JPS6026410B2 - polymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polymerizable composition having excellent air curability, toughness, and good chemical resistance.

The so-called epoxy (meth)acrylate is, for example, a polyfunctional (
It is used in combination with meth)acrylate mo/mer and a photosensitizer to make an ultraviolet curable resin, and by adding a polymerization initiator it is used as a heating V thermosetting type or room temperature curing type resin, but it is also air curable. Although it has good internal hardening properties, it has poor surface hardening properties. Furthermore, since hydroxyl groups remain, there are many problems with water resistance and the like. There is a method of adding alkanolamines such as dimethylethanolamine, diisopolamine, triethanolamine, etc. to improve surface hardening, but the alkanolamines may bleed after hardening or internal hardenability may decrease, resulting in poor resistance. There are many problems such as decreased drug properties. The present inventors aimed to improve such drawbacks.As a result of intensive studies, we found that a compound obtained by adding a monofunctional secondary amine compound and a carpoxyl group-containing polymerizable compound to an epoxy compound, a diisocyanate and a hydroxyl group-containing compound, and a diisocyanate and a hydroxyl group-containing compound. The present invention aims to provide a polymerizable compound having excellent chemical resistance and air curability by reacting the polymerizable compound with an incyanate adduct composition obtained from the inocyanate adduct composition.

That is, in the present invention, a monofunctional secondary amine compound and a carboxyl group-containing polymerizable composition are added to an epoxy compound so that the amount of secondary amino groups and carboxyl groups is zero per equivalent of the epoxy group.
．． Compound A obtained by adding 4 to 1.0 equivalents and isocyanate adduct compound B obtained from diisocyanate and a hydroxyl group-containing polymerizable compound so that the amount of isocyanate group is 1 equivalent or less per 1 equivalent of hydroxyl group. The present invention relates to a polymerizable composition obtained by reacting as described above.

The epoxy compound used in the present invention has one or more epoxy groups in one molecule, and has, for example, the general formula (wherein R' is a group having 2 or more carbon atoms, and n is 1, 2 or 3 is an integer greater than or equal to

) Specifically, the compound represented by Epiquat 817
(manufactured by Shell Chemical Co., Ltd.), Epiclone 400 (manufactured by Dainippon Ink Chemical Co., Ltd.), Epiclone 441 (manufactured by Dainippon Ink Chemical Co., Ltd.): 1 general formula (wherein R'' is a group having 2 or more carbon atoms, n is an integer of 1, 2 or 3 or more.

), specifically epiclone 702,
Epiclone 705, Epiclone 707 (both manufactured by Dainippon Ink and Chemicals); Bisphenol A/(methyl)
epichlorohydrin condensate, bisphenol F/(methyl)epichlorohydrin condensate, hydrogenated bisphenol A
(Methyl) epichlorohydrin condensate, hydrogenated bisphenol F (methyl) epichlorohydrin condensate, novolac type pepoxy resin, and the like. In the present invention, where curability is important, polyfunctional epoxy compounds are preferred, but bifunctional epoxy compounds are more preferred because the more polyfunctional the epoxy compound, the higher the viscosity. Monofunctional secondary amine compounds include dimethylamine, di-n-propylamine, dibutylamine, di-2-methylbentylamine, di-2-ethylhexylamine, dibenzylamine, N-penzyl-N-
Isopropylamine, morpholine, 2,6-dimethylmorpholine, piperidine, N-methylethanolamine,
Examples include diethanolamine, diisopropanolamine, and the like.

