JPS5853010B2 - 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,
In addition to being easy to work with, reinforced plastics (FRP) combined with reinforcing materials such as glass have excellent performance.
While it is used for ships, bathtubs, septic tanks, building materials, corrosion-resistant tanks, pipes, electrical parts, etc., it is also used in a wide range of non-FRP fields such as gel coats, paints, casting, adhesives, and linings. There is.

In addition, the forming methods include band lay-up method, spray-up method, filament winding method,
Premix method, prepreg method, Matsushido die method, S
Methods such as MC method, BMC method, rotational molding method, and cast molding method are adopted.

Among these molding methods, unsaturated polyester resins used in the band lay-up method, spray amplification method, filament winding method, etc. In order to meet the requirements, a relatively low-viscosity resin is used, but a so-called "sagging" phenomenon occurs in which the low-viscosity resin flows down on vertical surfaces.

'Sag' causes local variations in the resin content and uneven thickness of the molded product, which not only has a very serious negative effect on the mechanical strength, but also causes uneven coating film for gel coat and paint resins. This is the cause of encroachment.

Therefore, in order to prevent such "sag", 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. It has the property of not flowing if left alone.

Currently, there is a known method for imparting thixotropy to unsaturated polyester resins by adding and dispersing inorganic coal-producing agents such as anhydrous silica fine powder and asbestos-based fine powder, or organic coal-producing agents such as hydrogenated castor oil derivatives. However, a method in which anhydrous silica fine 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 reproduced.

In order to increase this rocking effect, it is already known to add low molecular weight glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol, and polyols such as glycerin as coal mining aids.

For example, when ethylene glycol or diethylene glycol is used as a coal mining aid, usually 0.2 to 3.0% by weight of anhydrous silica fine powder and 0.2 to 30% by weight of the unsaturated polyester resin composition are used. Adds coal mining aid.

However, at present, there is almost no knowledge regarding imparting thixotropy to the aforementioned urethane-modified acrylate resin, but the compound used as a coal mining aid for the unsaturated polyester resin mentioned above is As an agent, it has no effect at all, or even if it does, it has very little effect.

A method for determining and evaluating whether or not it is effective as a coal mining aid is to determine whether thixotropy disappears when cobalt naphthenate, which is an accelerator for curing at room temperature, is added to a coal mining resin composition. However, when evaluated using this method,
In unsaturated polyester resins, a decrease in thixotropy can be prevented by adding the coal mining aid, whereas in urethane-modified acrylate resins, the thixotropy does not decrease at all even if the coal mining aid is added. The result is that it disappears.

By the way, when thixotropy is imparted by adding and dispersing anhydrous silica fine powder, the thickening effect and thixotropy are largely influenced by the properties of the medium.

In general, the greatest thickening and coal mining effects are obtained in media with a low possibility of hydrogen bonding, whereas in polar media with a tendency to form hydrogen bonds, the thickening effect is not as great in the former case; This is thought to be due to the interaction between silanol groups and polar molecules, which prevents the bonding between silica particles.

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 why ethylene glycol and glycerin are effective as coal mining aids only for the former and not for the latter is due to the molecular structure of these two resins. The difference is that unsaturated polyester resins have hydrogen-bonding hydroxyl groups and carboxyl groups at the ends of their molecular chains, while urethane-modified acrylate resins have their molecular chain ends blocked with acryloyloxy groups. It is also assumed that this is 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.

As described above, since the mechanisms for imparting coal mining properties are different between unsaturated polyester resins and urethane-modified acrylate resins, an effective coal mining aid for urethane-modified acrylate resins containing fine anhydrous silica powder has not yet been found.

Finding an effective coal mining aid that increases the coal mining properties of urethane-modified acrylate resins containing fine anhydrous silica powder will give urethane-modified acrylate resins the same workability as unsaturated polyester resins and improve the resin's excellent properties. Corrosion resistance,
Needless to say, it is attracting attention and is strongly desired as a device that will significantly expand the field of application that takes advantage of mechanical performance.

As a result of intensive research into imparting coal mining properties to urethane-modified acrylate resins, the present inventors found that a coal mining aid that enhances the coal mining effects of not only anhydrous silica fine powder but also asbestos-based coal mining agents and does not impair the performance of other resins. They discovered this and arrived at the present invention.

