JPS6140311A - Curable unsaturated epoxy resin composition - Google Patents

Abstract

PURPOSE:The titled composition having improved adhesivity, flex properties, corrosion resistance, and impact resistance, containing an esterified substance obtained by esterifying a urethane modified epoxy compound which is obtained by the use of a terminal NCO group-containing urethane prepolymer with an organic acid. CONSTITUTION:Firstly, (A) a urethane modified epoxy compound obtained by reacting (i) an epoxy compound containing a neighboring epoxy group and >=0.1 hydroxyl group with (ii) a terminal NCO group-containing urethane prepolymer consisting of both polyether polyol and an organic polyisocyanate is reacted with (B) an organic acid consisting of a polymerizable unsaturated monobasic acid alone or a mixture of it and a saturated monobasic acid, a saturated polybasic acid(anhydride) or a polymerizable unsaturated polybasic acid(anhydride), and (C) a glycidyl ether type epoxy group-containing epoxy compound. Then, the prepared ester compound is blended with a polymerizable monomer, to give the aimed composition.

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 curable unsaturated epoxy resin composition in which a urethane-modified epoxy compound obtained using a urethane prepolymer containing a terminal isocyanate-1 group is esterified 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. Furthermore, the control 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 polyester resins can be cured using a small amount of organic peroxide under a wide range of conditions. Therefore, epoxy resins that have the curing performance of unsaturated polyester resins by introducing polymerizable unsaturated bonds have superior properties compared to conventional resins, and are being developed for a wider range of uses. , such currently known unsaturated epoxy resins can be used as coating materials,
When used as an adhesive, it lacks adhesion and flexibility,
Furthermore, when used as a laminating resin or a molding material, it has a fatal drawback of insufficient impact resistance.

An object of the present invention is to provide a curable unsaturated epoxy resin composition that overcomes 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- Single polymerization with a urethane-modified epoxy compound (1-1) obtained by reacting 1> with a terminal isocyanate group-containing urethane prepolymer (I-1-2) obtained from a polyether polyol or a polyester polyol and an organic polyisocyanate. Among unsaturated basic acids, polymerizable unsaturated basic acids and saturated basic acids, saturated polybasic acids, saturated polybasic anhydrides, polymerizable unsaturated polybasic acids, and polymerizable anhydrous unsaturated polybasic acids. organic acids (1-2) containing one or more organic acids selected from;
A composition characterized by containing an esterified product obtained by reacting an epoxy compound (1-3) having one or more glycidyl ether type epoxy groups per molecule and a CII) polymerizable monomer. .

As the epoxy compound (I-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, the epoxy resin 180 to 50
Preferably, it is liquid at 0. Such liquid epoxy compounds include epoxy resins containing aromatic nuclei, particularly epoxy resins obtained by reacting polyhydric phenol alkylene oxide adducts obtained by adding alkylene oxide to polyhydric phenols with epihalohydrin. is preferred.

In addition, urethane prepolymer containing terminal isocyanate groups (1-1) obtained from the above polyether polyol or polyester polyol and organic polyisocyanate
-2”), the polyether polyol is:
A compound obtained by adding an alkylene oxide (e.g., ethylene oxide, propylene oxide) to a compound having two or more active hydrogens by a conventional method. Examples of active hydrogen-containing compounds include dihydric alcohols (e.g., ethylene glycol, Propylene glycol, 1,5
-bentanediol), 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. (nitrimethylolbenzene), polyhydric phenol (eg, phenol-formalin initial condensate), and the like.

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, sheric acid, sebacic acid, oxalic acid, methyladipic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, Any suitable carboxylic acid such as thiosypropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, or the like can be used.

