JPS6040125A - Epoxy curing - Google Patents

Abstract

PURPOSE:In curing a polyepoxy compound, to cure it rapidly and efficiently at the desired elevated temperature, by using a polyhydric phenol salt of a 2-substituted imidazoline compound as a curing agent (or curing promotor). CONSTITUTION:In curing a polyepoxy compound (e.g., bisphenol A, resorcin, hydroquinone, phenol formaldehyde resin, etc.) containing one or more epoxy group on average in the molecule, 2-40pts.wt. polyhydric phenol salt (e.g., catechol, resorcin, etc.) of a 2-substituted imidazoline compound [e.g., compound shown by the formula (R and R' are alkyl, aralky, or aryl)] is used as a curing agent or curing promotor based on usually 100pts.wt. polyepoxy compound. EFFECT:A resin useful as a coating compound, adhesive, etc. having improved shelf stability at room temperature, curable at 100-180 deg.C in a short time, is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized by the fact that more than one epoxy W is present in the molecule on average.
How to quickly and efficiently cure polyepoxy compounds at desired elevated temperatures? ) and
The objective is to use latent hardeners or latent hardeners that do not materially affect the shelf life or storage stability of one-component epoxy resins, i.e., systems in which the polyepoxy compound is premixed with a hardener. The purpose of this invention is to provide a C-accelerating agent (catalyst). 11 of the 11 pieces of flexibility of the present invention! , 'T, is stored in a stable state with little change, cures quickly and efficiently at high temperatures, and has a good balance of properties such as electrical insulation performance, adhesion, transparency, and chemical resistance. It can be used as an insulating coating for electronic parts such as ceramic capacitors, film capacitors, carbon film resistors, metal oxide film resistors, and hybrid IC1, as well as metal plates, tubes, containers, etc. It is useful as a powder coating for exterior coatings.

General formula 11□C-CH-R' (in the formula, R and R' are represented by alkyl) The use of 2-substituted imidazoline as an epoxy resin curing agent is already known, and as an epoxy resin, it is difficult to yellow. Although these compounds have the advantage of being able to obtain cured products, for example, in the case of lower alkyl group-substituted imidacillins, moisture in the system or in the curing atmosphere may cause undesirable side reactions such as those listed below. , 1I2c C112 CI+3 ; z, l 16 Because it contains ethylenediamine monosubstituted amide, the cured epoxy resin has the disadvantage of having low heat resistance.Especially for thin materials such as paints and inks. However, if the storage stability is less than 100%, and the effect of moisture is not taken into consideration, then if the storage stability is also good, then it is possible to use H-class furkyl)jS substituted imidacillin or 1. J, l,, l, article 1'l Work with F.
Even in the case of storage, the curing speed was 1 degree slow, and there was a problem in terms of energy consumption. In view of these points, as a result of intensive studies, the present inventors have discovered that these disadvantages can be overcome by using a polyhydric phenol salt of 2-substituted imidazoline.

The 2-substituted imidazoline/polyhydric phenol salt according to the present invention is prepared by adding 1/2 to 1 mol of the above imidacillin compound per equivalent of phenolic OH group of the polyhydric phenol compound, heating them to make them compatible, and then allowing them to cool. Suitable polyhydric phenol compounds include catechol, resorcinol, hydroquinone, pyrocatechin, bisphenol A1, bisphenol F1, bisphenol S, and novolak resin.

In addition to using a 2-imidacilline compound/polyhydric phenol salt alone as a curing agent, the present invention also uses other curing agent components such as aliphatic polyamine, aromatic polyamine, amine salt,
Curing (JCC Progress Options include use as a co-curing agent.

In the invention, when a 1ζ,2-imidacilline compound/multi-1 metasoenol salt is used as a curing agent, the appropriate blending ratio is 2 to 40 pl+r (lI per part of polyepoxy compound 1 (1+1 parts by weight). When using other hardeners as propellants or co-hardeners, the appropriate blending ratio is 0.1 to 20 phr, preferably 0.5 to 10 phr. .

The polyepoxy compound in the present invention contains an average of more than 111 M epoxy groups per molecule, and this group is located at the terminal position of the molecule.

Alternatively, it may be interposed in the middle of a set of molecules, generally called an internal epoxide, to form a ζ-shaped group. The polyepoxy compound may be aliphatic, cycloaliphatic, aromatic, or heterocyclic and may contain non-interfering substituents such as hydroxyl, alkyl, alkoxy, ester, acetal, or ether groups. It may be replaced with .

