JP3487376B2 - Air-drying resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition having a low odor and excellent surface drying properties, which is suitable for coating various base materials on site. About things. [0002] Conventionally, various coatings using an epoxy resin, a urethane resin, an unsaturated polyester resin or the like have been performed to prevent deterioration of concrete and steel used in buildings and facilities. . However, these resins contain a large amount of a polymerizable monomer, a reactive diluent, and a diluting solvent, so that they volatilize during work, which has an adverse effect on workers and the surrounding environment. Therefore, in order to improve these odors, attempts have been made to suppress volatilization by using a high molecular weight monomer. For example, JP-A-57-74316 discloses an acrylic polymer containing an aggregate material, a binder monomer comprising dicyclopentenyloxyalkyl acrylate or methacrylate and hydroxyalkyl methacrylate, and a polymerization catalyst. A concrete composition is disclosed. This is used for repairing floors and roads. On page 5, line 9 to 18 in the upper right column of the gazette describes improvement in working environment due to low volatility and low odor. I have. The lower left column of page 12 of the publication describes that the composition is surface-dried (= surface-hardened) in 2 to 4 hours. However, this resin composition also has a disadvantage that the surface drying time is much longer than that of a conventional unsaturated polyester resin. DISCLOSURE OF THE INVENTION The present invention relates to an air-drying resin composition (hereinafter referred to as a resin composition) which has a low odor, improves the mechanical strength of a cured product, and has a short surface drying time. ). [0005] The present invention has solved the above-mentioned problems by using dicyclopentenyloxyalkyl acrylate or dicyclopentenyloxyalkyl methacrylate in combination with a specific urethane compound. That is, the present invention relates to a polyfunctional isocyanate compound, a polyhydric alcohol, an allyl ether compound having an active hydrogen atom, and a urethane compound obtained by reacting an active hydrogen atom with a compound having an acryloyl group by a general formula (I) [0006] Wherein R ₁ comprises an alkylene group having 2 to 12 carbon atoms or at least two alkylene chains linked by at least one oxygen atom, wherein each alkylene chain has at least two carbon atoms. Having a total of 4 to 12
Represents oxaalkylene group having carbon atoms, R ₂
Represents a hydrogen atom or a methyl group. And a resin composition dissolved in the compound represented by the formula: In the present invention, as the polyhydric alcohol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, polyethylene glycol, polypropylene glycol and the like are used. In order to improve the mechanical properties of the obtained cured product, it is preferable to use polyethylene glycol or polypropylene glycol having a relatively large molecular weight. In particular, by using polypropylene glycol having a molecular weight of 500 or more, the strength can be improved without consuming a large amount of isocyanate in the polyfunctional isocyanate. Examples of the allyl ether compound having an active hydrogen atom include allyl ether compounds having a hydroxyl group such as glycerin diallyl ether, glycerin monoallyl ether, trimethylolpropane diallyl ether, and pentaerythritol triallyl ether. A compound synthesized by reacting a required amount of glycidyl ether can be used. In the reaction, a small amount of a Lewis acid or a complex thereof with an ether or acetic acid is used, and after the reaction, the mixture is neutralized, washed with water and dehydrated to obtain an allyl ether compound having an active hydrogen atom. The compound having an active hydrogen atom and an acryloyl group is 2-hydroxyethyl (meth) acrylate [(meth) acrylate means methacrylate or acrylate. The same applies to the following) and 2-hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, among which 2-hydroxyethyl methacrylate is preferable. The polyfunctional isocyanate compounds include diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexylmethane diisocyanate, and methylcyclohexane. Two or more isocyanate groups such as diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate), hexamethylene diisocyanate, a buret of hexamethylene diisocyanate, a trimer of isophorone diisocyanate containing an isocyanurate ring, and polymethylene polyphenyl polyisocyanate. And the like. The reaction temperature of the above polyfunctional isocyanate compound, polyhydric alcohol, allyl ether compound having an active hydrogen atom, and reaction of the active hydrogen atom with a compound having an acryloyl group is as follows. , Usually 0 to 120 ° C, preferably 20 to
