JPH0362823A - Resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition good in workability, capable of giving coating films with excellent mechanical properties, electrical properties, raw material adhesivity and flexibility, thus useful for coatings, electrical insulating materials, adhesives and casting materials, made up of an epoxy group-contg. compound and a cyclocarbonate group-contg. compound. CONSTITUTION:The objective composition made up of (A) a compound having two or more epoxy groups {pref. a compound of formula I [R1 is alkylene, i.e., CH2, CH(CH3) or C(CH3)2; n1 is 1-13], its epoxy equivalent being 100-5000g/eq} and (B) a compound having two or more cyclocarbonate groups [pref. a compound of formula II (A is 2-10C alkyl-carrying alkyl ether linkage, 1-10C alkylene, etc.; X1-X6 are each H, Cl, Br, methyl, ethyl or propyl; n2 is 15), its carbonate equivalent being >=5000g/eq].

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful resin composition. More specifically, the present invention includes an epoxy group-containing compound and a cyclocarbonate group-containing compound, or an epoxy group-containing compound, a cyclocarbonate group-containing compound, and a specific amino group-containing compound as essential components. It combines the characteristics of epoxy resin, which has excellent mechanical properties, electrical properties, and material adhesion, and urethane resin, which has excellent flexibility.
The present invention relates to resin compositions useful as insulating materials, adhesives, casting materials, etc.

[Conventional technology]

Generally, epoxy resins have excellent mechanical properties, electrical properties, and material adhesion, but the resin structure is rigid and has a problem with flexibility.

On the other hand, although urethane resins have excellent flexibility, they have problems in mechanical properties, corrosion resistance, solvent resistance, etc.

Various resins that have the characteristics of both of these resins have been studied. For example, cured products made by curing epoxy resins with a urethane structure with Adan compounds, amino resins, or phenolic resins are being studied. Or, or
There are cured products that are cured through a reaction between hydroxyl groups in an epoxy resin and an isocyanate compound.

By the way, in the former case, if a urethane bond is included in the resin structure, the viscosity of the resin will increase significantly, and the workability will be significantly deteriorated.

In contrast, in the latter case, the top two
There are several methods, one of which is a system in which an isocyanate compound is mixed with an epoxy resin and cured at room temperature, but because the reactivity of isocyanate is extremely high, the temperature is high It is extremely difficult to control the curing speed in the summer, and there is also the disadvantage that phenomena such as foaming occur due to the incorporation of small amounts of water.Another method is to heat the epoxy resin using a blocked isocyanate compound. Although this is a curing system, it requires a very high curing temperature and has the disadvantage that the dissociated blocking agent causes new undesirable problems.

As described above, the conventional method of simultaneously introducing an epoxy resin structure and a urethane resin structure into the same cured product has various problems.

[Problem to be solved by the invention]

Therefore, based on the recognition of the current situation, a fundamental solution to various unresolved problems in the prior art, and the earnest needs of the industry, the present inventors have developed a curable resin composition of this kind. In order to put this into practical use in the true sense of the word, we began earnest research.

Therefore, the problem to be solved by the present invention is to solve the following problems: The purpose is to obtain a cured resin product of
In addition, in obtaining such a useful cured resin product,
Resin curing with easy workability and excellent properties without significantly increasing the viscosity of the resin compound, without being significantly affected by environmental temperature or humidity, and without using high heating temperatures. It is to provide a system for obtaining things.

(Means for Solving the Problems) Therefore, the present inventors have conducted extensive studies in order to obtain the desired resin composition by adjusting standards to the above-mentioned problems to be solved by the present invention. Furthermore, an epoxy group-containing compound and a cyclocarbonate group-containing compound,
By also using a specific amino group-containing compound, an extremely useful curable resin composition was discovered, and the present invention was completed.

That is, the present invention comprises, as essential components, a compound (A) having two or more epoxy groups in the molecule and a compound (B) having two or more cyclocarbonate groups in the molecule. Alternatively, a compound (A) having two or more epoxy groups in the molecule, a compound (B) having two or more cyclocarbonate groups in the molecule, and one or more primary compounds in the molecule. In particular, it does not significantly increase the viscosity of the resin compound, is not significantly affected by environmental temperature or humidity, and can be heated at high temperatures. The object of the present invention is to provide a resin composition that is easy to work with, does not require any use, and provides an extremely useful cured resin product that has both the characteristics of an epoxy resin and a urethane resin.