Is Hisphenol A1 Bisphenol 1 the most desirable polyepoxy compound? , resorcinol, hydroquinone, bisphenol S1 phenol formaldehyde resin, and cresol formaldehyde resin.

Other suitable polyepoxy compounds include (poly)ethylene glycol, (poly)propylene glycol, glycerin, trimethylolpropane, glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, phthalic acid, and tetrahydrophthalic acid. , hexahydrophthalic acid, methyl-endomethylene-tetrahydrophthalic acid, adipic acid, polyglycidyl esters of polycarboxylic acids such as dimer acid, aniline, toluidine, 4,4
- Glycidylamines derived from polyamines such as diaminodiphenylmethane, to vinylcyclo; 1-ceneoxyl, 3,4-epoxycyclohexyl-3,
Epoxidized polyolefins such as 4-coniboxycyclohexanecarboxylate, his(3,4-epoxy-6-methylcyclohexylmenal)-adipate,
Alternatively, it may be epoxidized vegetable oil.

The strength of the present invention is as follows: coloring pigments, extender pigments, i
A reactive diluent such as a JJ plasticizer and a monoepoxy compound such as punar glycidyl ether or phenyl glycidyl ether, or a solvent such as a ketone type, a glycol type, or a YJ^'' group petroleum naphtha is added.

According to the practice of the present invention, 60 to 240°C, preferably 1
Harden in a short time at 00 to 180 degrees Celsius! yru epoxy tree III varnish, paint, adhesive, casting material,
Briple knobs for dry lamination, Comparan 1 for molding, etc. Can be formed without paint. The present invention will be specifically explained with reference to the following examples. In addition, the unit is not specified.
It is displayed by f.

Example 1 (2-Substituted/Imidacillin/Polyhydric) J, Synthesis Example of Nor Salt) A mixture of a 2-substituted imidazoline compound and a polyhydric phenol compound was dissolved by heating, and then allowed to cool to obtain the desired product. The experimental results (blending ratio, compatibility temperature, melting point of the salt produced, curability of the epoxy resin compound system, etc.) are shown below.