At 80 ° C., a urethane reaction catalyst such as dibutyltin dilaurate and a polymerization inhibitor such as aluminum salt of hydroquinone, methylhydroquinone and N-nitrosophenylhydroxylamine may be present in the reaction. It is preferable that the total amount of active hydrogen atoms of the compound used for the isocyanate group is in the range of 0.8 to 1.5 equivalents. The polyhydric alcohol, the allyl ether compound having an active hydrogen atom and the compound having an active hydrogen atom and an acryloyl group, the total amount is 100 equivalent%, the polyhydric alcohol is 1 to 40 equivalent%, the allyl ether compound having an active hydrogen atom is It is preferred to use 4 to 40 equivalent% and a compound having an active hydrogen atom and an acryloyl group in the range of 20 to 95 equivalent%. This reaction can also be carried out in the presence of the compound of the above general formula (I) in order to prevent a decrease in stirring efficiency due to an increase in the viscosity of the compound during the reaction. The resin composition of the present invention contains the urethane compound obtained as described above dissolved in the compound represented by the general formula (I). Examples of the compound represented by the general formula (I) include dicyclopentenyloxyethyl methacrylate, dicyclopentenyloxyisopropyl methacrylate, dicyclopentenyloxyisopropyl acrylate, dicyclopentenyloxyneopentyl methacrylate, and dicyclopentenyloxyneopentyl acrylate. And the like. In the resin composition of the present invention, the amount of the compound represented by the general formula (I) is preferably 10 to 90% by weight, more preferably 30 to 90% by weight, based on the air drying property of the resin composition. 80% by weight. The resin composition of the present invention may further contain an organic peroxide and a polymerization accelerator. Here, as the organic peroxide, for example, benzoyl peroxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, cumene hydroperoxide, etc. in the range of 0.3 to 10% by weight based on the resin composition. Preferably, it is used. As the polymerization accelerator, a polyvalent metal salt such as cobalt naphthenate or cobalt octenoate may be used in an amount of from 0.1 to 5% by weight based on the resin composition, such as an aromatic compound such as dimethylaniline or dimethylparatoluidine. It is preferable to use an amine or the like in the range of 0.01 to 5% by weight based on the resin composition. Further, the resin composition of the present invention can be cured by light. Curing by light is carried out by adding a photoinitiator, for example, benzophenone, benzyl, Michler's ketone, thioxanthone, anthraquinone, benzoin ether, methoxyacetophenone, to the resin composition, preferably in the range of 0.1 to 5% by weight based on the resin composition. And by irradiating with light using a sunlight, an ultraviolet lamp or the like. The resin composition of the present invention may optionally contain conventional low molecular weight polymerizable monomers such as styrene, chlorostyrene, divinylbenzene, tert-butylstyrene, styrene bromide, diallyl phthalate, methacrylic acid. Methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl acrylate, β-hydroxyethyl methacrylate, β
-Ethyl hydroxyacrylate, acrylamide, phenylmaleimide, maleimide, vinyl acetate and the like can be preferably used in an amount of 1 to 50% by weight based on the resin composition, but from the viewpoint of low odor, β-hydroxyethyl It is possible to use a compound obtained by esterifying part or all of the hydroxyl groups of a long-chain polyhydric alcohol such as methacrylic acid ester, methacrylic acid ester having a long-chain alkyl group, polyethylene glycol dimethacrylate with acrylic acid or methacrylic acid. preferable. Further, a filler and a reinforcing material can be added to the resin composition of the present invention, if necessary. As the filler, calcium carbonate, talc, silica sand, aluminum hydroxide and the like can be used. As the reinforcing material, a cloth, mat, nonwoven fabric, or the like made of glass fiber, polyester fiber, or the like can be used. The filler and the reinforcing material are 10 to 10 parts by weight of the urethane compound and the compound represented by the general formula (I), respectively.
It is preferable to use it in the range of 500 parts by weight. Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples. In the examples, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, unless otherwise specified. Synthesis Example 1 Synthesis of dicyclopentenyloxyethyl methacrylate In a 2 liter flask equipped with a rectification tube and a stirrer, 60 parts of dicyclopentadiene and 16 parts of ethylene glycol
After reacting 0 parts and 4 parts of paratoluenesulfonic acid at 120 ° C. for 4 hours, the temperature is lowered to 80 ° C., 430 parts of methacrylic acid and 4 parts of paratoluenesulfonic acid are added, and water is distilled at 100 ° C. The reaction was carried out for 5 hours while neutralizing the obtained reaction product with magnesium oxide. After the reaction product was washed with water, it was purified by distillation under reduced pressure. Example 1 Into a 2 liter flask equipped with a condenser, a stirrer, and a dropping device, 600 parts of dicyclopentenyloxyethyl methacrylate synthesized in Synthesis Example 1 above, and millionate M
240 parts of R-100 (trade name, manufactured by Nippon Polyurethane Co., Ltd .; polymethylene polyphenylene polyisocyanate having an NCO content of 31.0%) was charged, and 1 part of dibutyltin dilaurate was further added, followed by heating to 60 ° C. Next, 300 parts of dicyclopentenyloxyethyl methacrylate and polypropylene glycol PPG-10 were placed in the flask.