Here, we will only exemplify particularly representative compounds (A) having two or more epoxy groups in the molecule.
850 JC Dainippon Ink & Chemicals Co., Ltd. product; epoxy equivalent - 1,88g/eq) or "Epiclon 1
050J (same company product; epoxy equivalent = 475 g/
Bisphenol A-epichlorohydrin condensation type epoxy resin such as ``Epiclon 830j (product of the same company: Epoxy equivalent: -172 g/eq)''; Bisphenol F-epichlorohydrin condensation type epoxy resin such as ``Epiclon N-740'' (product of the same company) Crystallization; epoxy equivalent -180g/eq) or "Epicron N
-670j (same product; epoxy equivalent = 210
Novolac resin-epichlorohydrin condensation type epoxy resin such as "Epiclon 152J (product of the same company; epoxy equivalent -300g/eq)"; Tetrabromobisphenol A-epichlorohydrin condensation type epoxy resin such as "Epiclon 152J (product of the same company; epoxy equivalent - 300g/eq); or "Epiclon 430J ( Various aromatic glycidyl ether type epoxy resins such as glycidyl amine type epoxy resins, such as epoxy equivalent (epoxy equivalent: -120 g/eq), and various alicyclic epoxy resins having structures represented by general formulas, etc. , furthermore, phthalic acid diglycidyl ester or p
-Various glycidyl ester type epoxy compounds such as oxybenzoic acid diglycidyl ether ester, or hydantoin type epoxy resins, among others, bisphenol-epichlorohydrin condensation type epoxy resins, bisphenol F-epichlorohydrin condensation type epoxy resins, etc. It is desirable to use one or a mixture thereof, or a co-condensate of both.

The epoxy equivalent of the compound (A) is 100 g
/eq to 5,000 g/eq, preferably 120 g/eq to 3,000 g/eq.

On the other hand, only typical examples of the compound (B) having two or more cyclocarbonate groups in the molecule include those having the structure represented by the general formula. Compound (B) can be obtained by, for example, converting an oxirane compound to carbonate-1 with carbon dioxide [Journal of the Society of Organic Synthesis Chemistry, Vol. 34, No. 5 (1976)]
, carbonation by reaction of a chlorohydrin compound with sodium hydrogen carbonate (West German Patent Application Publication No. 3,
723.782) or carbonation by carbonate exchange between a polyhydroxy compound and an alkyl carbonate (Japanese Unexamined Patent Publication No. 118/1983).

The carbonate equivalent of the compound (B) is 5.00
0 g/eq or less, preferably 3,000 g/eq or less is appropriate. If it exceeds 5,000 g/eq, the amount of urethane bonds introduced will be insufficient, which is not preferable.

In addition, as the compound (B), a polycyclocarbonate higher than dicyclocarbonate is used, and when a monocyclocarbonate such as ethylene carbonate or propylene carbonate is used, the heat resistance and water resistance of the cured product will be insufficient. So I don't like it.

Furthermore, the weight mixing ratio of the compound (A) and the compound (B) is as follows:
Ratio: (A)/(B) -50150~98/
It is appropriate to fall within the range of 2.

When the amount of compound (A) is less than 50% by weight, the properties of this epoxy group-containing compound (A) tend to be insufficiently expressed, whereas when it exceeds 98% by weight, the properties of the compound (B) ) are likely to fail to be fully expressed, so either case is unfavorable.

If we only exemplify particularly typical compounds (C) having one or more primary amino groups in the molecule described above, only one or more primary amino groups can be used as amino groups. a compound (C-2) having one or more primary amino groups and two or more secondary amino groups as an acino group, or a polyester having an alkylene group of 04 or more. Any one of alkylene polyamines (C-3) or a mixture thereof.

Among them, first of all, the above-mentioned compound (C-1), to mention only the most representative ones, are propylatan,
Agono compounds such as butyl diamine, ethylene diamine, propylene diamine, hexamethylene diamine, xylene diamine, isophorone diamine, or menthene diamine, which are particularly representative as the compound (C-2). To name just a few, adduct-type modified acids obtained through the reaction of a compound having two or more primary amino groups with an epoxy group; an amide type modified amine obtained; or a Michael addition type modified amine obtained through the reaction of a compound having two or more primary amino groups with a double bond, and further, the compound (C-3) Typical examples include diethylene triamine, triethylenetetramine, tetraethylenepentane, and dipropylenetriamine.

