JPS60106834A - Room temperature-curable composition - Google Patents

Abstract

PURPOSE:A composition excellent in room temperature curability and suitable for adhesives, paints, etc., obtained by mixing a polyallyl compound and/or a polyallylidene with a polythiol compound, an organic peroxide and a metallic compound. CONSTITUTION:The purpose room temperature-curable composition is obtained by mixing a polyallyl compound having at least two allylically unsaturated bonds in the molecule (e.g., diallyl phthalate) and/or a polyallylidene compound having at least two allylidenically unsaturated bonds (e.g., diallylidenepentaerythritol) with a polythiol compound having at least two thiol groups in the molecule (e.g., hexanediol dithioglycolate), an organic peroxide (e.g., t-butyl hydroperoxide), and a metallic compound (e.g., copper naphthenate or chromium oleate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides adhesives and coatings. 1] It relates to a composition that can be cured at room temperature and can be used in a wide range of fields, such as cast products, fiber-reinforced plastics, etc.

Among resin systems that can be cured at room temperature, there are some that are easy to cure, and others that cannot be cured unless they are cured at high temperatures and over a long period of time.There is a difference in the difficulty of curing. It has been known. For example, curing of unsaturated polyester resin is easy, but when curing epoxy resin with amine,
It is difficult to control the curability by increasing or decreasing the amount of amine, which is a curing agent, and the viscosity is high, and the problem of amine irritation to the skin and toxicity remains.

The present inventors added a polyallylidene compound to polyallyl compound 1 in order to improve its handling properties, that is, the difficulty in controlling its curing properties, its high viscosity, etc., while maintaining the excellent physical properties seen in epoxy resins. We have been conducting research on so-called polyene-polythiol type resins made of polythiol compounds, but this type of resin is unique in terms of high-temperature curing using organic peroxides and cationic curing using cationic catalysts. Due to the conventional wisdom that it would not exhibit the physical properties necessary to reach practical use, research and practical application have only been attempted from the aspect of photocuring.

Light curing is certainly an advantageous method, and where it is applied, other curing methods are justifiable, but in cases where light curing is difficult to apply, e.g. Therefore, it is essential to establish a different curing system, especially a type of resin that hardens easily at room temperature.

From this point of view, the present inventors have found that by applying a curing system that is considered to be a kind of redox reaction between polyethylene and metal compounds, it is possible to cure the polyester resin very easily and in some cases in an extremely short time. They discovered that curing at room temperature can be performed, and completed the present invention.

That is, the present invention provides (1) a polyallyl compound having two or more allylic unsaturated bonds in one molecule and/or one
A polyarylidene compound having two or more adenically unsaturated bonds in the molecule, (2) a polythiol compound having two or more thiol groups in one molecule, (3) an organic peroxide, and (3) The present invention relates to a composition that is curable at room temperature and that contains a metal compound.

This discovery was unexpected because it is generally believed that allylic unsaturated bonds or allylidene unsaturated bonds do not harden at room temperature (aside from gelation).

One of the fundamental differences between the curing of the polyallyl compound or polyallylidene compound and polythiol compound type resin of the present invention and the curing of conventional radical curing resins, such as unsaturated ester resins and vinyl ester resins, is that Radical curing resins do not show any curing accelerating ability, or conversely, a curing system consisting of an organic peroxide and a metal compound that inhibits polymerization has a hardening effect on diaryl compound or polyallylidene compound and polythiol compound type resins. It can be mentioned that it has a remarkable curing accelerating effect.

Examples of such metal compounds include metal salts of nickel, chromium, tin, and the like.

Even from such a small flame, polyallyl compound or polyallylidene compound and polythiol compound type resin can be
It is thought that the mechanism of curing with an organic peroxide and a metal compound is different from that of conventional radical-curing resins. In particular, the polythiol compound is used to form one component of the cured resin, and is not used simply as a chain transfer agent. The I-allylic compound used in the present invention is one having two or more allylic unsaturated bonds in one molecule, and specific examples include the following allyl ether group, allyl ester group, or allyl urethane group. 2 in one molecule
Examples include monomers, prepolymers, and polymers having more than one polymer.

CH=CI(-CH2-0-allyl ether group CI(=
CI(-CI(2-0-C-allylnisder group') Monomers or prepolymers having an allyl ether group include, for example, trimethylol-Lrusolo/F triaryl ether, pentaerythrittetraallyl ether,
Examples include esterification products of trimethylolprono and monoallyl ether with polybasic acids.

Typical examples of heptamers having an allyl ester group include polyhydric carbamic acids or their acid anhydrides and allyl alcohol esters.
There are also compounds synthesized from phosphoric acid and located allyl compounds. Typical examples of monomers having an allyl ester group include diallyl slate,
Examples include nolyl isophthalate, endomethylenetetrahydrophthalic anhydride diallyl ester, nolyl ester of het acid, nolyl maleate, nolyl fumarate, triallyl isocyanurate, l-lylyl esdel of trimellidic anhydride, and the like.