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

In addition, as the organic polyisocyanate here, the general formula (where ○ is a benzene ring or naphthalene ring, -NGO
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 0.1 or 2) diisocyanate (e.g., 2.4-)ylene diisocyanate; 2. 6-
) Louis diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate,
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-isopropylbenzole,
2゜4-diisocyanate) general formula (where 0 is a benzene ring or naphthalene ring, -(CH
z) -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, and n is 1 or 2
) (Example: ω, ω゛-diisocyanate 1,2-dimethylpenzole, ω, ω゛-
diisocyanate)-1,3-dimethylpenzole)2; 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-4,4'-diisocyanate, diphenyldimethylmethane to 4,4'-diisocyanate, 3.3" −
dichlorodiphenyldimethylmethane-4,4-diisocyanate), general formula (where 2 is a nuclear-substituted halogen atom or an alkyl or alkoxy group having 3 or less carbon atoms, m is 0 or 1, n is 0
．． 1 or 2) (e.g. biphenyl-2,4-diisocyanate, biphenyl-4)
, 4'-diisocyanate, 3,3'-methylbiphenyl-4,4'-diisocyanate, 3.3"-dimethoxybiphenyl-4,4'-diisocyanate), diphenylsulfone-4,4'-diisocyanate, to the above isocyanate Diisocyanates such as those obtained by hydrogenating the aromatic rings contained therein (e.g. dicyclohexane-4,4゛-diisocyanate, ω, ω°-diisocyanate 1.2
-dimethylbenzene, ω, ωゝ-diisocyanate 1
．． 3-dimethylbenzene), diisocyanates containing substituted urea groups obtained by reaction of 2 mol of diisocyanate and 1 mol of water (e.g. 1 mol of water and 2 mol of 2.4-
urea diisocyanate obtained by reaction with 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-dinitropenkune-1,5-diisocyanate, octane-1,
Examples include 6-diisocyanate and hexamethylene diisocyanate.

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

Furthermore, this terminal isocyanate group-containing urethane prepolymer (1-1-2) is converted into an epoxy compound (1-1-1) having an average of more than 1 adjacent epoxy group and an average of 0.1 or more hydroxyl groups in the molecule. and the OH/NCO ratio is greater than 1 using a conventional method, e.g. 40 to 1 in a nitrogen stream.
The urethane-modified epoxy compound (I-1) can be obtained by reacting at a temperature of about 00°C for about 3 to 5 hours.

In the production of the urethane-modified epoxy compound (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) obtained in this way is a single polymerizable unsaturated basic acid, a polymerizable unsaturated basic acid and a saturated basic acid, a saturated polybasic acid, an anhydrous saturated polybasic acid, a polymerizable unsaturated basic acid, a saturated polybasic acid, an anhydrous saturated polybasic acid, Organic acids (I-2) containing one or more organic acids selected from polyunsaturated polybasic acids and polymerizable anhydrous unsaturated polybasic acids, and one or more glycidyl ether type per molecule The esterification reaction is carried out with the epoxy compound (I-3) having an epoxy group, and 0.2 to 1.2 equivalents, preferably 0.5 to 1.0 equivalents of carboxyl groups per 1 equivalent of epoxy group. The reaction is carried out within the range of .

The reaction temperature for the above esterification reaction is suitably in the range of 80 to 150°C, preferably 80 to 120°C. Although a catalyst is not necessarily required, organic amines and their salts, mercaptans, phenols, metal soaps such as tin octylate, Lewis acid catalysts such as boron trifluoride, etc. may be used.

Polymerizable unsaturated basic acids used in the present invention include acrylic acid, methacrylic acid, crotonic acid, etc. Polymerizable unsaturated polybasic acids and their acid anhydrides include maleic acid,
Examples include maleic anhydride, fumaric acid, and itaconic acid. The saturated 4-basic acids, saturated polybasic acids, and their acid anhydrides used in the present invention include benzoic acid, stearic acid, phthalic acid, isophthalic acid, phthalic anhydride, and adipic acid.

These acids are 0.5 to 1.0 equivalents of polymerizable unsaturated-basic acids or unsaturated polybasic acids and their anhydrides, and O
It can be used in a proportion of ~0.5 equivalent.

