JPS5853011B2 - Fragile urethane acrylate resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thixotropic urethane-modified acrylate resin composition.

Conventionally, unsaturated polyester resins have been generally known as radical polymerizable thermosetting resins, but in recent years, various urethane-modified resins with excellent mechanical performance and corrosion resistance have been used as substitutes for corrosion-resistant unsaturated polyester resins. Acrylate resins have been proposed.

By the way, unsaturated polyester resin is easy to handle, has good workability, and has excellent performance in reinforced plastics (FRP) combined with reinforcing materials such as glass, so it is used in ships, bathtubs, septic tanks, building materials, corrosion-resistant tanks, and pipes. , used in electrical parts, etc.

On the other hand, in the non-FRP field, there are also gel coat, paint,
It is used for a wide range of purposes including casting, adhesion, and lining.

The molding methods include band ray amplifier method, spray up method, FW method, premix method, prepreg method,
Various methods have been adopted, such as the MMD method, SMC method, BMC method, rotational molding method, and cast molding method.

Among these molding methods, unsaturated polyester resins used in the band lay-up method, spray-up method, FW method, etc. satisfy conditions such as workability, defoaming property, and impregnability into reinforcing materials. Therefore, relatively low-viscosity resin is used, but low-viscosity resin tends to flow down on vertical surfaces, causing a so-called "sagging" phenomenon.

``Tapping not only causes local variations in the resin content and thickness unevenness of the molded product, which has a very serious negative effect on the mechanical strength, but also causes non-uniform coatings for resins used in gel coats and paints. It causes encroachment.

Therefore, in order to prevent such "sagging", it is common practice to impart thixotropy to resins.

Thixotropy is defined by the fact that the apparent viscosity, expressed as the ratio of shear stress to shear rate, temporarily decreases due to external force, and more specifically, it flows when external force is applied, but remains stationary. It has a non-fluid property.

Currently, methods of adding and dispersing inorganic thixotropes such as anhydrous silica fine powder and asbestos-based fine powder, or organic thixotropes such as hydrogenated castor oil derivatives are known to impart thixotropy to unsaturated polyester resins. However, a method in which fine anhydrous silica powder having a silanol group and having a particle size of 10 to 20 mμ is dispersed on the surface is widely used.

When anhydrous silica fine powder is dispersed in unsaturated polyester resin, thixotropy is imparted because the anhydrous silica fine powder particles dispersed in the resin form a continuous structure through hydrogen bonds. It is explained that this structure is easily destroyed by a weak external force, and the viscosity temporarily decreases, but when the external force is removed, a continuous structure is restored.

In order to increase this viscosity effect, it is already known to add low molecular weight glycols such as ethylene glycol, flopylene glycol, and diethylene glycol, and polyols such as glycerin and trimethylolpropane as seeding aids.

For example, when ethylene glycol or diethylene glycol is used as a seeding agent, it is usually 0.2 to 3.0% by weight of anhydrous silica fine powder and 0.2 to 3.0% by weight of ethylene based on the unsaturated polyester resin composition. Species modification aids such as glycol are added.

However, at present, little knowledge has been obtained regarding imparting thixotropy to the aforementioned urethane-modified acrylate resins, and the compounds used as seed modification aids for the unsaturated polyester resins are urethane-modified acrylate resins. As a resin seed modification aid, it is either not effective at all, or even if it is, it is extremely small, so the amount added must be increased, and as a result, it has negative effects such as a significant reduction in the corrosion resistance, which is a characteristic of urethane-modified acrylate resins. effect.

As a method for determining and evaluating the presence or absence of an effect as a seed modification aid, there is a method of determining whether thixotropy disappears when cobalt naphthenate, which is an accelerator for curing at room temperature, is added to a seed modification resin composition. However, when evaluated using this method, in the case of unsaturated polyester resins, a decrease in thixotropy can be prevented by adding the above-mentioned coal mining agent, whereas in urethane-modified acrylate resins, the reduction in thixotropy can be prevented by adding the above-mentioned coal mining agent. However, the result is that thixotropy completely disappears.

