5% as compared with the hydrazide compound of Comparative Example 3 (raw material). In Comparative Examples 4 and 8, the longer the incubation time was, the lower the rate of decrease of heat of fusion and the rate of decrease of heat of fusion were shown. Comparing Example 4 with Comparative Example 4, Was 83.5%, whereas the rate of decrease of the heat of fusion of Comparative Example 4 was as small as 57.9%.

Further, in the hydrazide compound of the present invention, the liquid stability of the resin composition using the hydrazide compound of the present invention as a curing agent was improved as the incubation time became longer.

Comparing the liquid stability of Examples 1 and 2 and Examples 3 and 4 using the same kind of metal element, the liquid stability of Example 2 was improved by 92.8% compared with Example 1. In addition, the liquid stability was improved by 98.3% in Example 4 with respect to Example 3. On the other hand, in comparison of Comparative Examples 4 and 8, the liquid stability was lowered in Comparative Example 8 in which the incubation time was shorter than that in Comparative Example 4 in which the incubation time was longer, and the tendency was reversed from that in Example.

From these results, it was confirmed that the hydrazide compound of the present invention can form a desired curing agent by the kind of the metal element forming the complex with the hydrazide compound, the time of the constant temperature treatment, the temperature of the heat treatment, and the like.

&Lt; Industrial applicability >

The hydrazide compound of the present invention can stably react with a resin having an unsaturated bond with high activity, can lower the curing temperature and shorten the curing time, and is also stable over the available time, . Therefore, the hydrazide compound of the present invention can be preferably used as a sealing material for electronic parts such as a liquid crystal display device and a heat curing agent for a resin composition used as a sealing agent.

Claims (17)

(C) at least one crystalline hydrazide compound selected from the group consisting of a monobasic acid hydrazide, a dibasic acid hydrazide, a tribasic acid hydrazide and a polyfunctional hydrazide as a curing agent which reacts with a (meth) acryloyl group and / And a metal oxide or metal hydroxide containing a metal element capable of forming a complex with the crystalline hydrazide compound. The curing agent according to claim 1, which is obtained by heating a crystalline hydrazide compound, a metal oxide or a metal hydroxide, and mixing the dissolved crystalline hydrazide compound with a metal oxide or a metal hydroxide. The curing agent according to claim 1, which has a peak in a range of 5.5 to 7.5 ° of Bragg angle 2? (Error 2? ± 0.2 °) in an X-ray diffraction spectrum with respect to a CuK? Ray (wavelength 1.541 Å). The curing agent according to claim 1, wherein the crystalline hydrazide compound has a melting point of 60 to 260 ° C. The curing agent according to claim 1, wherein the crystalline hydrazide compound is a dibasic acid hydrazide. 6. The composition of claim 5 wherein the dibasic hydrazide is selected from the group consisting of oxalic acid dihydrazide, malonic acid dihydrazide, succinic dihydrazide, adipic acid dihydrazide, pimelic dihydrazide, suberic dihydrazide, There may be mentioned hydrazide, sebacic dihydrazide, dodecanedioic acid dihydrazide, hexadecanedioic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, carbohydrazide, maleic acid dihydrazide, fumaric acid dihydrazide , Diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, 2,6-naphthoic acid dihydrazide, 1,4-naphthoic acid dihydrazide, 4,4'-bisbenzene dihydrazide, hydroquinone Diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, catechol diglycolic acid dihydrazide, 4,4'-ethylidene bisphenol-diglycolic acid dihydrazide and 4,4'-vinylidene bisphenol - a curing agent which is a dibasic acid hydrazide selected from diglycolic acid dihydrazide. The curing agent according to claim 1, comprising at least two kinds of crystalline hydrazide compounds. The curing agent according to claim 7, wherein the content of one kind of crystalline hydrazide compound in the total of two or more kinds of crystalline hydrazide compounds is 1 to 99% by mass. The method of claim 1, wherein the metal element is selected from the group consisting of aluminum, titanium, tin, zirconium, zinc, iron, magnesium, cobalt, nickel, bismuth, molybdenum, copper, antimony, barium, boron, manganese, indium, cesium, , Calcium, silver, germanium and gold. The curing agent according to claim 1, wherein the content of the metal element is 0.1 to 20.0% by mass relative to the total amount of the metal oxide or metal hydroxide containing the crystalline hydrazide compound and the metal element. The curing agent according to claim 1, wherein the curing agent has an average particle diameter of 0.5 to 20.0 占 퐉. A resin composition comprising the curing agent according to any one of claims 1 to 11 and a resin having at least one (meth) acryloyl group and / or epoxy group in the molecule. A liquid crystal encapsulant using the resin composition according to claim 12. A cured product obtained by curing the resin composition according to claim 12. (Meth) acryloyl group and / or an epoxy group, which comprises reacting at least one compound selected from the group consisting of monobasic acid hydrazide, dibasic acid hydrazide, tribasic acid hydrazide and polyfunctional hydrazide A step of heating a metal oxide or metal hydroxide containing a hydrazide compound and a metal element capable of forming a complex with the crystalline hydrazide compound to obtain a molten mixture; subjecting the molten mixture to an incubation treatment; Followed by cooling to obtain a solidified product. The method for producing a curing agent according to claim 15, comprising a step of pulverizing the solidified material into particles having an average particle diameter of 0.5 to 20.0 탆. The method for producing a curing agent according to claim 15 or 16, wherein the temperature for the incubation in the step of incubating the molten mixture is 100 to 280 ° C and the time for the incubation is 0.01 to 10 hours.

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