Examples of carboxyl group-containing polymerizable compounds include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, tetrahydrophthalic anhydride, cis-3-methyl-4-cykhexensis, cis-1,2- Dicarboxylic acid anhydride, glutaconic acid, citraconic acid, itaconic acid,
Ethylidene malonic acid, mesaconic acid, allilma. Examples include phosphoric acid, propylidenemalonic acid, hydromuconic acid, pyrosinchoninic acid, allylsuccinic acid, carbocaprolactonic acid, tetraconic acid, xeronic acid, and cetylmalonic acid.
In addition, phthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebazic acid, dimethylsuccinic acid, benzoic acid,
Hexanoic acid, caprylic acid, halauric acid, caproic acid, myristic acid, palmitic acid, stearic acid, arachidic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, liganic acid, ricinoleic acid, hexenoic acid, hexagene Acids, saturated polycarboxylic acids such as octenoic acid, aromatic polycarboxylic acids, and their acid anhydrides, as well as castor oil, dehydrated castor oil, coconut oil, bran oil, linseed oil, citrus oil, scallion oil, olive oil, Acid mixtures such as flower oil, sardine oil, soybean oil, tall oil, and perilla oil can also be used in combination with the carboxyl group-containing polymerizable compound. Among these, acrylic acid and methacrylic acid are more preferred. Examples of diisocyanate compounds include xylene diisocyanate, 2,4 toluylene diisocyanate, 2,6 tolylene diisocyanate, 1,4 naphthylene diisocyanate, 1,5 naphthylene diisocyanate, 1,
3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1-isopropylbenzole-2,
4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2-dimethyldiphenylmethane-4,4'-diisocyanate, diphenylmethylmethane-4,4'-diisocyanate, 3,3'-dichlorodif enyldimethylmethane-4,4'-diisocyanate, biphenyl-2, page isocyanate, biphenynyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylsulfone-4,4' Aromatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate,
aliphatic such as dicyclohexylmethane diisocyanate,
Examples include alicyclic diisocyanates.

Further, the hydroxyl group-containing polymerizable compound used in the present invention is a hydroxyl group-containing compound having at least one polymerizable unsaturated bond, and specifically, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( meth)acrylate, t-butylhydroxy(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxylauryl(meth)acrylate, trimethylolpropane di(meth)acrylate, allyl alcohol, allyl cellosolve, trimethylolpropane diallyl Examples include ether.

In the present invention, first, an epoxy compound is
amine compound and a carboxyl group-containing polymerizable compound. The reaction ratio at that time is preferably 0.4 to 1.0 equivalents, which is the sum of the secondary amino groups of the secondary amine compound and the carboxyl groups of the carboxyl group-containing polymerizable compound to 1 equivalent of the epoxy group of the epoxy compound. is 0.6 to 1.0 equivalent. In such a reaction, a compound having a hydroxyl group is bound by the reaction between an epoxy group and a secondary amino group and the reaction between an epoxy group and a carboxyl group.
The ratio of the secondary amine compound to the carboxyl group-containing polymerizable compound is preferably 2 to 100, preferably 3 to 50 equivalents of carboxyl groups per equivalent of secondary amino group. The hydroxyl group-containing compound obtained by the above reaction is then reacted with an isocyanate adduct compound obtained from the diisocyanate compound and the hydroxyl group-containing polymerizable compound to obtain a polymerizable composition.

At that time, the reaction ratio of the compound having a hydroxyl group obtained from the epoxy compound, the secondary amine compound and the carboxyl group-containing polymerizable compound and the isocyanate adduct compound is preferably 1 equivalent or less of isocyanate group per 1 equivalent of hydroxyl group, preferably It is 0 to 0.5 equivalent. In addition, the incyanate adduct compound is a hydroxyl group 1 of a hydroxyl group-containing polymerizable compound.
The isocyanate group of the diisocyanate compound is reacted in an amount of 1.3 to 2.5 equivalents, preferably 1.6 to 2.0 equivalents. Thus, the obtained polymerizable composition is one obtained by reacting the incyanate adduct compound and/or one in which the incyanate adduct compound has not reacted.

Furthermore, the polymerizable composition may contain a high boiling point polymerizable monomer.

Such high-boiling point polymerizable monomers have a boiling point of 200 oo or more, and specifically include lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, and trilubitol. (meth)acrylate, 1,6
-benzoic acid/(meth)acrylic acid ester of hexanediol, benzoic acid/(meth)acrylic acid ester of neobentyl glycol
Acrylic acid ester, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,4-butadiol di(meth)acrylate,
1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, bentaerythritol tetra(meth)acrylate, 8-hydroxyethyl(meth)acrylate, 8-hydroxypropyl(meth)(acrylate, t -Butyl hydroxy(meth)acrylate, propylene glycol mono(
meth)acrylate, polypropylene glycol mono(
meth)acrylate, 8-hydroxylauryl(meth)
Examples include acrylate, trimethylolpropane diallyl ether, diallyl terephthalate diallyl fumarate, diallyl maleate, pentaerythritol diallyl ether, and the like. Such a high boiling point polymerizable monomer is used in an amount of 400 parts by weight or less based on 100 parts by weight of the polymerizable composition, and the polymerizable composition of the present invention has the general formula (RO) 3.
P (wherein R is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group.

