JPS6049644B2 - Curable unsaturated epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to curable unsaturated epoxy resin compositions.

Specifically, the present invention relates to a curable unsaturated epoxy resin composition in which an epoxy compound is esterified using an organic acid.

More specifically, the present invention relates to a cured unsaturated epoxy resin composition obtained by esterifying a urethane-modified epoxy compound obtained using a urethane prepolymer containing terminal isocyanate groups with an organic acid.

Epoxy resins widely used today require the use of acidic or basic curing agents for curing.

In this case, great care must be taken in selecting the curing agent and determining the amount used, otherwise the performance of the cured product will inevitably deteriorate. Further, the adjustment of the curing time is limited by the selection and amount of the curing agent mentioned above. Furthermore, the use of certain curing agents may be limited by their own toxicity. On the other hand, unsaturated polyester resin has excellent properties in terms of curability.

Unsaturated polyesterfur resins can be cured using a small amount of organic peroxide under a wide range of conditions. Therefore, engineered poxy resins that have the curing performance of unsaturated polyester resins by introducing polymerizable unsaturated bonds have superior properties compared to conventional resins, and a wider range of applications will be developed. However, currently known unsaturated epoxy resins lack adhesion and flexibility when used as coating materials or adhesives, and have poor resistance to punching when used as laminated resins or molding materials. It has a fatal drawback of lacking impact resistance. An object of the present invention is to provide a curable unsaturated epoxy resin composition which improves the above-mentioned disadvantages and has excellent adhesion, flexibility, corrosion resistance and impact resistance.

The curable unsaturated epoxy resin composition of the present invention contains (1) an epoxy compound (1-1 -1) and a urethane-modified epoxy compound (1-1) obtained by reacting a polyether polyol or a polyester polyol with a terminal isocyanate group-containing urethane prepolymer (1-1-2) obtained from an organic polyisocyanate; Polymerizable unsaturated monobasic acid, or polymerizable unsaturated monobasic acid and saturated monobasic acid, saturated polybasic acid, anhydrous saturated polybasic acid, polymerizable unsaturated polybasic acid, polymerizable anhydrous unsaturated polybasic acid Containing an esterified product obtained by reacting an organic acid (1-2) containing one or more organic acids selected from the above, and (■) a polymerizable monomer. There is a composition characterized by:
The epoxy compound (1-1-1) having an average of more than one adjacent epoxy group and an average of 0.1 or more hydroxyl groups in the molecule used in the present invention has an epoxy equivalent of 180 to 50.
Preferably, it is liquid at 0.

This! Preferred liquid epoxy compounds include epoxy resins containing aromatic nuclei, particularly epoxy resins obtained by reacting epihalohydrin with polyhydric phenol alkylene oxide adducts obtained by adding alkylene oxide to polyhydric phenols. 3. In addition, in the terminal isocyanate group-containing urethane prepolymer (1-1-2) obtained from the above-mentioned polyether polyol or polyester polyol and organic polyisocyanate, the polyether 4-ter polyol may contain alkylene in a compound having two or more active hydrogens. It refers to a compound obtained by adding an oxide (e.g. ethylene oxide, propylene oxide) by a conventional method, and active hydrogen-containing compounds include, for example, dihydric alcohol (e.g. ethylene glycol, propylene glycol, 1●5-pentanediol), Trihydric alcohols (e.g. glycerin, trimethylolpropane, hexanetriol), other polyhydric alcohols (e.g. pentaerythritol, xylitol,
Sorbitol), alicyclic polyhydric alcohols (e.g. inositol, 2●2-bis(4-hydroxyhexyl)propane), aromatic polyhydric alcohols (e.g. tronomethylolbenzene), polyhydric phenols (e.g. phenol) (formalin initial condensate), etc.

These polyether polyols have a molecular weight of 1000~
5000 is preferably used.