Furthermore, as the epoxy compound (I-3) having one or more glycidyl ether type epoxy groups per molecule, glycidyl ether (1-3- 1) Polyglycidyl ether of alcoholic polyhydroxyl compound (I-3 -2, ), polyglycidyl ethers of aliphatic polyhydroxyl compounds (I-3 to 3) that do not contain a nucleus, or glycidyl ethers of aliphatic monoalcohols, alicyclic monoalcohols, and -valent phenols (1-3-4 ) etc.

Glycidyl ether of polyhydric phenol (I-3-1) is, for example, polyhydric phenol (a) having at least one aromatic nucleus and shrimp halohydrin (b) treated with a basic catalyst such as sodium hydroxide or An epoxy resin containing as a main reaction product a polyglycidyl ether, such as can be obtained by reacting in a conventional manner in the presence of a reactive amount of a basic compound, or a polyhydric phenol (a) having at least one aromatic nucleus and an epihalohydrin ( An epoxy resin such as that obtained by reacting a polyhalohydrin ether obtained by reacting b) with a basic compound such as sodium hydroxide by a conventional method in the presence of a catalytic amount of a basic catalyst such as triethylamine. .

Similarly, polyglycidyl ether (1-3-2') or polyglycidyl ether (I-3-3) is, for example, a polyhydric phenol having at least one aromatic nucleus and an alkylene having 2 to 4 carbon atoms. A polyhydroxyl compound (a'') derived by an addition reaction with an oxide or an aliphatic polyhydroxyl compound (a'') without a nucleus and an epihalohydrin (b) in the presence of an amount of an acidic catalyst such as boron trifluoride. This is an epoxy resin containing as a main reaction product a polyglycidyl ether obtained by reacting a polyhalohydrin ether obtained by a conventional method with a basic compound such as sodium hydroxide.

Here, the polyhydric phenol (a) having at least one aromatic nucleus includes a mononuclear polyhydric phenol (a-1) having one aromatic nucleus and a polyhydric phenol having two or more aromatic nuclei. phenol (a-2).

Examples of such mononuclear polyhydric phenol (a-1) include pyrogallol, phloroglucin, etc., and examples of polynuclear polyhydric phenol <a-2) include phenol, aldehyde such as formaldehyde of phenols such as cresol, etc. Compounds having an average of more than two hydroxyl groups in one molecule obtained by condensing aromatic compounds having one or more hydroxyl groups, such as condensation reaction products with In addition, the polyhydroxyl compound (a゛) herein refers to the above polyhydric phenol (al) having at least one aromatic nucleus and an alkylene oxide in the presence of a catalyst that promotes the reaction between an OH group and an epoxy group. -RQH bound to a nuclear phenol residue through an ether bond obtained by reaction
(where R is an alkylene group derived from alkylene oxide) or (and) -(RO), H (where R is an alkylene group derived from alkylene oxide and one polyoxyalkylene chain contains different alkylene groups) It is a compound having an atomic group (n is 2 or an integer of 2 or more indicating the number of polymerized oxyalkylene groups). In this case, the ratio of the polyhydric phenol (a) and alkylene oxide is 1:1 (mol:mol) or more, but
Preferably, the ratio of alkylene oxide to 0 groups of the polyhydric phenol (al) is 1:1 to 10, preferably 1:1 to 3 (equivalent to equivalent).

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., but those that generate side chains when reacting with the polyhydric phenol (a) to form an ether bond are particularly preferred; Examples include propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide, with propylene oxide being particularly preferred.

In addition, the polyhydroxyl compound (a'') includes all those containing an alicyclic nucleus obtained by hydrogenating the aromatic nucleus of the above-mentioned compounds containing an aromatic nucleus.