Examples of prepolymers having allyl ester groups include:
Noaryl phthalate 0 ren 1? A remarker is added.

Sole with allyl urethane group, +? As a rimmer,
For example, additives of trimethylolpropane diallyl ether and diisocyanate, pentaerythri, totriallyl ether and noisocyanate, or adducts of this in combination with polyhydric alcohol and hydroxyl polymer,
Examples include additives in which allyl cellosolve and polyvalent isocyanate or polyvalent hydroxyl compounds are used in combination.

Examples of polymers containing allyl urethane groups include hydroxyl groups. polymer, allyl alcohol or allyl cellosolve, and neuisocyana-1.
Examples include those represented by the following general formula, which are obtained by reacting 1 mole of additive with an unsaturated incyanate having a free isocyanate group.

H2R2 N-C-0-CH2-CH2-0-CH2-CH=CH
2111 (wherein, n is 1 to 100, m is O to 99, R
1 is 3 R3 is an alkyl group or an aralkyl group), -CN
.

-Ct) The compound used in the present invention has two or more adenic unsaturated bonds in one molecule, and a typical example is sialylidene pentaerythrin. , can be given.

Among the above-mentioned polyallyl compounds and polyallylidene compounds, diallylide 7-pentaerythrite, which is a cycloether, is preferably used in the present invention because it has excellent reactivity with polythiol compounds.

Of course, the above polyallyl compounds having allyl ether groups, allyl ester groups and allyl urethane groups can be used in combination as necessary. Moreover, a polyallyl compound and a polyallylidene compound may be used together. moreover,
These polyallyl compounds and/or polyallylidene compounds can also be used in combination with unsaturated alkyds containing α/β-unsaturated polybasic acid residues.

The 49 lithiol compound used in the present invention is a compound having two or more thiol groups in one molecule. Rimmer can be given.

Representative examples of compounds include esterification products of thioglycomonolic acid or thionoropionic acid and polyhydric alcohols. Specific examples include hexanenoolnotioglycolate, hexanediolthioglopionate,
trimethylolgulon and trithioglycole-1.
Trimethylolgulononotritiopropionate, pentaerythri.

Examples include trithitrathioglycolate, pentaerythritol tetrathiozolopione-1, and the like. In addition, thiobisphenol A1 isocyanuric acid (3-mercaptozolopyl) ester, triazine trithiol, thiopentaerythri, and tomo can be used.

Examples of sol polymers include thioalkyl, deresin, fLti
Examples include alkyd resins having a thiol group obtained by esterifying methylolgulonocne-phthalic anhydride-mercaptopropionic acid.

Is the mixing ratio of the polyallyl compound and 7-inch polyallylidene compound and the polythiol compound the allyl group of the polyallyl compound or the month? It is preferable to mix the arylidene group of the realylidene compound or the combined unsaturated group of allyl group and arylidene group: thiol group in a molar ratio of 1:1, but depending on the purpose, the above molar ratio may be adjusted. may be slightly changed. For example, when the composition of the present invention is used as an adhesion agent, a polythiol compound may be added so that some thiol groups remain, and if the composition of the present invention can be post-cured. , allyl group and /′!
! Alternatively, the polyallyl compound and/or polyallylidene compound may be blended in excess so that the allylidene group remains.

Examples of the organic peroxides used in the present invention include ketone t9-oxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone/F-oxide, and cyclohexanone peroxide;
Peroxyfuketals such as bis(1-butyl-E-ogyne) 3,3.5-trimethylcyclohexane, t-butyl hydroperoxide, cumene hydroperoxide, noisozolobylbenzene hydroperoxide, , paramenthane hydroperoxide 1.1,1,3,3°hydrono-oxides such as tetramethylbutylhydrono and -oxide,
t-butylno and monooxybenzoate, t-butylno9
- Oxydiesters such as oxylaurate etc. can be used. Two or more of these organic peroxides may be used in combination.

The amount of organic peroxide used is 1. I? l) Allyl compound and/or polyallylidene compound, ? The amount is in the range of 01 to 10 parts by weight, T1 or 0.5 to 3 parts by weight, based on 100 parts by weight of the mixture of lithiol compounds. If the amount of organic peroxide used is less than 0.1 part by weight, complete curing is difficult, while if the amount of organic peroxide used is more than 10 parts by weight, the physical properties of the cured product will deteriorate, which is not preferable.

The metal compounds used in the present invention include those that are soluble in organic solvents, polyallyl compounds, polyallylidene compounds, and polythiol compounds, or mixtures thereof, preferably those that are soluble in organic solvents and are soluble in polyallyl compounds. compound, boria IJ IJden compound and ]? Examples include organic acid salts of metals having a valence of two or more and chelate compounds that are soluble in lithiol compounds or mixtures thereof.