Examples of polyester polyols include polyester polyols obtained by reacting the aforementioned dihydric alcohols, trihydric alcohols, alicyclic polyhydric alcohols, aromatic polyhydric alcohols, and polyhydric phenols with polyhydric carboxylic acids in a conventional manner. It will be done. Examples of polycarboxylic acids include benzenetricarboxylic acid, adipic acid, succinic acid, suberic acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, Any suitable rubonic acid such as thiodipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, or the like can be used. These polyester polyols have a molecular weight of 1000
It is preferable to use one with a value of 5000 to 5000.

In addition, as the organic polyisocyanate in this), the general formula (
In this), O is a benzene ring or naphthalene ring, -NCO is a nuclear-substituted isocyanate group, Z is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, and n is 0.
11 or 2) (e.g. 2.
4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 1,4-naphthylene diisocyanate, 1◆5-naphthylene diisocyanate, 1◆3-phrenylene diisocyanate, 1,4-phenylene diisocyanate, l-isopropylbenzole, 2,4-diisocyanate) In the general formula (this), ○ is a benzene ring or a naphthalene ring, -(CH2
). ．． NCO is a nuclear substituted alkylene isocyanate group,
Z is a nuclear-substituted halogen atom or an alkyl or alkoxyl group having 3 or less carbon atoms, m is 1 or 2, n is 1 or 2) diisocyanate (e.g. ω●ω''-diisocyanate 1●2- Dimethylpenzole, ω●ω5-diisocyanate 1◆3-dimethylpenzole) In the general formula, A is an alkylene group having 3 or less carbon atoms such as -CH2-, CH39-℃H3, and O is a benzene ring or naphthalene. ring, Z is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, n is 0, 1 or 2) diisocyanate (e.g. 4.4"-diphenylmethane diisocyanate, 2◆2"- Dimethylphenylmethane-44"-diisocyanate, diphenyldimethylmethane-4.4"-diisocyanate, 3.3"-dichlorodiphenyldimethylmethane-4.4"-diisocyanate), general formula (where Z is the nucleus) Substituted halogen atom or alkyl or alkoxy group having 3 or less carbon atoms, m is O or 1, n is O, 1 or 2) diisocyanate (e.g. biphenylene-2●4-diisocyanate, bipheny-4● 4″-diisocyanate, 3・3″-methylbiphenyl 4●4″-diisocyanate, 3●3
``-dimethoxybiphenyl-4,4''-diisocyanate), diphenylsulfone-4,4''-diisocyanate, and diisocyanates such as those obtained by hydrogenating the aromatic ring contained in the above isocyanate (e.g. dicyclohexane-4,4''-diisocyanate). diisocyanate, ω●ω5-diisocyanate 1●2-dimethylbenzene, ω●ω''-diisocyanate 1,3-dimethylbenzene), a substituted urea group obtained by the reaction of 2 mol of diisocyanate and 1 mol of water. diisocyanate containing (e.g. urea diisocyanate obtained by the reaction of 1 mol of water and 2 mol of 2●4-toluylene diisocyanate), uretdione diisocyanate obtained by bimolecular polymerization of aromatic diisocyanate by a known method; Propane-1,2-diisocyanate, 2●3-dimethylbutane-2●3-diisocyanate, 2-methylpentane-2●4-diisocyanate, Octane-3,6-diisocyanate, 3,3-dinitropentane-1 - Examples include 5-diisocyanate, octane-1,6-diisocyanate, hexamethylene diisocyanate, etc.

The above-mentioned terminal isocyanate group-containing urethane prepolymer (1-1-2) can be obtained by combining such polyether polyol, polyester polyol, or a mixture thereof and an organic polyisocyanate using the usual method for producing an NCO-containing urethane prepolymer. It is obtained by reacting in the same manner so that the NCO group content is 1 to 10%.