When thixotropy is imparted by adding and dispersing anhydrous silica fine powder, the thickening effect and thixotropy are greatly influenced by the medium.

In general, the greatest thickening and speciation effects are obtained in nonpolar media with less possibility of hydrogen bonding, whereas
In polar media that tend to form hydrogen bonds, the thickening effect is not as great as in the former case, and in this case it is thought that this is because interactions between silanol groups and polar molecules occur and the bonds between silica particles are hindered.

As described above, the imparting of thixotropy by anhydrous silica fine powder is not uniform, and the blending amount of anhydrous silica fine powder, dispersion method, additives, etc. must be changed depending on the properties of the medium.

As mentioned above, the reason that ethylene glycol or glycerin is only effective as a seed modification aid for unsaturated polyester resins and urethane-modified acrylate resins, but not for the latter, is due to the difference between these two resins. The difference in molecular structure is that unsaturated polyester resins have a hydrogen-bonding hydroxyl group or carboxyl group at the end of the molecular chain, while urethane-modified acrylate resin has the end of the molecular chain blocked with an acryloyloxy group. This is also presumed to be due to the difference in polarity within the resin system due to the fact that the former is composed of ester bonds and the latter is composed of urethane bonds.

Further, since ethylene glycol or glycerin is extremely hydrophilic and increases the coal mining effect, it is never desirable to add a large amount in consideration of the consequences on corrosion resistance.

As mentioned above, unsaturated polyester resins and urethane-modified acrylate resins have different mechanisms for imparting coal mining properties, so no effective coal mining aid has yet been found for urethane-modified acrylate resins containing inorganic coal mining agents.

Finding a coal mining aid that increases the coal mining properties of urethane-modified acrylate resins containing inorganic coal mining agents and does not reduce resin performance such as corrosion resistance will give urethane-modified acrylate resins the same workability as unsaturated polyester resins. Needless to say, this resin is attracting attention and is strongly desired as it will significantly expand the field of application that takes advantage of the resin's excellent corrosion resistance and mechanical performance.

As a result of extensive research into imparting coal mining properties to urethane-modified acrylate resins, the present inventors have discovered a coal mining aid that enhances the coal mining effect and does not impair the various properties of the resin, and have arrived at the present invention.

That is, the present invention is based on the following general formula (■): (wherein, R1 is a divalent organic group, R2 is an organic diisocyanate residue, R3 is a polyhydric alcohol residue, R4 is hydrogen or a methyl group, and m is 5 or less. The number n represents an integer of 1 to 4.

) A thixotropic urethane modified acrylate resin containing an inorganic coal mining agent, which is a radically polymerizable thermosetting resin made by blending a urethane modified acrylate represented by , general formula CI), (II) and [■]: (wherein R1 and R2 are saturated or unsaturated hydrocarbon residues having 1 to 25 carbon atoms, R3 and R4 are hydrogen or/and methyl, n , m is an integer, and n+m≧9) This is a coal extractable urethane-modified acrylate resin composition blended with one or more compounds selected from the group consisting of compounds represented by the following formulas.

Examples of the compound represented by the general formula CI) used in the present invention include polyethylene glycol diacetate, polyethylene glycol di-n-propionate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacetate, and polyethylene glycol caproate. , polyethylene glycol caproate, polyethylene glycol di-2-ethylhexanoate, polyethylene glycol di-n-octanoate, polyethylene glycol gecalate, polyethylene glycol dilaurate, polyethylene glycol similystate, polyethylene glycol civalmitate, polyethylene Diesters of polyethylene glycol monocarboxylic acids such as glycol distearate, polyethylene glycol diralate, polyethylene glycol silicylate, polyethylene glycol gel calate, polyethylene glycol dibenzoate, polypropylene glycol diacetate, polypropylene glycol di-
n-propionate, polypropylene glycol diacrylate, polypropylene glycol diacrylate,
Polyethylene glycol dilaurate, polypropylene gelicol caproate, polypropylene glycol diacrylate, polypropylene glycol di-2-ethylhexanoate, polypropylene glycol di-n
- octanoate, polypropylene glycol diacetate, polypropylene glycol dilaurate, polyethylene glycol similystate, polypropylene glycol dipalmitate, polypropylene glycol distearate, polyethylene glycol diralate,
Polypropylene glycol monocarboxylic acid diesters such as polypropylene glycol diricinoate, polypropylene glycol shell kalate, polypropylene glycol diacetate, etc.; monocarboxylic acid diesters of polyethylene glycol/polypropylene glycol block copolymer There are various types.