In the present invention, the usage amount of the compound (C) is as follows:
The number of equivalents of epoxy groups in the formulation (EA) and twice the number of equivalents of carbonate groups in the formulation (EB), i.e.
Ratio of the total number of active hydrogens (H7) possessed by the 7-mino groups in the compound (C) to the sum of 2Ea: (H,,/
(EA+2El+)] is preferably within the range of 0.4 to 1.5.

The conditions for curing the thus obtained resin composition of the present invention are such that the curing temperature is within the range of room temperature to 180°C, and the curing time is within the range of 30 minutes to 10 days.

If the curing temperature is set high, the curing time will be shortened, and conversely, if the curing temperature is set low, the curing time will be lengthened.

The resin composition of the present invention may further contain a monocyclocarbonate compound, various reactive and/or non-reactive diluents, organic solvents, pigments, fillers, or additives, as necessary. The purpose of the present invention is not impaired by using such various ingredients.

〔Effect of the invention〕

The resin composition of the present invention has the excellent mechanical properties, electrical properties, and material adhesion of epoxy resins, without significantly increasing the viscosity of the resin compound, without using high heating temperatures, and with easy workability. It can provide a cured product that has the excellent flexibility of urethane resins, and is useful for paints, insulating materials, adhesives, casting materials, etc.

〔Example〕

Next, the present invention will be explained by reference examples, examples, and comparative examples.
The layer will be explained in detail.

Reference Example 1 [Preparation example of cyclocarbonate group-containing compound (B)] In a glass reaction vessel equipped with a stirrer and a thermometer, 100 phr of diglycidyl [i.e., bis(2,3-dihydroxypropyl) ether] and diethyl carbonate were added. Q of 87 phr and Tetraisop Obiru Titanate
, 2 phr was charged, and the reaction was continued by holding at 125°C for 3 hours while distilling out the ethyl alcohol produced.Then, the temperature was further raised to 180°C, and at the same temperature, ethyl alcohol was added under reduced pressure. was removed.

Next, the mixture was cooled and filtered to obtain the target compound.

This product was analyzed by c,3NMR to determine the carbonate equivalent, which was 135 g/eq. Also, as a result of GPC analysis, the purity of dicyclocarbonate in this product was 90%. There was found.

Reference Example 2 (same as above) In a reaction vessel similar to Reference Example 1, 100 phr of dimethyl sulfoxide, 100 phr of diglycidyl ether of dipropylene glycol, and 500 phr of sodium hydrogen carbonate were added.
0 phr was charged and the reaction was continued by holding at 120°C for 0 hours. Then, dimethyl sulfoxide was distilled off under reduced pressure and then subjected to PA to obtain the target compound.

When this product was subjected to C+3 NMR analysis and GPC analysis, 270 g/eq of 1-equivalent carbonate and 95% dicyclocarbonate purity were confirmed.

Example 1 "Epiclon 85" as an epoxy group-containing compound (A)
0'' and 10 phr of the dicyclocarbonate obtained in Reference Example 1 as the cyclocarbonate group-containing compound (B) were thoroughly mixed. The Brookfield viscosity of this mixture at 25°C is 11,2
It was 00cps.

This mixture was then treated with 15% of triethylenetetramine.
4 phr was added and mixed thoroughly.

Thereafter, 80 g of the base agent/curing agent mixture thus obtained was added to 100 mjl! The linear curing rate was measured by placing a sample in a glass sample bottle, inserting a thermometer, and drawing a curing exothermic curve at 25°C. The results are shown in Table 1.

Separately, the same base agent/curing agent mixture was defoamed and poured into a glass mold, and left to stand at room temperature for 7 days to cure, thereby obtaining a casting plate of 30 cynX 3 QcmX 3sm.

Cut out a test piece from this casting plate and use it as JIS X69.
11, the heat distortion temperature, bending strength, bending modulus, tensile strength, tensile modulus, tensile elongation, and boiling water absorption were measured. The results are also shown in the same table.

Example 2 The same amount of "Epiclone 830" was used instead of "Epiclone 850", and the same amount of dicyclocarbonate obtained in Reference Example 2 was used instead of the dicyclocarbonate obtained in Reference Example 1. Changed to use dicyclocarbonate, and increased the amount of triethylenetetrachloride to 13.0 ph
A curable resin composition was prepared in the same manner as in Example 1, except that r was changed, and then, on the one hand, the linear curing speed was measured, and on the other hand, various physical properties of the cured product were also measured.