Examples of the pJ metals used in the present invention include copper, cobalt, nickel, manganese, chromium, and chromium.

Zirconium, iron, noyaranoum, molybdenum, tin.

Examples include cerium and aluminum.

These metals include naphthenic acid, octylic acid, lauric acid,
It is used as a metal salt or chelate compound of organic acids such as oleic acid and rosin acid.

However, since the organic acid salt of vanazoum is unstable and has poor storage stability, it is better to use it in a stabilized form by dissolving a chelate compound such as vanazoum acetylacetonate in an acidic alkyl phosphate ester. This tendency is also observed in the unstable acid salts of molybdenum and /F radium, so it is preferable to use them in the same form as vanazium acetylacetonate-1. The amount of the metal compound to be used cannot be determined unconditionally as it varies significantly depending on the type of metal, but in general, the amount of the polyallyl compound and/or polyallylidene compound; ! Mixture of J thiol compounds Joo'
[5 parts by weight from ippm as metal to 7j parts, most desired 101) P! It is 1 part by weight from Tl. If the amount of the metal compound used is less than 1 ppm, the curing accelerating effect will not be sufficient. On the other hand, if the amount of the metal compound used is more than one part of pentaite, the effect of increasing the amount will no longer be observed.

The organic peroxide and the metal compound are polyallyl compounds and /' or I? It may be added as is to the mixture of the realylidene compound and the 7e lithioyl compound in order,
Alternatively, the organic peroxide and the metal compound may be added separately, and the two may be mixed at the time of use.

That is, an organic peroxide may be added to the polyallyl compound and/or polyallylidene compound component, a metal compound may be added to the polythiol compound component, and both components may be mixed at the time of use. At this time, the organic peroxide and the metal compound may be added in the opposite order.

It goes without saying that reinforcing materials, fillers, colorants, mold release agents, etc. may be used as appropriate in the composition of the present invention in order to meet the required physical properties.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 Diarylidene pentaerythri, I-20g, -2-2-pentaerythritol tetrathioglycosidium ---1.20,
'/.

2.5-di-L-butylhydroquinone 0.02.9'
After heating and dissolving at 550°C to make a homogeneous solution, the temperature f
: Lower the temperature to 25℃ and add 0.0% of cumene hydroperoxide.
5.9 was added and stirred uniformly. To this, add 0.5 fl (50 ppm) of copper naphthenate (1% Cu benzene solution).
), mixed, and injected into a test tube.

Celification occurred after 14 minutes, and continued heat generation reached a maximum temperature of 103°C.

The cured resin was yellowish brown and hard, and the hardness of the cut surface was 89 on the Rockwell hardness (M scale).

In addition, in the above method, unsaturated polynisder resins and vinyl ester resins cannot be cured with the above-mentioned combination of Giemen hydrono and copper oxaidonaphthenate, no matter which type 7!1 resin is used. Example 2 Synthesis of unsaturated alkyl, do(5) and unsaturated polynisder resin (B) A stirrer, a fractionating condenser, a temperature side, and a gas inlet pipe were installed in the 114-liter system. Propylene glycol 25
0g, maleic anhydride 147g, phthalic anhydride 22:1
7 was charged, and Nisderization was carried out at 190 to 210'C in a nitrogen gas stream to synthesize an unsaturated alkyd (A) with an acid value of 344. After adding 0.3.9 of hydroquinone to this unsaturated alkyd (4) and lowering the temperature to 120°C, 370 g of diallylphthale-1 and 200 g of diallylidene pentaerythritol were added at 80°C to form an unsaturated polyester resin. (B) was obtained. The obtained unsaturated polyester resin (B) had a Hazen color number of 200 and a viscosity of 29 poise. Put 50.9 g of unsaturated polyester resin (B) into a 200 CC beaker, add 30.9 g of pentaerythri, trithiopropionate, and 1.6 g of t-butyl hydroperoxide, and mix uniformly, then add vanadium acetyl. Acidic phosphoric acid butyl ester solution (3% v') of acetonate was added and dissolved in 0.49 g.

Gelation started after 3 minutes with a temperature of 9, rapidly generating heat and increasing the temperature to 127°C.

A hard, tough, brown casting resin with a slightly dark green tint was obtained. This casting resin had a Rockwell hardness (M scale) of 104 and a heat distortion temperature of 104°C.

In addition, in the above method, unsaturated polyester resin (
When t-butyl...hydroperoxide vananoum acetylacetonate l- was added in the same proportion to B), no thickening occurred.

Example 3 Synthesis of unsaturated polyurethane (C) In a 11-meter flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a temperature side, 336 g of hexamethylene noisocyab-l, hydroquinone OIg, butyltin nolaure) 0 .7.9 was prepared, and 410 g of allyl cellosolve was added dropwise at a temperature of 60°C.