Furthermore, this terminal isocyanate group-containing urethane prepolymer (1-1-2) is converted into an epoxy compound (1-1-1 ) and the 0H/NCO ratio is greater than 1 in a conventional manner, e.g.
The urethane-modified epoxy compound (1-1) can be obtained by reacting at a temperature of about 100'C for about 5 hours. Note that the above urethane-modified epoxy compound (
In the production of 1-1), after the reaction, an alcohol such as n-butanol may be reacted for the purpose of blocking unreacted isocyanate groups.

The urethane-modified epoxy compound (1-
1) is a single polymerizable unsaturated monobasic acid, or a polymerizable unsaturated monobasic acid and a saturated monobasic acid, a saturated polybasic acid, an anhydrous saturated polybasic acid, a polymerizable unsaturated polybasic acid, a polymerizable anhydrous The esterification reaction is carried out with organic acids (1-2) containing one or more organic acids selected from saturated polybasic acids, and 0.00% carboxyl group per equivalent of epoxy group. The reaction is carried out in a range of 2 to 1.2 equivalents, preferably 0.5 to 1.0 equivalents. The above esterification reaction is carried out at a reaction temperature of 80 to 150°C, preferably 80 to 120°C.
The range is appropriate.

A catalyst is not necessarily required, but organic amines and their salts, mercaptans, phenols, metal stones such as tin octylate, soaps, Lewis acid catalysts such as boron trifluoride, etc. can be used. good. Examples of polymerizable unsaturated monobasic acids used in the present invention include acrylic acid, methacrylic acid, and crotonic acid, and examples of polymerizable unsaturated polybasic acids and their acid anhydrides include maleic acid, maleic anhydride, and fumaric acid. , itaconic acid, etc.

The saturated monobasic acids, saturated polybasic acids, and their acid anhydrides used in the present invention include benzoic acid, stearic acid, phthalic acid, isophthalic acid, phthalic anhydride, adipic acid, and the like. These acids are polymerizable unsaturated monobasic acids or unsaturated polybasic acids and their acid anhydrides 0.5 to 1.0
It can be used in a ratio of 0 to 0.5 equivalents of the saturated monobasic acid or saturated polybasic acid and its anhydride.

Next, as the polymerizable monomer (■), vinyl, acrylic, or allyl polymerizable monomers can be used, such as vinyl compounds such as styrene and vinyltoluene, methyl acrylate, and methacrylic acid. Methyl, ethyl acrylate, methacrylate. Hydroquinone, naphthoquinone, benzoquinone, etc. It can be added in the presence of a known radical polymerization inhibitor such as -t-butylcatechol.

In the present invention, various additives such as flame retardants can be added as necessary.

The effect of the present invention lies in providing a curable unsaturated epoxy resin composition having excellent adhesiveness and impact resistance.

The composition of the present invention can be used in a wide range of applications such as coating materials, laminating resins, adhesives, and molding materials. Examples of the present invention are shown below, and all parts in the middle of the examples are parts by weight.

Example 1 A portion marked with polypropylene glycol (average molecular weight 2000) and 21 parts of toluylene diisocyanate were heated and stirred at 85)C for 3 hours to obtain 81 parts of a polyurethane prepolymer.

81 parts of this polyurethane prepolymer was added to 2●2 bis(
Diglycidyl ether of 4-hydroxyphenyl)pronopane (epoxy equivalent: 1901, hydroxyl value: 14) 5 (4)
After heating and stirring at 150-160'C for 3 hours, 5 parts of triethylene glycol was added, and the reaction was continued for an additional hour. The obtained urethane-modified epoxy resin was liquid and had an epoxy equivalent of 230. This resin 58
1 part contains 217 parts of methacrylic acid and 2 parts of triethanolamine.
When a reaction was carried out at 120° C. for 8 hours under a nitrogen stream, the acid value decreased to 5.0. To this was added 02 parts of hydroquinone, and the mixture was diluted with 3 (4) parts of styrene. 2% by weight of methyl ethyl ketone peroxide and 1% by weight of cobalt naphthenate were added to the obtained resin to prepare a casting plate, and its physical properties were measured after one week at room temperature. It is shown in Table 1. Example 2 1●Polyester polyol obtained by dehydration condensation reaction of 5-pentanediol and adipic acid (molecular weight 28
00) (branch) part and toluylene diisocyanate w part 8
The mixture was heated and stirred at 5° C. for 4 hours to obtain a polyurethane prepolymer stamp containing terminal isocyanate.