・Imidacillin compound Methyl (1-1) Nomnol compound Bis-phenol A blending ratio (Imidacillin 0.5/1 mole/phenolic 011 mole) Compatibility temperature (°C) 125 1-i, point b ('c ) 126 (Composition) One! 2hi I I#821 + 100 I1 Tasoline salt (Town + Ic) 0.241, '1l) i: Lylation time (
sec> 14.8251: IrJ l, tll, ) (ItSl:if) 24No, 2゜Imidacillin compound methyl (R=) Phenol compound Bis-phenol A blending ratio (Imidacillin 1/1 mole/phenolic 011 equivalent) Compatibility temperature (℃) 115 Melting point ('C) 73.5 (Formulation) Epicote 9 828 100 Imidacillin salt (mole) 0.12 150℃ gelation time (seconds) 9.8 25℃ pot life (hours) 48 NO9 Reference example f Adidasulin compound Methyl (1-)Nol Compound - Blending ratio (Imidacillin - mole/) J-Nor 011 equivalent) Phase h'i temperature (
'C) - Melting point ('C) 103 (Formulation) Ebiro 1・#828 100 □ (Mitazoline salt (mola) 0.2415 fl
'C gelation time (seconds) '35.525℃ IJJ usage time (hours) 3 No, 3゜Imidacillin compound Phenyl (R-) Phenol compound Bis-phenol A compounding ratio (Imidacillin 0.5/1 mole/phenolic 011M) Compatibility temperature ('C) 150 Melting point (''C) 133 (Formulation) Epicote 1 828 100 Imidacillin salt (mole) 0.24 150℃ gelation time (minutes) 0.55 25℃ pot life (days) ) 7 No,' 4゜Imidacillin compound Phenyl (R-) Soenol compound Bis-phenol A white ratio (Imidacillin l/1 mole/phenolic 011 equivalent) Compatibility temperature ('C) 137 Minor ξ point (℃ ) 73.5 (Composition) Ebini l l#828 100 ・Imidaprine salt (mole) 0.12150” (:
Compounding time (min) 1.5211' (: rrJ opening time) 14 No. Reference example imidacillin compound Phenyl (R-) Phenol compound - Blending ratio (imidacillin - mole/phenolic 011 equivalent) Compatibility temperature (°C ) - Melting point ("C) 103 (Formulation) Epicote 9 828 100 Imidacillin salt (mole) 0.24 150℃ gelation time (minutes) 4.2 25℃ pot life (days) 2 No. 5゜Imidacillin compound Undecyl (R=) Soenol Compound Bis-phenol A blending ratio (Imidacillin 0.5/1 mole/'phenolic river 1 equivalent) Japanese and Western temperature ('c) 118 111i:li point (°C) Liquid at room temperature (compounding) Shrimp, J l-# 82tl 100 Iζ Dashirin ILf (m(Mountain 0.12I!i()
Shigelization 11. E+ (min) 1.92,',l'7.
'ljl envoy U, stomach ff1(It)' 2(1No,
6゜Imidacillin compound Undecyl (R-) Phenol compound His/phenol A compounding ratio゛ (Imidacillin 1/1 mole/phenolic O1 + equivalent) Compatibility temperature (℃) 100 Melting point (''C) Liquid at room temperature (compounding) Epicoat 9 828 100 Imidaprine salt (mole> 0.06 150°C gelation time (min) 3.4 25°C pot life (days) 12 N (), Reference example fχS'purine compound + 1" undecyl (l?) 1/ l, y, nor compound ~ blending ratio (imidacillin - rI + o I + Tsuno J,)-ru O1 + equivalent) phase l
ii iII 5th degree ('C) - 1 point (℃) 83 (Blend) Koni Vinyl -1# 1328 100 Imidacillin salt (mole) 0.1215 (1'C reeling time (minutes) > 5 25℃ Between i1J and llh (11) 3 Real hi!! 1 row 2 This example shows 2-phenylimidacillin bisso, a,
This is an example in which Nord A salt is blended into an epoxy resin as a hardening agent, and by selecting appropriate fillers, pigments, FlowCon I roll agents, and leveling agents, it can be used to create Bottmelt casting materials (E-pellets, Nitto This is an example of possible applications for epoxy resin, known as Denki Kogyo KK (trade name), powder coatings, etc.

Polyepoxy compound (product name: Epicoat 1004, Yuka Shell K
2-Phenylimidacillin bispheno-J (manufactured by K) was crushed to 150 mesh or less, and the amount listed in the table was added to it, passed through a heated two-roll machine to make a homogeneous system, and after quenching. An epoxy powder lacquer was obtained by pulverizing the powder to a size of 80 mesosi or less. The storage stability, kelpability (curability), and properties of the cured product of this lacquer were measured and the results are shown in Table 1.The physical properties of the coating film were measured using a coating film formed by the fluid dipping method.

(Formulation) Epico-t1004 100 100 2-phenyl imidacillin 68 Hisphenol Δ salt iff 106 1o11 (Properties of the formulation) Appearance, Ll view White powder - Apparent specific gravity 0.42 0.42 Gelation time, sec / 150 ℃ 392 223 Storage stability, IJ / 25 ℃ > 120 > 120 (cured strip 1 cow) 10 minutes / 15 o ℃ (cured product performance) Appearance, 1st view Pale yellow transparent - 11) Brush hardness 311 211 Soeid -・Cool temperature, 'CIO2205
2111 + 1φ-IK with 15 weights (IOVri II Scano 1- Peeling test, Pass Pass 1 (River/1 (10 Kami Rifsen steel ball indentation test, Pass > 10 > 10 Man 1)
bending test, m-φ 〈2<2 bending strength, Kg/mn?
8 9 Flexural modulus, Kg/rn n (305265 permittivity,
6011z 3 3 Breakdown voltage, KV/am > 20 > 20 Volume resistivity, Ω-(Jll > 10 > to” Volume resistivity after boiling, Ω-cm > 10” > 10’” Water absorption, %/
lhr boil O,30,2 (compound) Epicote 1004 100 100 2-phenylimidacillin 10 20 bisphenol A salt meter 110 120 (Properties of the formulation) Appearance, visual observation White powder - Apparent specific gravity 0.42 0 .43 Gelation time, sec/150'' CI53 86 Storage stability, day/25°C >120>g.