When heated and stirred at the same temperature for 3 hours, the number of infrared analyzes was 25.
0, viscosity was 47;

Unsaturated polyurethane (C) 75.9, hexanedio-
Lunotioglycolate 53.9. After t-butyl perbenzoate 13 and 006 g of hydroquinone were made into a homogeneous solution, a solution of vanadium acetylacetonate acidic butyl phosphate (1% v) was added dropwise and stirred.

The chelation occurred after 5 minutes, generating heat and reaching a maximum temperature of 79°C.

The obtained cured resin was extremely elastic, and the elongation rate of the plate was vacuum cast to a thickness of 3 mm and reached 490@).

Example 4 Synthesis of unsaturated, j9-riether 0) Noarylidenepentaerythri, tri-233 was placed in a 11-three flask equipped with a stirrer, a reflux condenser, and a thermometer.
．． 9. Ethylene glycol 62〃, No-Itroquinone 0
．． After adding 0.5 g of Noguradolenesulfonic acid and 0.6 g of Noguradolenesulfonic acid, the mixture was heated and stirred at 90 to 95°C for 3 hours, and as a result of infrared analysis, most of the hydroxyl groups of 9+iL of light disappeared.

Bicarbonate of soda 2. ! Neutralize by adding 9/After this, 50-5
After washing twice with warm water at 5 °C, approximately 1') mmIIg
The pressure was reduced and water was distilled off.

Then, 05 g of tributylamine was added to obtain a light reddish brown, sill-like unsaturated polyether υ).

Unsaturated polyether (■) 1309.1-rimethylolpropanetrimercafutopropione) 20 #, chromium naphthenate (4% Cr) 1.5.9 were mixed uniformly, and 3 g of baramentanhydrocarbon oxide was added. Ta.

Gluing occurred after 11 minutes, followed by a slow exotherm reaching a maximum temperature of 69°C.

The obtained cured resin was semi-hard, rich in hardness, and strong.

In addition, in the above method, the same formulation except for trimethylolpropane trimercacitone 0 ropionate did not undergo gluing even after 3 days had passed.

Example 5 Synthesis of side chain unsaturated bond type resin @) Styrene 166,!
i', 2-hydroxypropiomethacrylate) 58.9
, azobisisobutyronitrile 2g, lauryl mercaptan 02g 1 benzene 126. ! 9 was charged, the temperature was gradually raised in a nitrogen stream, and polymerization was continued for 12 hours under reflux of benzene.

The temperature was then lowered to 60°C and hydroquinone 0.1.9
After adding 93 g of a 1:1 (number of moles of functional groups) addition product of allyl alcohol and 2,4-tolylene diisocyanate and 0.3 g of butyltin nolaurate,
After reacting at 60° C. for 5 hours, infrared analysis showed that free isocyanate groups completely disappeared.

Add 30g of noaryl phthalate and make about 200mm H
When the benzene was distilled off under reduced pressure of 100 g, a noaryl phthalate solution of a polymer having an allylic unsaturated bond in the side chain was obtained. This (ijl chain unsaturated bond type resin <E) is
Hazen color number is 400. The viscosity was 173 noise.

Resin■) 10o9, incyanuric acid (3-/Luca7')
propyl) ester 70,9, tin naphthenate (12%
5n) Mix 1.7.9 well and add Nclohexanone・e.
- Oxide 5E was added and uniformly dissolved.

Cell formation occurred after about 7 minutes, and heat generation continued until the maximum exothermic temperature reached 123°C.

The cured resin was yellowish brown and hard, with a Rockwell hardness (M scale) of 101.

In addition, in the above method, the same formulation except for incyanuric acid (3-mercaptozolopyl) ester is
Even after ``31,'' it didn't turn into an affair.

Example 6 - Vanadium pentoxide II was placed in a test tube, 10.9% of acidic dithyl phosphate was added, and the mixture was heated at 100°C for 30 minutes and then cooled. Reddish-brown vanadium pentoxide was precipitated, and a light green colored supernatant was formed. Obtained.

The composition of this dissolved material was unknown. The procedure was the same as in Example 3, except that the same amount of the above supernatant was used instead of the vananium acetylacetonate solution used in Example 3. As a result, the material was kelized in about 12 minutes and hardened with heat to become an elastic PIJ material.

Patent applicant: Showa Kobunshi Co., Ltd. Agent: Patent Attorney Sei Kikuchi

Claims (4)

[Claims] (1) A polyallylic compound having two or more allylic unsaturated bonds in one molecule and/or a polyallylidene compound having two or more 7lylidene unsaturated bonds in one molecule, (2) a polythiol compound having two or more thiol groups in one molecule; (3) organic peroxide, and (4) Metal compounds A composition that can be cured at room temperature.