That is, the present invention provides the following general formula (I): (wherein, R1 is a divalent organic group, R2 is an organic diincyanate residue, R2 is a polyhydric alcohol residue, R4 is hydrogen or a methyl group, and m is a A number of 5 or less, 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 , polyethers having one alcoholic hydroxyl group in the molecule selected from the group consisting of (1) to (■) below, or alcoholic hydroxyl group in the molecule selected from the group consisting of (V(1-4X)) below. This is a carbonable urethane-modified acrylate resin composition blended with polyethers containing two or more hydroxyl groups.

(1) Alkylene oxide adduct of monohydric alcohol (i
i) Alkylene oxide adduct of phenol or substituted phenol (iii) Alkylene oxide adduct of monovalent fatty acid 0v) Alkylene oxide adduct of sorbitan trifatty acid ester (v) Alkylene oxide adduct of fatty acid ester of dihydric or higher polyhydric alcohol (V!l) Polyalkylene glycol (v+i) Alkylene oxide adduct of trivalent or higher polyhydric alcohol 9ii) Alkylene oxide adduct of sorbitan mono- or difatty acid ester 11X) Alkylene of trivalent or higher polyhydric alcohol fatty acid ester Oxide adduct Polyethers containing an alcoholic hydroxyl group in the molecule used in the present invention include polyethers containing one alcoholic hydroxyl group in the molecule or polyethers containing two or more alcoholic hydroxyl groups in the molecule. There are polyethers.

Polyethers containing one alcoholic hydroxyl group in the molecule used in the present invention include (1) alkylene oxide adducts of one alcohol, such as polyoxyethylene monomethyl ether, polyoxyethylene monoethyl ether, polyoxy Ethylene oxide adducts of lower monohydric alcohols such as ethylene mono-n-propyl ether and polyoxyethylene mono-n-butyl ether, polyoxyethylene monooctyl ether, polyoxyethylene monodecyl ether, polyoxyethylene monolauryl ether, polyoxy Ethylene oxide adducts of higher monohydric alcohols such as ethylene monotritethyl ether, polyoxyethylene monocetyl ether, polyoxyethylene monostearyl ether, polyoxyethylene monooleyl ethyl, polyoxyethylene castor oil, (ii) phenol or substituted phenol Alkylene oxide adducts 16 of, for example, polyoxyethylene mono(octylphenyl)-ether, polyoxyethylene-mono(nonylphenyl)-ether, polyoxyethylene-mono(tesylphenyl)-ether, polyoxyethylene-mono(p - ethylene oxide adducts of phenols or substituted phenols, such as -cumylphenyl)-ether, polyoxyethylene mono(methylphenyl)-ether, polyoxyethylene-mono(ethylphenyl)-ether; For example, polyoxyethylene monoacetate, polyoxyethylene mono-n-propionate,
Polyoxyethylene monoacrylate, polyoxyethylene monomethacrylate, polyoxypropylene monoacetate, polyoxypropylene mono-n-propionate, polyoxyfuropylene monoacrylate, polyoxyethylene monocaproate, polyoxyethylene monooctanoate, poly Oxyethylene monoacetate, polyoxyethylene monolaurate, polyoxyethylene monomyristate, polyoxyethylene monopalmitate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene monolysylate, poly ethylene oxide or propylene oxide adducts of fatty acids such as oxyethylene monoercarate, ov) alkylene oxide adducts of sorbitan trifatty acid esters, such as polyoxyethylene sorbitan trilaurate, polyoxyethylene sorbitan) IJ harmitate, polyoxyethylene sorbitan tri Stearate, ethylene oxide adducts of sorbitan triesters such as polyoxyethylene sorbitan trioleate, (v) alkylene oxide adducts of fatty acid esters of dihydric or higher polyhydric alcohols, such as polyoxyethylene trimethylol propane dilaurate, polyoxypropylene Trimethylolpropane dilaurate, polyoxyethylene trimethylolpropane dilaurate
Polyoxypropylene trimethylol propane dilarate, polyoxyethylene hentaerythritol trilaurate, polyoxypropylene pentaerythritol trilaurate, polyoxyethylene pentaerythritol tristearate, polyoxypropylene pentaerythritol tristearate, Alkylene oxide adducts of trihydric or higher polyhydric alcohol esters such as oxyethylene pentaerythritol trioleate and polyoxypropylene pentaerythritol trioleate, as well as polytrimethylene glycol monoalkyl or aryl ethers, polytrimethylene glycol monocarboxylic acid esters, It broadly includes polytetramethylene glycol monoalkyl or aryl ether, polytetramethylene glycol monocarboxylic acid ester, salani, and, although slightly more effective, ethylene oxide or propylene oxide adducts of secondary amines.