(Curing conditions> 20 minutes/15 (Pc (cured physical properties 11) Appearance, LJ view Light yellow and transparent - - 1 pencil II history 211 311 '/- (＼ - Cut through? j A degree, ℃ 176
1722 Dragon φ -IKa weight 1 liter / 500V ri 11 kanol ・Peeling test, passed Pass H1t+ /
100, :I-'J'/L-nire ball indentation test, +i
n > 10 >10-1' IL-Le bending test, fin φ 〈
2〈3 bend'+4jisa, KB/m, nζ 77 bends) bullet 111 i;, KB/m n? 21J7 3
2011,';tun・IX,('+ tl I+, (3
4ra k, j, 11 & Itj Dengetsu, kV/'I
Im>2(1>l111)1. b'f 115;
I efficiency, 12 (m >10'> 10 parts g,
1. :,;Jl: fp body, r! 'f 1Isi anti-4
-X, Ω cm '>10'>IQ"1!1 water ↑-・,%/111I+Joil O,20,4 Buddha 19
, Ho 1. Stability (lacquer at 25°C!)
1 generation 2, measure the change in the flow 1 characteristic and change the flow to the initial 1
/2 (the end point was taken as the end point; 1 g of the sample was placed in a tablet molding die with a diameter of 10, the tablets obtained by pressurizing to 1 ton were adjusted in advance to 150 ± 0.5 ° C. After the tablets have hardened, the average diameter is measured and expressed as flow rate %.

Flow rate % = (Average diameter after curing 1)
Spread the sample to a size of 30 m rrr, knead it by pushing the sample evenly at a speed of one reciprocation every 2 seconds, and lift the spatula from time to time until no thread is pulled between the sample and the spatula. This is what was measured.

Example 3 This example shows 2-methylimidacyline bisphenol F (1
/1 molar ratio) salt is used to accelerate curing of dicyandiamide.

Polyepoxy Compound A (Product Name: "-Piquat 828
, manufactured by Yuka Shell KK) 70 parts, polyepoxy compound 1;
(Product name: Shrimp m1-1, 834, same) 30 parts, thixotropy l: iJ 'i punishment (Product name: Benton 3) 3, national ret; 1-IJ) 2Bli, Body' (pigment (product name) 30 parts of dicyandiamide (manufactured by Nippon Calm f1), 2 parts of the above imidacillin salt were uniformly kneaded using three 11-mill machines to form an adhesive composition. f'71:L. The adhesive had a shelf life of more than 2 degrees Celsius at room temperature, cured rapidly when heated at 120 degrees Celsius or more, and exhibited strong adhesive strength.

Storage stability, Ll/25° (: >9Q reel ■
), min/120'C(i, 4m1n/1
50°C 1.8 m1n/18 (1°C 0.7 13 months adhesive strength, B/m rl (curing conditions 0
．． 5hr/150℃) Steel Steel 720℃ 240 81 - 81 720℃ 105 1 piece, [! “Metric resistance, i2 cm/2 (1℃
>10% 1. Voltage at break 1, KV/IIm > 20
Example 4 In this example, 2-ethyl-4-methylimidapurine bisphenol A salt (2 parts 1 molar ratio) was used as the sole curing agent and as the acid anhydride curing accelerator). be.

1? obtained by sufficiently melting and kneading the ingredients listed in the table in a two-roll machine preheated to 85-95°C. , 1 mixture was rapidly cooled, pulverized, and classified to obtain a powder coating for fluidized dipping in a range of 80 to 270 mesoyu. The coating material is useful for coating ceramic parts such as film resistors, varistors, capacitors, and HYBRINOL C.

(Composition) Epicote 1004 (Note 1) 100 100Sl
l-6018 (Note 2) 0.5 0.52-ethyl-4
-Methylimidacillin 61 bisphenol A salt (2
part 1 mole 6) L-limerisotonic anhydride 08 Silica powder (Note 3) 50 80 Iron oxide (Note 4) 22 Total 158.5 191.5 (Characteristics) Curing conditions: lhr / 150°C Appearance, visual observation Red-colored powder - Gelation time, min/150°C 3. (13.5 Specific gravity 1.5 1.8 Heat distortion temperature, 'c 98 115 Corner coverage ratio, % 4245

Claims (1)

[Claims] When curing a polyepoxy compound having on average more than 1 epoxy groups in its molecule, 2-substituted imidazoline compounds are used as curing agents or curing accelerators.
An epoxy curing method characterized by the use of phenol salts.