) may be added.
Such compounds improve storage stability and at the same time improve air curing properties. Examples include tributyl phosphite, tris(2-ethylhexyl) phosphite,
Tridecyl phosphite, tristearyl phosphite, triphenyl phosphite, diphenyldecyl phosphite, diphenyl tridecyl phosphite, tris(2,3-dichloropropyl) phosphite, distearylbentaerythrityl diphosphite etc. Other thiophosphites such as trilauryl trithiophosphite can also be used. Such a compound is added to the polymerizable composition in an amount of 0.1 to 1 per 100 parts by weight.
Usually used in proportions of parts by weight. In order to cure the polymerizable composition of the present invention, ultraviolet irradiation, electron beam, gamma irradiation,
Any of the following methods can be employed: irradiation with ionizing radiation such as radiation, a method of adding a radical polymerization initiator and heating, a method of adding a redox polymerization catalyst, or a method of further heating. In the case of ultraviolet irradiation, a so-called photosensitizer added to the ultraviolet curable resin, such as penzoin, penzoin methyl ether, penzoin alkyl ethers such as benzoin isopropyl ether, etc. , piparoins, butyroins, benzophenone, anthraquinone and its derivatives, polynuclear quinones, disulfides, benzyl, etc. can be used in the range of 0.1 to 10% by weight in the total composition. It cannot prevent the addition of curing accelerators and polymerization inhibitors used at that time. In the case of irradiation with ionizing radiation, the acceleration voltage is 0.1 to 2. It is appropriate to irradiate the beam with a dose rate of 0.1 to 30 Mrad/sec using an eV electron beam accelerator. Examples of radical polymerization initiators include penzoyl peroxide, lauroyl peroxide, mono-1-butyl perbenzoate, cumene hydroperoxide,
Examples include methyl ethyl ketone peroxide, azopisisobutyronitrile, and azobiscyclohesylnitrile. The amount used is usually 0.5 to 5% by weight. As a redox-based polymerization catalyst, peroxides such as those mentioned above, N,
There are combinations with N-dimethylaniline, N,N-dimethylbenzylamine, N,N'-diisopropyl-P-toluidine, triethanolamine, diisopro/gnolamine, cobalt naphthenate, etc., and the content is 0.5 to 1% by weight. used in amounts of Example 1 194 parts by weight of Epiclone 850 (manufactured by Dainippon Ink & Chemicals, Gepoxy type epoxy resin; epoxy equivalent: 194) and 13 parts by weight of diisopropanolamine were placed in a conventional reaction vessel. Round weight part, acrylic acid I. 0.0 part by weight of hydroquinone, 0.0 part by weight of tri-n-butylamine. Parts by weight of milk were charged and reacted at 90q0 until the acid value became 1 or less to obtain a polymerizable resin composition (1).

Next, 3 parts by weight of neobentyl glycol diacrylate, 2 parts by weight of benzophenone, and 0.003 parts by weight of hydroquinone were added to 7 parts by weight of the composition (1) to obtain an ultraviolet curable resin composition. Table 1 shows the physical properties of cured coatings of such compositions. Example 2 331 parts by weight of Epiclone 707 (manufactured by Dainippon Ink and Chemicals, epoxy type epoxy resin: epoxy equivalent unevenness 1), 21 parts by weight of jetanolamine, and 57. A polymerizable resin composition (D) was obtained in the same manner as in Example 1, adding 0.041 part of hydroquinone and 0.41 part of tri-n-butylamine.

Meanwhile, 174 parts by weight of 2,4-toluene diisocyanate and 0.0 part by weight of hydroquinone were placed in another container.
Next, 2-hydroxypropyl acrylate 13 parts by weight was added over 3 hours at 65°C, and 6yo
Incyanate duct compound a was obtained.

Parts by weight of the above polymerizable resin composition (0) 41, parts by weight of incyanate adduct compound a15a, 37.47 parts by weight of 1,6-hexanediol diacrylate, 0.030 parts by weight of hydroquinone, 0 parts by weight of dibutyltin diacetate
．． The NCO content was 0.0 parts by weight at 65 qo.
After reacting until the weight of the blade is below %, 2-hydroxypropyl acrylate muscle. A polymerizable resin composition A was obtained by inactivating the remaining isocyanate groups with 2 parts by weight.