The above compounds are exemplified, and of course the present invention is not limited to these compounds, and it is also possible to use two or more of them in combination.

Regarding polyethers containing one alcoholic hydroxyl group in the molecule used in the present invention, the larger the number of moles of alkylene oxide added, that is, the higher the molecular weight, the greater the effect as a coal mining aid. If the molecular weight is too large, the solubility in the resin composition will decrease, so it is usually desirable to use one with a molecular weight of about 200 to about 3000. Also, if the number of moles of alkylene oxide added is indicated by n, then n = 5. It is desirable to use a range of 50 to 50.

The polyethers containing two or more alcoholic hydroxyl groups in the molecule used in the present invention include (vD polyalkylene glycol, for example polyethylene glycol with a molecular weight of about 200 to about 2,500, polypropylene glycol with a molecular weight of about 200 to about 2,000, Molecular weight about 400 to about 2000
polytrimethylene glycol and polytetramethylene glycol, polyethylene glycol/polypropylene glycol block copolymers with a molecular weight of about 200 to about 12,000, 9ii) alkylene oxide adducts of trihydric or higher polyhydric alcohols, e.g. Ethylene oxide or/and propylene oxide adduct of glycerin, molecular weight about 200 to about 20
00 trimethylolpropane ethylene oxide or/and propylene oxide adduct, molecular weight approx. 200
~ Alkylene oxide adducts of trihydric or higher polyhydric alcohols, such as ethylene oxide and/or propylene oxide adducts of pentaerythritol of about 2000, $
ii) alkylene oxide adducts of sorbitan mono- or difatty acid esters, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate, polyoxyethylene Molecular weight of sorbitan dilaurate, polyoxyethylene sorbitan dipalmitate, polyoxyethylene sorbitan distearate, polyoxyethylene sorbitan diralate, etc. from about 600 to about 4
000 alkylene oxide adducts of sorbitan mono- or difatty acid esters, and 0x) alkylene oxide adducts of fatty acid esters of trihydric or higher polyhydric alcohols, such as polyoxyethylene trimethylolpropane monooleate, polyoxyethylene trimethylolpropane Monolaurate, polyoxyethylene pentaerythritol monolaurate, polyoxyethylene pentaerythritol monostearate, polyoxyethylene pentaerythritol monooleate, polyoxyethylene pentaerythritol dilaurate, polyoxyethylene pentaerythritol distearate, polyoxyethylene Pentaerythritol diralate, polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, polyoxyethylene vine★
・Molecular weight of hythol dilaurate, polyoxyethylene sorbitol distearate, polyoxyethylene sorbitol dioleate, polyoxyethylene sorbitol trilaurate, polyoxyethylene sorbitol tristearate, polyoxyethylene sorbitol trioleate, etc. from about 300 to about It broadly includes alkylene oxide adducts of fatty acid esters of polyhydric alcohols having a valence of 4,000 or more.

Furthermore, alkylene oxide adducts of primary amines and alkylene oxide adducts of hydroxyl group-containing amines such as triethanolamine and jetanolamine are also included, although the effect is slightly inferior.

The molecular weight of these compounds, expressed as the number of moles of ethylene oxide or propylene oxide added, is n=5 to 200.

Of course, the molecular weight is not limited to this range, but if the molecular weight is less than 200, it will be less effective as a coal mining aid, and if the molecular weight is too large, the solubility of the resin composition will decrease, which is not desirable.

The above compounds are exemplified, and of course the present invention is not limited to these compounds, and two or more thereof can also be used in combination.

In addition, in the present invention, the blending amount of the polyethers is 0.0% based on the urethane-modified acrylate resin containing an inorganic coal mining agent.
1 to 20.0% by weight, especially 0.105 to 50% by weight.

If the amount is less than 0.01% by weight, the effect will be small, and if it exceeds 20.0% by weight, it will adversely affect the performance of the cured resin composition, which is not preferred.