Examples of the compound represented by the general formula (I[) include polyethylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol c-n-7'' propyl ether, polyethylene glycol c-n-butyl ether, polyethylene glycol di-
n-pentyl ether, polyethylene glycol di-n
-hexyl ether, polyethylene glycol di-n-
Octyl ether, polyethylene glycol cytesyl ether, polyethylene glycol dilauryl ether,
Polyethylene glycol dioleyl ether, polyethylene glycol distearyl ether, polyethylene glycol diglycidyl ether, polyethylene glycol-n-octyl pencil ether, polyethylene glycol decyl benzyl ether, polyethylene glycol lauryl benzyl ether, l-' IJ ethylene' )-1-l(methylphenyl)glycidyl ether, polyethylene glycol phenyl glycidyl ether, polyethylene glycol methyl allyl ether, polyethylene glycol methyl-n-propyl ether, polyethylene glycol methyl-n-butyl ether, etc. Dialkyl or diaryl or alkylaryl ethers of glycol, polypropylene glycol dimethyl ether, polypropylene glycol diethyl ether, polypropylene glycol di-n-propyl ether, polypropylene glycol di-n-butyl ether, polypropylene glycol di-n-pentyl ether, polyglopylene glycol Licor di n-hexyl ether, polypropylene glycol di-n-octyl ether, polypropylene glycol didecyl ether, polypropylene glycol dilauryl ether, polypropylene glycol distearyl ether, polypropylene glycol dioleyl ether, polypropylene glycol diglycidyl ether, polypropylene glycol ( methylphenyl)
Glycidyl ether, polypropylene glycol phenyl glycidyl ether, polypropylene glycol methyl glycidyl ether, polypropylene glycol methyl allyl ether, polypropylene glycol methyl-
Examples include dialkyl, diaryl, or alkylaryl ethers of polypropylene glycol typified by n-propyl ether, polypropylene glycol methyl-n-butyl ether, and polyethylene glycol/polypropylene glycol block copolymers.

Examples of the compound represented by the general formula (III) include polyethylene glycol methyl ether acetate, polyethylene glycol ethyl ether acetate, polyethylene glycol-n-butyl ether acetate, polyethylene glycol lauryl ether acetate, polyethylene glycol lauryl ether caproate,
polyethylene glycol oleyl ether laurate,
Polyethylene glycol oleyl ether stearate, polyethylene glycol stearyl ether stearate, polyethylene glycol stearyl ether laurate, polyethylene glycol lauryl ether benzoate, polyethylene glycol (n-octylphenyl) ether laurate, polyethylene glycol (n-octylphenyl) ether Stearate, polyethylene glycol (n-octylphenyl) ether oleate, polyethylene glycol (nonylphenyl) ether laurate, polyethylene glycol (nonylphenyl) ether stearate, polyethylene glycol (nonylphenyl) ether oleate, polyethylene glycol (dotesil) Monoalkyl or monoaryl of polyalkylene glycols such as phenyl)ether laurate, polyethylene glycol (dodecylphenyl)ether oleate, polypropylene glycol (n-octylphenyl)ether laurate, polypropylene glycol (n-octylphenyl)ether stearate Carvone ☆ of ether includes acid esters.

The above compounds used in the present invention may be used alone or in combination.
It is also possible to use more than one species in combination.

The average degree of polymerization of the polyoxyalkylene compound represented by the general formula CI, 1, (II, 1, or (I[I)), ie, the value of n+m, is 9 or more, preferably 14 or more.