Examples of the aliphatic polyhydroxyl compound (a'') that does not contain a nucleus include polyhydric alcohols such as trimethylolpropane, glycerin, and pentaerythritol, and these polyhydric alcohols or other active hydrogen-containing compounds (such as amino Examples include polyhydric polyhydroxyl compounds in which alkylene oxide is added to a compound having a group such as a carboxyl group, a carboxyl group, or a thiohydroxyl group, and polyhydroxyl compounds such as polyether polyols.

In addition, here, epihalohydrin (bl is represented by the general formula (here, Z is a hydrogen atom, a methyl group, an ethyl group, and X'' is a halogen atom), and examples of such epihalohydrin Tb) are: , e.g. epichlorohydrin,
Epibromohydrin, 1,2-epoxy-2-methyl-
3-chloropropane, 1,2-epoxy-2-ethyl-
Examples include 3-chloropropane.

Examples of acidic catalysts that promote the reaction between the epihalohydrin (b) and the polyhydroxyl compound (a゛) or polyhydroxyl compound (a'') include boron trifluoride, stannic chloride, zinc chloride, and ferric chloride. Lewis acids such as, derivatives exhibiting these activities (e.g. boron trifluoride-ether complex compound)
Alternatively, a mixture thereof can be used.

Similarly, epihalohydrin (bl and polyhydric phenol (a)
Basic catalysts that promote the reaction include alkali metal oxides (e.g. sodium hydroxide), alkali metal alcoholades (e.g. sodium ethylate), tertiary amine compounds (e.g. nitriethylamine, triethanolamine).
, a quaternary ammonium compound (e.g., tetramethylammonium bromide), or a mixture thereof, such that either the glycidyl ether is produced simultaneously with the reaction, or the helohydrin ether produced as a result of the reaction is Basic compounds that can be ring-closed by dehydrohalogenation reaction to produce glycidyl ether include alkali metal hydroxides (e.g. sodium hydroxide), alkali metal salts of aluminates (e.g. aluminates 1
-Rium) etc. are conveniently used.

Furthermore, as the aliphatic monoalcohol in the glycidyl ether (1-3-4), aliphatic monoalcohols having 3 to 22 carbon atoms are preferable, and among them, butyl alcohol, allyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, etc. Alcohol is particularly preferred; as the alicyclic monoalcohol, alicyclic monoalcohols having 5 to 22 carbon atoms are preferred; cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, and cyclooctyl alcohol are especially preferred; teeth,
m phenols with one or more aromatic nuclei are preferred, in particular phenol (carbolic acid), cresol, xylenol, ethylphenol, propylphenol, thymol, carvacrol, butylphenol,
Particularly preferred are amylphenol and octylphenol.

Next, the polymerizable monomer (II) is a vinyl type.

Acrylic and allyl polymerizable monomers can be used, such as styrene, vinyl compounds such as vinyltoluene, acrylic acids such as methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate, and nuccrylic acid. Monoesters, fumaric acid such as dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, etc., or diallyl phthalate, etc., and known compounds such as hydroquinone, naphthoquinone, benzoquinone, 4-t-butylcatechol, etc. It can be added in the presence of a radical polymerization inhibitor.

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 variety of fields, including 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, Comparative Example 1 Polyester polyol (molecular weight 28
00) and 10 parts of toluylene diisocyanate were heated and stirred at 85° C. for 4 hours to obtain 60 parts of a polyurethane prepolymer containing terminal isocyanate. 60 parts of this polyurethane prepolymer was added to 150 parts of diglycidyl ether (epoxy equivalent: 340, hydroxyl value: 51) of 2,2-bis-(4-hydroxylphenyl)propane propylene oxide adduct, and the mixture was heated at 120 to 130°C for 3 hours. After heating and stirring, 2 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 480.

To this 480 parts, 190 parts of diglycidyl ether of bisphenol A having an epoxy equivalent of 190, and 17 parts of methacrylic acid.
When 2 parts of triethanolamine and 3 parts of triethanolamine were mixed together and the reaction was carried out at 120°C for 8 hours under a nitrogen stream, the acid value was 10.
It dropped to 0.