2 parts by weight of penzoin methyl ether was added to parts by weight of this polymerizable resin composition AIOO to obtain an ultraviolet curable resin composition. Table 1 shows the physical properties of cured coatings of such compositions. Example 3 24 parts by weight of Epicron 750 (manufactured by Dainippon Ink and Chemicals, dipoxy type resin: epoxy equivalent: 240), 64.8 parts by weight of acrylic acid, 10.7 parts by weight of N-methylaniline, 0.032 parts by weight of hydroquinone. parts by weight and 0.32 parts by weight of tri-n-butylamine were charged, and the reaction was carried out in the same manner as in Example 1 to obtain a polymerizable resin composition (m).

8 parts by weight of this polymerizable resin composition (m), 2 parts by weight of ethyl acetate
and 2 parts by weight of benzophenone were mixed to obtain an ultraviolet curable resin composition.

Table 1 shows the physical properties of cured coatings of such compositions. Example 4 Hexamethylene diisocyanate 1 part by weight of paper, 76.2 parts by weight of ethyl acetate, 0.0 part by weight of hydroquinone, N
-0.08 parts by weight of methylmorpholine was charged, 136.8 parts by weight of 2-hydroxyethyl acrylate was added over 3 hours, and the mixture was further reacted at 65°C for 5 hours to obtain incyanate adduct compound b.

319.4 parts by weight of the polymerizable resin composition (b) in Example 3, 74.9 parts by weight of ethyl acetate, and the above incyanate adduct compound b95. 0.05 parts by weight of dibutyl tin diralate were added, and the NCO content was 0.6500. After reacting to less than % milk weight, the remaining isocyanate was inactivated with 1 part by weight of methanol to obtain a polymerizable resin composition B.

1 part by weight of penzophenone per part by weight of this polymerizable resin composition BIOO. A UV curable resin composition was obtained by adding a weight part of UV curable resin.

Table 1 shows the physical properties of cured coatings of such compositions. Example 5 Parts by weight of polymerizable resin composition (1) 7 in Example 1, 30 parts by weight of neobentyl glycol diacrylate, 2 parts by weight of triphenylphosphite, 2 parts by weight of penzophenone, 0.0 parts by weight of hydroquinone. 003 parts by weight were mixed to obtain an ultraviolet curable resin composition.

This product had better storage stability than the ultraviolet curable resin of Example 1. Table 1 shows the physical properties of the mold resin composition of this example. Comparative example Epiclone 707 (
331 parts by weight (same as in Example 2), 72 parts by weight of acrylic acid, 0.04 parts by weight of hydroquinone, and 4 parts by weight of tri-n-butylamine were reacted in the same manner as in Example 1, and after the reaction was completed, 1,6-hexanediol diacrylate 2nd route. 0.0 part by weight of hydroquinone, and 13.5 parts by weight of benzoin methyl ether were added to obtain an ultraviolet curable resin composition.

The physical properties of such compositions are shown in Table 1. Table 1 Note) Curing test - 1 *1: Coated on an iron plate to a dry film thickness of 20 mm using a 4KW high-pressure mercury lamp (manufactured by Iwasaki Electric, output per unit length 80W/2) using a condensing type. This shows the state of the hardened coating when irradiated once at a comparison speed of 4 mh/min at a distance of 1.

Curing test-2*2: Shows the state of the cured coating film when irradiation was performed once at a line speed of 3 h/mjn in curing test-1.

Pencil hardness *3: Indicates the pencil hardness of the cured coating film obtained by irradiating once at a line speed of 18 h/min in curing test 1.

Acetone wrapping*4: Shows the number of times the same cured coating film as used in measuring pencil hardness is reciprocated with acetone until the base surface becomes visible.

Water resistance *5: Shows the state of the cured coating film when it is immersed in 50 qo warm water for 2 hours for the same cured coating film as in the measurement of pencil hardness.

Claims (1)

[Claims] 1. A monofunctional secondary amine compound and a carboxyl group-containing polymerizable compound are added to the epoxy compound so that the proportion of the secondary amino group and the carboxyl group is 0.4 to 1.
Compound A obtained by adding 0 equivalent and isocyanate adduct compound B obtained from a diisocyanate compound and a hydroxyl group-containing polymerizable compound are reacted so that the amount is 1 equivalent or less of isocyanate group per 1 equivalent of hydroxyl group. A polymerizable composition.