The urethane-modified acrylate resin in the present invention has the following general formula (I): (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 -OH groups/
-Urethane modification obtained by reacting NCO groups <1 (molar ratio) in a medium inert to isocyanate groups and reacting the obtained terminal isocyanate group-containing urethane prepolymer with 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 ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-propanediol, ■,3-butanediol, 1,4-butanediol, -Butynediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-bentanediol, cyfuromoneopentyl glycol, dichloroneopentyl glycol, ■,4-cyclohexane dimetatool, 1,4 -Cyclohexanediol, 1.2.
6-hexanetriolbis(2-hydroxyethyl)
Terephthalate, bis(2-hydroxyethyl) inphthalate, bis(2-hydroxyethyl) orthophthalate, bis(2-hydroxypropyl) terephthalate, bis(2-hydroxypropyl) isophthalate, bis(2-hydroxypropyl) orthophthalate , bis(2,2-dimethyl-3-hydroxyfurobyl) terephthalate, bis(2,2-dimethyl-3-hydroxypropyl)isophthalate, bis(2,2-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)propyl coisophthalate, bis(2-(2
-hydroxyethoxy)ethyl] orthophthalate, bis(2-(2-hydroxypropoxy)propylforthophthalate, terephthalic acid oligoester, isophthalic acid oligoester, orthophthalic acid oligoester,
Adipic acid oligoester, sebacic acid oligoester, toticanedicarboxylic acid oligoester, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 2,2-(4-(2-hydroxyethoxy)phenyl) Propane, bis[4(2-hydroxypropoxy)
Phenylcomethane, bis(4-(2-hydroxyethoxy)phenylcomethane, bis[2,6-dibromo-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,
Examples include 2,2-bis[4-(2-hydroxypropoxy)cyclohexyl]propane.

Examples of organic diisocyanate compounds include 2,4-tolylene diisocyanate, 2°6-tolylene diisocyanate, diphenylmethane-4,4' diinocyanate, diphenyl ether-4,4' diisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, Examples include 3-bis(isocyanatomethyl)cyclohexane.

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 inert to the isocyanate groups used 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 compounds.

The above reaction is carried out at a reaction temperature of 20 to 80°C, especially 50 to 80°C.
It is desirable to use C.

The alcoholic hydroxyl group-containing acrylate or methacrylate that can react with the terminal isocyanate group-containing urethane polymer 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 gellicol monomethacrylate, 1,3 propanediol monoacrylate, 1,3 propanediol monomethacrylate, and 1,3 butane. Diol monoacrylate, 1,3-butanediol monomethacrylate, 1
・4-butanediol monoacrylate, 1,4-butanediol monomethacrylate, 1,6-hexanediol monoacrylate, 1,6-hexanesiol monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, dipropylene glycol monoacrylate, Monoacrylates and monomethacrylates of dihydric alcohols such as dipropylene glycol monomethacrylate, polyethylene glycol monoacrylate or monomethacrylate, polypropylene glycol monoacrylate or monomethacrylate, trimethylolethane monoacrylate, trimethylolethane monomethacrylate, trimethylolfuropane Monoacrylate, trimethylolpropane monomethacrylate, trimethylolethane bis(acrylate), trimethylolpropane bis(
Monoacrylates and bisacrylates, monomethacrylates and bismethacrylates of trihydric alcohols, such as glycerin monoacrylate, glycerin monomethacrylate, glycerin bis(acrylate), glycerin bis(methacrylate), monomethacrylate and bismethacrylate, or pentaerythritol bis(acrylate)
, pentaerythritol bis(methacrylate), pentaerythritol tris(acrylate), pentaerythritol tris(methacrylate), bis-acrylates and tris-acrylates of polyhydric alcohols of four or more valences, or bis-methacrylates and tris-methacrylates.

The reaction ratio of the urethane prepolymer containing a terminal inocyanate group and the alcoholic hydroxyl group-containing acrylate or methacrylate is such that the hydroxyl group is equivalent to or more than the isocyanate group (-〇H group/NCO group≧1 (molar ratio)), preferably It is 1.05 to 1.8.

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

The reaction temperature is preferably 80°C or lower.

The polymerizable monomers to be blended with the above urethane-modified acrylate include styrene monomers such as styrene, vinyltoluene, chlorostyrene, tert-butylstyrene, and cyhinylbenzene, methyl methacrylate, ethyl methacrylate, and acrylic. 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 above urethane-modified acrylate can be mixed with these polymerizable monomers to form a urethane-modified acrylate resin.

However, when the second stage reaction of the prepolymer containing a terminal isocyanate 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 is Unless 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 isocyanate 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 combine an organic diisocyanate and a hydroxyl group-containing acrylate or methacrylate in which the hydroxyl group is less than the equivalent mole of the incyanate group (-OH group/-NCO group <1 (molar ratio)). 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 inorganic thiomorphic 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 enhances the coal mining effect of the inorganic coal mining agent by blending polyethers containing alcoholic hydroxyl groups in the molecule as a coal mining aid, and hardens cobalt naphthenate, etc. Even with the addition of accelerators, the decrease in thixotropy is very small, and
It has the characteristics that it does not impair various properties such as water resistance and corrosion resistance of the resin composition after curing.