When the average degree of polymerization of the polyoxyalkylene chain is less than 9, the effect as a coal mining aid is extremely small.

In terms of average molecular weight of polyoxyalkylene chain, it is 40
It is 0 or more, preferably 600 or more.

The upper limit of the value of n+m is not particularly limited, but is usually 5
The average molecular weight is desirably 0 or less, or 3000 or less in terms of average molecular weight.

Even if the value of n+m is 50 or more, the effect does not particularly increase,
Further, solubility is also lowered, which is not preferable.

Further, the blending amount of the coal mining aid in the present invention is 0.01 to 20.
0% by weight, practically 0.05~io.

Weight%.

If the blending amount is less than 0.01% by weight, the effect will be small;
If it exceeds 0.0% by weight, it will adversely affect various resin properties after curing.

The urethane-modified acrylate resin in the present invention has the following general formula [■]: (wherein, R1 is a divalent organic residue, R2 is an organic diisocyanate residue, R3 is a polyhydric alcohol residue, and R4 is hydrogen or A methyl group, m is a number of 5 or less, and n is an integer of 1 to 4.

This is a radical polymerizable thermosetting resin made by blending a urethane-modified acrylate represented by ) with a polymerizable monomer.

As a method for producing such a urethane-modified acrylate resin, for example, a compound having two or more alcoholic hydroxyl groups and an organic diisocyanate compound are mixed with 10H groups/
-Urethane modification obtained by reacting the terminal isocyanate group-containing urethane prepolymer with an alcoholic hydroxyl group-containing acrylate or methacrylate by reacting the resulting urethane prepolymer with an alcoholic hydroxyl group-containing acrylate or methacrylate. There is a method of dissolving acrylate in a polymerizable monomer.

2 alcoholic hydroxyl groups that can react with incyanate groups
Examples of compounds having 1 or more are ethylene glycol, propylene glycol, diethylene glycol, cyfropylene glycol, neopentyl glycol, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 1・4-butynediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-bentanediol, dibromoneopentyl glycol, dichloroneopentyl glycol, ■・4-cyclohexane dimetatool, 1・4-cyclohexanediol, 1.
2,6-hexanto IJol, bis(2-hydroxyethyl) terephthalate, his(2-hydroxyethyl)isophthalate, his(2-hydroxyethyl)orthophthalate, bis(2-hydroxypropyl)terephthalate, bis(2-hydroxyethyl) Hydroxypropyl) isophthalate, bis(2-hydroxypropyl)orthophthalate, bis(2,2-dimethyl-3-hydroxypropyl)terephthalate, bis(2,2-dimethyl-3-hydroxypropyl)isophthalate, bis(2-hydroxypropyl)isophthalate,・2-dimethyl-3-hydroxypropyl) orthophthalate, bis(2-(2-hydroxyethoxy)ethyl) terephthalate, bis(2-(2-hydroxypropoxy)propyl) terephthalate, bis[2-(2-hydroxyethoxy) ) Ethyl coisophthalate, bis[2(2-hydroxypropoxy)propylcoisophthalate, bis(
2-(2-hydroxyethoxy)ethyl]orthophthalate, bis(2-(2-hydroxypropoxy)propyl)orunphthalate, terephthalic acid oligoester,
Isophthalic acid oligoester, orthophthalic acid oligoester, adipic acid oligoester, sepatic acid oligoester, dodecanedicarboxylic acid oligoester, 2.
2-bis(4-(2-hydroxypropoxy)phenyl]propane, 2,2-(4-(2-hydroxyethoxy)phenyl)furopane, bis[4-(2-hydroxypropoxy)phenylcomethane, bis(4 -(2-hydroxyethoxy)phenylcomethane, bis[2,6-Schiff"o -E -4-(2-hydroxypropoxy)phenylcomethane, 2,2-bis[2,6-dipromo4-
(2-hydroxypropoxy)phenyl]propane, 2
・2-bis(4-hydroxycyclohexyl)furopane, 2,2-bis(4-(2-hydroxyethoxy)cyclohexyl)furopane, 2,2-bis(4-(2-hydroxypropoxy)cyclohexyl)propane, etc. .