This polyurethane prepolymer 6C8 was added to 1 (4) parts of diglycidyl ether (epoxy equivalent: 3401, hydroxyl value: 51) of 2,2-bis-(4-hydroxylphenyl)propane propylene oxide adduct;
After heating and stirring at 300C for 3 hours, 2 parts of triethylene glycol was added, and the reaction was continued for an additional 1 hour. The obtained urethane-modified epoxy resin is liquid and has an epoxy equivalent of 48.
It was 0. 174 parts of methacrylic acid, 25 parts of maleic anhydride, and 3 parts of dimethylbenzylamine were mixed with 581 parts of this resin, and a reaction was carried out at 120°C for 7 hours under a nitrogen stream, and the acid value decreased to 5.0. . 02 parts of hydroquinone was added to this, and the mixture was diluted with styrene 35(2).
The obtained resin was treated in the same manner as in Example 1, and then its physical properties were measured. It is shown in Table 1. Example 3 A urethane-modified epoxy resin was prepared in the same manner as in Example 2, and this 21z? 33 parts of methacrylic acid and 0.5 parts of triethanolamine were added to the mixture, and the mixture was heated at 120°C under a nitrogen stream at 9°C.
When the reaction was carried out for several hours, the acid value decreased to 5.0.

0.06 part of hydroquinone was added to this, and the mixture was diluted with 1 part of styrene. The obtained resin was treated in the same manner as in Example 1, and then its physical properties were measured. It is shown in Table 2. Example 4 A urethane-modified epoxy resin was prepared in the same manner as in Example 2, and this 21? Methacrylic acid 3 Maleic anhydride 5
When the reaction was carried out at 120'C for 8 hours under a nitrogen stream, the acid value was 5.
．． It dropped to 0.

Add 0.06 parts of hydroquinone to this, and add 1 m of styrene.
diluted in parts. The obtained resin was treated in the same manner as in Example 1, and then its physical properties were measured. It is shown in Table 2. Comparative Example 1 For comparison, bisphenol A with an epoxy equivalent of 190
To 400 parts of diglycidyl ether, 18 parts of methacrylic acid
When 1 part of V1 dimethylbenzylamine was blended and a 120'Cl reaction was carried out for 6 hours under a nitrogen stream, the acid value decreased to 5.0.

Add 0.15 parts of hydroquinone to this, and add 23 parts of styrene.
Comparative Example 1 was obtained by diluting the solution with 0 parts and then carrying out the same treatment as in Example 1. Its physical properties are shown in Table 3. Comparative Example 2 For comparison, bisphenol A with an epoxy equivalent of 450
To 450 parts of diglycidyl ether, 86 parts of methacrylic acid
1 part of dimethylbenzylamine was mixed and the reaction was carried out at 120°C for 6 hours under a nitrogen stream, and the acid value was 5.
It dropped to 0.

Claims (1)

[Claims] 1. An epoxy compound (I) having an average of more than 1 adjacent epoxy group and an average of 0.1 or more hydroxyl groups in the molecule as an essential component (I)
-1-1) and a polyether polyol or a polyester polyol and an organic polyisocyanate (I
-1-2) and a single polymerizable unsaturated basic acid, or a polymerizable unsaturated basic acid and a saturated basic acid, or a saturated polybasic acid. organic acids (I-2) containing one or more organic acids selected from acids, anhydrous saturated polybasic acids, polymerizable unsaturated polybasic acids, and polymerizable anhydrous unsaturated polybasic acids; A curable unsaturated epoxy resin composition comprising an esterified product obtained by reaction and (II) a polymerizable monomer.