The coal-bearing 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, filament-wining molded products, etc. For molded products such as mix molded products, prepreg molded products, matte die molded products, rotary molded products, SMC molded products, and 8MC molded products, as well as applications such as adhesives, paints, gel coats, linings, and casting. Can be used widely.

EXAMPLES In order to explain the present invention in further detail, examples are given below.

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

The viscosity and thixotropy were measured in accordance with JIS-6901 using a B-type rotational viscometer in a constant temperature water bath at 25°C.

v6o and ■6 are the viscosity (voice) 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 the table, the following symbols mean the following.

EO: Ethylene oxide PO: Propylene oxide n: Number of moles added of alkylene oxide MW: Average molecular weight Reference example 1 Preparation of coal extractable urethane-modified acrylate tree MAIN In a reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. , 641 parts of styrene, 1-33 parts of bis(3-hydroxy-2,2-dimethylpropyl)terephthalate
8 parts and 0.16 parts of hydroquinone were charged, the temperature was raised to 50'C while stirring, and 2,4-tolylene diisocyanate [trade name: TAIS MODULE T-1] was added.
00 (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) was added dropwise while maintaining the reaction temperature at 80° C. or lower to obtain a urethane prepolymer containing terminal isocyanate groups dissolved in styrene in about 1 hour.

Next, ethylene glycol monomethacrylate-428
6 parts was added dropwise at a reaction temperature of 80°C or lower, and the reaction was continued for about 1 hour.
Completed in 0 minutes.

The viscosity of the obtained resin was 5.5 poise.

Adding styrene to the resin results in a styrene content of 45% by weight.
Dilute to give 0.5P of anhydrous silica fine powder [Product name: Aerosil #200 (manufactured by Nippon Aerosil Co., Ltd.)]
HR was added and the mixture was sufficiently dispersed using a three-roll roll to obtain a coal-bearing urethane-modified acrylate resin (4).

Example 1 0.2P of various polyoxyethylene monoalkyl ethers shown in Table 1 was added to coal-minable urethane-modified acrylate resin N containing 0.5PHR of anhydrous silica fine powder.
HR was added and the thixotropy was measured.

The results are shown in Table 1.

For comparison, the thixotropy was significantly increased by the addition of the polyoxyethylene monoalkyl ethers according to the present invention, and the cases where ethylene glycol, glycerin, or dipropylene glycol were added were also shown. It can be seen that the coal mining property does not disappear even after addition.

Example 2 Same as Example 1, coal extractable urethane modified acrylate-hm
0.2 PHR of various polyoxyethylene mono-substituted phenyl ethers were added to pig 1';), and the thixotropy was measured.

The results are shown in Table 2. Example 3 In the same manner as in Example 1, 0.2 PHR of various polyoxyethylene monofatty r-acid esters were added to the coal-bearing urethane-modified acrylate tree A), and the thixotropy was measured.

The results are shown in Table 3. Example 4 Similar to Example 1, 0.2 PHR of polyethers containing two alcoholic hydroxyl groups in the molecule shown in Table 4 was added to urethane-modified acrylate Jugetsu Wm, and the thixotropy was measured. are shown in Table 4.

It can be seen that the addition of the coal mining aid according to the present invention significantly increases the thixotropy and that the coal mining properties do not disappear even after the addition of Co--N.

Example 5 In the same manner as in Example 1, 0.2 PHR of various polyoxyethylene sorbitan esters were added to coal-minable urethane-modified acrylate resin N, and the thixotropy was measured.

The results are shown in Table 5. Example 6 In the same manner as in Example 1, 0.2 PHR of alkylene oxide adducts of various polyhydric alcohols were added to the coal extractable urethane-modified acrylate resin powder, and the thixotropy was measured.

The results are shown in Table 6. Reference Example 2 Preparation of coal extractable urethane-modified acrylate tree B) In the same reaction vessel as in Reference Example 1, 64. s part, 2・2-bis(1-(
2-Hydroxypropoxy)phenyl]furopane [Product name: Uniol DB350 (manufactured by NOF Corporation)] 25
8 parts of styrene, 638 parts of styrene, 348 parts of 2,4-tolylene diisocyanate [trade name: Teis module T-100 (manufactured by Nippon Polyurethane Industries Co., Ltd.]) and 286 parts of ethylene glycol monoacrylate were used as raw materials to prepare a resin in the same manner. Obtained.