Add 0.15 parts of hydroquinone to this, and add 25 parts of styrene.
0 parts, and then 2% by weight of methyl ethyl ketone peroxide and 1% by weight of cobalt naphthenate were added to the resulting resin, a cast plate was prepared, and the physical properties were measured after one week at room temperature.

For comparison, 180 parts of methacrylic acid and 1 part of dimethylbenzylamine were mixed with 400 parts of diglycidyl ether of bisphenol A having an epoxy equivalent of 190, and a reaction was carried out at 120°C for 6 hours under a nitrogen stream. The value decreased to 5.0. 0.15 parts of hydroquinone was added to this, diluted with 230 parts of styrene, and then the same treatment as in Example 1 was performed to obtain Comparative Example 1. Table 1 shows the physical properties of each.

Table 1 Example 1 Comparative Example 1 Tensile strength (kg/Tsururi 5.0 3.2 Elongation (%) 3.0
2.0 Bending strength (kg/in”) 13
12 Flexural modulus (kg/ms+”) 30
0 356 Tensile shear strength (kg/cm”) 1
00 74 Note 1) A test piece made by adding 100 parts of resin to 100 parts of silica and bonding a steel plate treated with sandpaper and trichlorene was used, and the curing conditions were the same as for the cast plate (see the table below). (same as well).
l Example 2, Comparative Example 2 Polypropylene glycol (average molecular weight 2000) 60
and 21 parts of toluylene diisocyanate were heated and stirred at 85° C. for 3 hours to obtain 81 parts of polyurethane prepolymer. 81 parts of this polyurethane prepolymer was mixed with 50 parts of diglycidyl ether of 2-bis-(4-hydroxyphenyl)propane (epoxy equivalent: 190, hydroxyl value: 14).
After heating and stirring at 150 to 160° C. for 3 hours, 5 parts of triethylene glycol was added, and the reaction was further continued for 1 hour. The obtained urethane-modified epoxy resin was liquid and had an epoxy equivalent of 230.

To this 170 parts, 225 parts of diglycidyl ether of bisphenol A having an epoxy equivalent of 450, and 86 parts of methacrylic acid.
When the reaction was carried out at 120°C for 8 hours under a nitrogen stream, the acid value was 5.5 parts and 1.5 parts of triethanolamine.
It dropped to 0. 0.15 parts of hydroquinone was added to this, diluted with 250 parts of styrene, and then the same treatment as in Example 1 was performed to obtain Example 2.

For comparison, 86 parts of methacrylic acid and 1 part of dimethylbenzylamine were mixed with 450 parts of diglycidyl ether of bisphenol A having an epoxy equivalent of 450, and a reaction was conducted at 120°C for 6 hours under a nitrogen stream. The value is 5
．． It dropped to 0. 0.15 parts of hydroquinone was added to this, diluted with 230 parts of styrene, and then the same treatment as in Example 1 was performed to obtain Comparative Example 2. Table 2 shows the physical properties of each.

Table 2 Example 2 Comparative example 2

Claims (1)

[Claims] 1. As an essential component (I) an epoxy compound having an average of more than 1 adjacent epoxy group and an average of 0.1 or more hydroxyl groups in the molecule (I
-1-1) and a urethane-modified epoxy compound (I-1) obtained by reacting a polyether polyol or a polyester polyol with a terminal isocyanate group-containing urethane prepolymer (I-1-2) obtained from an organic polyisocyanate. , a single polymerizable unsaturated basic acid, a polymerizable unsaturated basic acid and a saturated basic acid, a saturated polybasic acid, an anhydrous saturated polybasic acid, a polymerizable unsaturated polybasic acid, a polymerizable anhydrous unsaturated polybasic acid, Organic acids (I-2) containing one or more organic acids selected from basic acids, and an epoxy compound (I-3) having one or more glycidyl ether type epoxy groups per molecule. A curable unsaturated epoxy resin composition comprising an esterified product obtained by reacting the following: and (II) a merging monomer.