Examples of organic diisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-)lylene diisocyanate, diphenylmethane-4,4'-diincyanate, diphenyl ether-4,4'-diincyanate, metaxylylene diisocyanate, and hexamethylene diinocyanate. Examples include cyanate, 1,3-bis(incyanatomethyl)cyclohexane, and the like.

The reaction ratio of the compound having two or more alcoholic hydroxyl groups and the organic diisocyanate is preferably less than 1 in molar ratio of hydroxyl groups to incyanate groups (-OH group/-NCO group <1 (molar ratio)). It is 0.4-0.8.

Examples of media that are inert to incyanate groups in the above reaction include polymerizable monomers such as styrene, vinyltoluene, methyl acrylate, methyl methacrylate, diallyl phthalate, and non-polymerizable monomers such as benzene, toluene, and methylene chloride. Examples include sexual compounds.

The above reaction is carried out at a reaction temperature of 20-80'C, especially 50-80'C.
It is desirable to do so.

The alcoholic hydroxyl group-containing acrylate or methacrylate that can react with the terminal isocyanate group-containing urethane prepolymer obtained by the above reaction is one obtained by reacting acrylic acid or methacrylic acid or a functional derivative thereof with a polyhydric alcohol, or an acrylate There are those obtained by reacting an acid or methacrylic acid with a compound having an epoxy group.

Examples of such compounds include ethylene glycol monoacrylate, ethylene glycol monomethacrylate, propylene glycol monoacrylate, propylene glycol monomethacrylate, 1,3-propanediol monoacrylate, 1,3-propanediol monomethacrylate, 1,3- Butanediol monoacrylate, 1,3-butanediol monomethacrylate, 1,4-butanediol monoacrylate, 1,4
-butanediol monomethacrylate, 1,6-hexanethiol monoacrylate, 1,6-hexanesiol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate,
Monoacrylates and monomethacrylates of dihydric alcohols such as dipropylene glycol monoacrylate, dipropylene glycol monomethacrylate, polyethylene glycol monoacrylate or monomethacrylate, polypropylene glycol monoacrylate or monomethacrylate, trimethylolethane monoacrylate, trimethylolethane monoacrylate Methacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, trimethylolethane bis(acrylate), trimethylolpropane bis(methacrylate), glycerin monoacrylate, glycerin monomethacrylate, glycerin bis(acrylate), glycerin bis(meth) Monoacrylates and bisacrylates, monomethacrylates and bismethacrylates of trihydric alcohols such as (acrylate), or pentaerythritol bis(acrylate), pentaerythritol bis(methacrylate), pentaerythritol tris(acrylate), pentaerythritol tris(methacrylate) Bis-acrylates and tris-acrylates, bis-methacrylates and tris-methacrylates of polyhydric alcohols having a valence of 4 or more, such as polyhydric alcohols.

The reaction ratio of the urethane prepolymer containing a terminal isocyanate group and the alcoholic hydroxyl group-containing acrylate or methacrylate is such that the hydroxyl group is equivalent to or more than the inocyanate group (-OH group/NCO group ≧1 (molar ratio)), preferably 1 It is .05 to 1.8.

The reaction is carried out in the medium used in the first stage reaction, in another medium, or in the absence of a medium.

It is desirable that the reaction temperature is 80°C or less.

The polymerizable monomers to be blended with the urethane-modified acrylate include styrene monomers such as styrene, vinyltoluenechlorostyrene, tert-7" tylstyrene, and divinylbenzene, methyl methacrylate, ethyl methacrylate, These include acrylic acid ester monomers such as methyl acrylate and ethyl acrylate, allyl monomers such as diallyl phthalate and triallyl cyanurate, vinyl acetate, and dibutyl fumarate.

The urethane-modified acrylate can then be mixed with a polymerizable monomer to form a urethane-modified acrylate resin.

However, when the second stage reaction of the prepolymer containing a terminal inocyanate group and the acrylate or methacrylate containing a hydroxyl group is carried out in a polymerizable monomer that is inert to isocyanate groups, after the reaction is completed, the monomer Unless the body is removed, the urethane-modified acrylate is a urethane-modified acrylate resin mixed with a polymerizable monomer.