The viscosity of the obtained resin was 5.2 poise.

The resin styrene was added and diluted so that the styrene content was 45% by weight, and anhydrous silica fine powder [trade name: Aerosil #200 (manufactured by Nippon Aerosil Co., Ltd.)] 0.5PH was added.
R was added and thoroughly dispersed using a three-roll roll to obtain a coal-producing polyurethane-modified acrylate (mB).

Example 7 Polyoxyethylene monooleyl ether, polyoxyethylene mono(nonylphenyl) ether, polyoxyethylene monostearate was added to a coal-minable urethane-modified acrylate tree J]tmB) containing 0.5 PHR of anhydrous silica fine powder. was added to investigate the effect of the amount added on the thixotropy.

For comparison, we also investigated cases where no coal mining aid was added and cases where ethylene glycol or glycerin was added.

The results are shown in Table 7.

It is clear that even if the amount of the coal mining aid of the present invention is reduced, its effectiveness remains the same.

Example 8 In the same manner as in Example 7, polyethylene glycol, poly7゜lopylene glycol, polyethylene glycol, polypropylene glycol, polypropylene glycol block copolymer polyoxyethylene sorbitan monoole, etc. ate and polyoxypropylene glycerin ether were added, and the effect of the amount added on the thixotropy was investigated.

The results are shown in Table 8.

It is clear that even if the amount of the coal mining aid of the present invention is reduced, its effectiveness remains the same.

Reference example 3 Preparation reference example 1 of thixotropic urethane modified acrylate resin q
In the same reaction vessel as above, add 344 parts of 2,2-bis[4-(2-hydroxypropoxyphenyl)]propane (as above), 638 parts of styrene, 348 parts of 2,4-tolylene diisocyanate (as above), and ethylene glycol monoacrylate. Using 286 parts as a raw material, a resin was obtained in the same manner, and further diluted by adding styrene so that the styrene content was 45% by weight.

The viscosity of the resin was 2.4 poise.

Asbestos-based swaying agent [Product name: Calidria RG] is added to the resin.
-244 (manufactured by Union Carbide)) was added and thoroughly dispersed with a triple roll to obtain a thixotropic urethane-modified acrylate resin (Q).

Example 9 A thixotropic urethane-modified acrylate resin containing 0.5 PHR of an asbestos-based coal mining agent (q is 0.5 PHR of a compound containing one alcoholic hydroxyl group in the molecule shown in Table 9).
2 PHR was added and the thixotropy was measured.

The results are shown in Table 9. For comparison, the case where no coal mining aid was added and the case where ethylene glycol was added are also shown.

From these results, it is clear that the coal mining aid of the present invention is highly effective even in asbestos-based thixotropic resins.

Example 10 In the same manner as in Example 9, 02 PHR of a compound containing two or more alcoholic hydroxyl groups in the molecule shown in Table 10 was added to seed-modified urethane-modified acrylate resin q, and the thixotropy was measured. .

The results are shown in Table 10.

From these results, it is clear that the seed modification aid of the present invention is highly effective even in resins containing asbestos-based coal mining agents.

Claims (1)

[Scope of Claims] 1 The following general formula (I) (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 a 5 or less, n is an integer from 1 to 4.) Anhydrous silica fine powder or asbestos-based thixotropic resin is added to a radically polymerizable thermosetting resin made by blending a urethane-modified acrylate represented by 5 or less with a polymerizable monomer. The following (1
) ~ (■) Polyethers having one alcoholic hydroxyl group in the molecule or the following (VO
A thixotropic urethane-modified acrylate resin composition comprising a polyether containing two or more alcoholic hydroxyl groups in the molecule selected from the group consisting of -0x). (1) Alkylene oxide adduct of monohydric alcohol (i
i) Alkylene oxide adduct of phenol or substituted phenol (iii) Alkylene oxide adduct of monovalent fatty acid 6v) Alkylene oxide adduct of sorbitan trifatty acid ester (v) Alkylene oxide adduct of fatty acid ester of dihydric or higher polyhydric alcohol (VD Polyalkylene glycol ~ i9 Alkylene oxide adduct of trivalent or higher polyhydric alcohol &ii) Alkylene oxide adduct of sorbitan mono- or difatty acid ester (X) Alkylene oxide addition of trivalent or higher polyhydric alcohol fatty acid ester thing.