The results are shown in Table 1.

Example 3 A curable resin composition was prepared in the same manner as in Example except that 16.1 phr of hexamethylene diamine was used instead of triethylenetetramine.
Next, on the one hand, the linear curing rate was measured, and on the other hand, various physical properties of the cured product were measured. The results are shown in Table 1.

Comparative Example 1 No cyclocarbonate group-containing compound (B) was used, and the amount of triethylenetetramine used was 13.
A control curable resin composition was prepared in the same manner as in Example 1, except that the composition was 0 phr, and then, on the one hand, the linear curing rate was measured, and on the other hand, the physical properties of the cured product were measured.

The results are shown in Table 1.

Comparative Example 2 The same amount of monocyclocarbonate propylene carbonate was used instead of dicyclocarbonate, and the amount of triethylenetetramine was changed to 16
．． A control curable resin composition was prepared in the same manner as in Example 1, except that the curing rate was 6 phr, and then, on the one hand, the linear curing rate was measured, and on the other hand, the physical properties of the cured product were measured. The results are shown in Table 1.

/ / / / As is clear from Table 1, the resin composition of the present invention has the following properties:
You will find that it is extremely superior.

teenager Reason Man

Claims (1)

[Claims] 1. Compounds having two or more epoxy groups in the molecule (A
) and a compound (B) having two or more cyclocarbonate groups in the molecule. 2. Compounds having two or more epoxy groups in the molecule (A
), a compound (B) having two or more cyclocarbonate groups in the molecule, and a compound (C) having one or more primary amino groups in the molecule. 3. Claim 1 or 2, wherein the compound (A) having two or more epoxy groups in the molecule has an epoxy equivalent in the range of 100 to 5,000 g/eq.
The resin composition described in . 4. The compound (A) having two or more epoxy groups in the molecule described above has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼... [I] [However, R_1 in the formula is -CH_2-, - CH(CH_
3) - or -C(CH_3)_2-, and n1 is 0 or an integer from 1 to 13. ] The resin composition according to claim 1 or 2, which is a compound having the structure shown below. 5. Claim 1 or 2, wherein the compound (B) having two or more cyclocarbonate groups in the molecule has a carbonate equivalent of 5,000 g/eq or less.
The resin composition described in . 6. The compound (B) having two or more cyclocarbonate groups in the molecule described above has the general formula ▲ mathematical formula, chemical formula, table, etc. ▼... [II] [However, A in the formula is C_2 to C_1_0 Alkyl ether bond with alkyl, alkylene group or alkenylene group C_1 to C_1_0, or general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [However, B_1 and B_2 in the formula may be the same or different. General formulas ▲ Numerical formulas, chemical formulas, tables, etc.▼ (However, Y in the formula shall represent a hydrogen atom or a methyl group, and i shall be 0 or an integer from 1 to 8.) ), and D represents a divalent linking group represented by -
CH_2-, -CH(CH_3)- or -C(CH_
3) _2- represents an alkylene group. ], X_1 to X_6 each represent a hydrogen atom, chlorine atom, or bromine atom, or a methyl group, ethyl group, or propyl group, and n2 is 1 to Assume that it is an integer of 5. ] The resin composition according to claim 1 or 2, which is a compound having the structure shown below. 7. The compound (C) having one or more primary amino groups in the molecule described above is a compound (C-1) having only one or more primary amino groups, and one or more primary amino groups. At least one compound selected from the group consisting of a compound (C-2) having two or more secondary amino groups, and a polyalkylene polyamine (C-3) having an alkylene group of C_4 or more, The resin composition according to claim 2. 8. Weight blending ratio (A) of the above compound (A) having two or more epoxy groups in the molecule and the above compound (B) having two or more cyclocarbonate groups in the molecule
The resin composition according to claim 1 or 2, wherein /(B) falls within the range of 50/50 to 98/2. 9. The compound (C) having one or more primary amino groups in the molecule described above has the equivalent number of epoxy groups in the compound (A) having two or more epoxy groups in the molecule (E_
The amino group in the compound (C) relative to the sum of A) and twice the number of equivalents (E_B) of carbonate groups in the compound (B) having two or more cyclocarbonate groups in the molecule described above. The ratio of the total number of active hydrogens (H_n) [H_
The resin composition according to claim 2, wherein n/(E_A+2E_B)] is within a range of 0.4 to 1.5.