When the second stage reaction is carried out in a non-polymerizable compound inert to the incyanate group, the compound is mixed with the polymerizable monomer after or without removal.

The blending ratio of urethane-modified acrylate and polymerizable monomer is 90:10 to 20:80 (wt%).

Another method for producing a urethane-modified acrylate resin is to react an organic diisocyanate with a hydroxyl group-containing acrylate or methacrylate in an amount where the hydroxyl group is less than equimolar to the incyanate group (-OH group/-HC0 group <1), Next, there is a method in which a urethane-modified acrylate obtained by reacting with a compound having two or more alcoholic hydroxyl groups is dissolved in a polymerizable monomer.

The urethane-modified acrylate resin in the present invention is not limited to that produced by the above method.

Examples of inorganic coal mining agents used in the present invention include anhydrous silica fine powder and asbestos coal mining agents.

The amount of the inorganic coal mining agent added to the urethane-modified acrylate resin is 0.1 to 1
0.0% by weight, preferably 0.3-5.0% by weight.

The coal mining urethane-modified acrylate resin composition of the present invention not only has excellent thixotropy and thixotropy stability, but is also a compound with lower hydrophilicity than conventional coal mining aids and Since the amount is small, it has extremely excellent corrosion resistance such as boiling water resistance and alkali resistance.

The coal-minable urethane-modified acrylate resin composition of the present invention may contain polymerization inhibitors, curing accelerators, light stabilizers, fillers, pigments, flame retardants, etc. as necessary to produce laminate molded products, FW, etc.
Molded products, premix molded products, prepreg molded products, MM
It can be widely used in molded products such as D-molded products, rotational molded products, SMC molded products, and BMC molded products, as well as applications such as adhesives, paints, gel coats, linings, and casting.

In order to explain the present invention in more detail, Examples will be given below, but of course the present invention is not limited thereto.

In the examples, PHR means parts by weight based on 100 parts by weight of urethane-modified acrylate resin in the case of coal mining rules, and parts by weight based on 100 parts by weight of urethane-modified acrylate resin containing a coal mining agent in the case of coal mining aids.

Measurement of viscosity and thixotropy is based on JIS K-6901.
Measurement was carried out using a B-type rotational viscometer in a constant temperature water bath at 25°C.

■6o and ■6 are the viscosity (poise) at 600 rotations and 6 rotations, respectively.

As cobalt naphthenate, cobalt naphthenate, mineral spirit solution (cobalt content 6% by weight, hereinafter C
(abbreviated as o-N) was used.

In addition, POE in the table indicates polyoxyethylene chain, MW
It is the average molecular weight.

Example 1 In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 641 parts of styrene and 3 parts of bis(3-hydroxy-2.2-dimethylpropyl) terephthalate were added.
38 parts of hydroquinone and 0.16 parts of hydroquinone were charged, the temperature was raised to 50'C without stirring, and 2,4-tolylene diisocyanate (trade name: Dismodur T-10) was added.
0 (manufactured by Nippon Polyurethane Industry ■)) at a reaction temperature of 80☆? The mixture was added dropwise while maintaining the temperature below .degree. C., and a urethane prepolymer containing terminal isocyanate groups dissolved in styrene was obtained in about 1 hour.

Next, 286 parts of ethylene glycol monomethacrylate was added dropwise at a reaction temperature of 80° C. or lower, and the reaction was completed in about 1 hour and 30 minutes.

The viscosity of the obtained urethane-modified acrylate resin was 5.5.
It was Poise.

Adding styrene to the resin results in a styrene content of 45% by weight.
Add 0.5 PHR of anhydrous silica fine powder [trade name: Aerosil #200 (manufactured by Nippon Aerosil ■) so that it becomes And so.

Various coal mining aids shown in Table 1 were added to the resin at 0.2 PH.
R was added and the thixotropy was measured.

The results are shown in Table 1. It is clear that the addition of the coal mining aid of the present invention significantly increases the thixotropy and that the coal mining properties do not disappear even after the addition of Co--N.

Example 2 Same coal-bearing urethane-modified acrylate as in Example 1) [J
0.2 PHR of polyethylene glycol diacrylate and polyethylene glycol dimethacrylate having different molecular weights were added to I'R8, and differences in effects due to molecular weights were investigated.

The results are shown in Table 2.

As is clear from Table 2, when the molecular weight of the polyoxyethylene chain is less than 400, that is, when the degree of polymerization is 8 or less, the effect is significantly reduced.

Example 3 In a reaction vessel similar to Example 1, 64.8 parts of 2,2-bis(4-hydroxycyclohexyl)propane and 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane [trade name: Uniol DB-350 (manufactured by NOF ■)) 258 parts, styrene 638 parts, 2,4-tolylene diisocyanate [Product name: Dismodur T-100
(manufactured by Nippon Polyurethane ■) and 286 parts of ethylene glycol monoacrylate were charged, and a urethane-modified acrylate resin was obtained in the same manner as in Example 1.

The viscosity of the obtained resin was 5.2 poise.

Adding styrene to the resin results in a styrene content of 45% by weight.
Dilute to give anhydrous silica fine powder [Product name: Aerosil #200 (manufactured by Nippon Aerosil ■)] 0.5PHR
The resin was added and sufficiently dispersed using a three-roll roll to obtain a coal-collectable urethane-modified acrylate resin (B).

Various coal mining aids shown in Table 3 were added to the resin as coal mining aids, and the effect of the amount added on the thixotropy was investigated.

The results are shown in Table 4.

It is clear that even if the amount of the coal mining aid of the present invention is reduced, the results are still good.

Example 4 0.5 PHR of various coal mining aids were added to the same coal mining urethane-modified acrylate resin (A) as in Example 1, and methyl ethyl ketone peroxide [55% dimethyl phthalate solution, trade name: Sanhard SL (Sanken Co., Ltd.) Made by Kako ■)) 1.
A test piece (3 mm x 25 mm x 80 mm) was cut out from a casting plate prepared according to a conventional method by curing at room temperature using a combination of 0PHR, Co-No, and 5rPHR.
Water resistance was tested in boiling water at °C.

The results are shown in Table 4. It is clear that the coal mining agent according to the present invention has extremely excellent water resistance.

Example 5 In a reaction vessel similar to Example 1, 2,2-bis[4-(2
-Hydroxyglopoxyphenyl]furopane (mentioned above)
344 parts of styrene, 638 parts of styrene, 348 parts of 2,4-tolylene diinocyanate (mentioned above) and 286 parts of ethylene glycol monoacrylate were charged, and the same procedure as in Example 1 was carried out to obtain a urethane-modified acrylate resin. It was diluted by adding styrene so that the amount was 45% by weight.

The viscosity of the resin was 2.4 poise.・Add 0.5 PHR of asbestos-based coal mining agent [trade name: Calidria RG-244 (manufactured by Union Carbide Co., Ltd.)] to the resin, and thoroughly disperse it with three rolls to obtain coal mining property urethane-modified acrylate Jutsu Q. Ta.

Next, a coal mining aid was added and the thixotropy was measured.

The results are shown in Table 5.

It is clear that the coal mining aid of the present invention is also effective in asbestos-based coal mining agent-containing urethane-modified acrylate resins.

Claims (1)

[Claims] 1 The following general formula (■): (wherein, R7 is a divalent organic group, R2 is an organic diisocyanate residue, R3 is a polyhydric alcohol residue, R4 is hydrogen or a methyl group, m is a number of 5 or less, and n is an integer of 1 to 4. General formulas (I), (n), and (■): (wherein, R1 and R2 are saturated or unsaturated acrylate resins having 1 to 25 carbon atoms). A thixotropic urethane containing one or more compounds selected from the group consisting of hydrocarbon residues, R3 and R4 are hydrogen or/and methyl, n and m are integers, and n+m≧9) Modified acrylate resin composition.