00 (manufactured by Sanyo Chemical Industries, Ltd .; molecular weight: about 1000) 135
A mixed solution of 167 parts of 2-hydroxyethyl methacrylate and 57 parts of neoallyl P-30 (trade name of pentaerythritol triallyl ether manufactured by Daiso Corporation) was added dropwise over 2 hours. 2240 using an infrared spectrometer
The reaction was followed by examining the absorption of isocyanate groups near cm ^-1 . After 2 hours, the absorption of the isocyanate group had almost disappeared, but the reaction was further continued for 1 hour to complete the synthesis. In 100 parts of the obtained viscous urethane compound (A),
Further 490 parts of dicyclopentenyloxyethyl methacrylate was added to obtain a resin composition (I). This resin composition (I) exhibited a viscosity of 2.0 poise at 25 ° C.
Next, 0.5 part of cobalt octylate and 80% cumene hydroperoxide 1 were added to 50 parts of the resin composition (I).
When the mixture was added and cured, no fluidity was exhibited in 15 minutes. In addition, 400μ on the surface of the concrete sidewalk board
m, a touch dryness was obtained in about 2 hours. Further, 50 parts of the resin composition (I) is
0.5 parts of paraffin wax (melting point 47 ° C.) manufactured by Co., Ltd. was dissolved (dissolved by heating to about 55 ° C.), and 0.5 parts of cobalt octylate and 80% cumene hydro were dissolved in the same manner as described above. 1 part of peroxide was added and applied to the surface of the concrete sidewalk board to a thickness of 400 μm.
Dryness to the touch was obtained in 1.5 hours. Further, a resin composition obtained by adding 0.5 part of cobalt octylate and 1 part of 80% cumene hydroperoxide to 50 parts of the resin composition (I) was poured into a mold, and the width was 12 mm, the thickness was 5 mm,
A cured resin having a length of 120 mm was obtained. This resin composition is
1.3 kgf / mm ² in bending strength showed a flexural modulus of 150 kgf / mm ^2. To 100 parts of the resin composition (I) were added 100 parts of silica sand No. 6 and 150 parts of silica sand, and 1.0 part of cobalt octylate and 2 parts of 80% cumene hydroperoxide were added and mixed well. Was applied with a trowel to a thickness of 3 mm on a concrete sidewalk board. The composition was internally cured in about 15 minutes, surface-hardened in about 1.5 hours, and was dry to the touch. After standing at room temperature for 24 hours, a jig is attached to the surface of the composition with an epoxy adhesive,
A Kenken-type tensile test was performed. The test was performed at n = 5, and all tests showed cohesive failure of the concrete sidewalk board, and the adhesive strength was a value of 31 kgf / cm ^{2 on} average. In addition, this composition was previously placed in the center of a 30 cm square concrete sidewalk board.
A 0 cm square polypropylene film was applied with a trowel to a thickness of 3 mm on a concrete sidewalk board to which a double-sided tape was attached. After this composition was cured, a heat cycle test was performed using a heat cycle tester. The high temperature side was set to room temperature, and the heating / cooling rates were 10 ° C./hour and −10, respectively.
° C / hour, and the low temperature side was lowered from 20 ° C in steps of 10 ° C. When the portion of the polypropylene film was observed for each cycle when the temperature returned to room temperature, cracks occurred in the coating film when the temperature was returned from -30 ° C to room temperature. Comparative Example 1 Using the same synthesis apparatus as in Example 1, 600 parts of dicyclopentenyloxyethyl methacrylate, 240 parts of millionate MR-100 and 1 part of dibutyltin dilaurate were added in the same manner as in Example 1, Heated to ° C. Next, a mixed solution of 300 parts of dicyclopentenyloxyethyl methacrylate, 213 parts of 2-hydroxyethyl methacrylate and 57 parts of neoallyl P-30 was dropped into the flask over 2 hours, and the reaction was followed by an infrared spectroscope. After 2 hours, the absorption of the isocyanate group had almost completely disappeared, and the reaction was further continued for 1 hour to obtain a urethane compound (B). To 100 parts of the obtained urethane compound (B), 150 parts of dicyclopentenyloxyethyl methacrylate was further added to obtain a resin composition (II). To 50 parts of the obtained resin composition (II), 0.5 parts of cobalt octylate and 1 part of 80% cumene hydroperoxide were added and cured in the same manner as in Example 1, and the fluidity was similarly increased in 15 minutes. No longer shown. In addition, when applied to the surface of the concrete sidewalk board to a thickness of 400 μm, it took about 2 hours for touch drying. Further, in the same manner as in Example 1, the prepared resin cured product had a bending strength of 2.0 kgf / mm ² and a 320 kgf / mm ²
/ mm ² . Furthermore, in a cold and hot cycle test of a cured and applied coating film applied to a concrete sidewalk board on which a polypropylene film was stuck, cracks occurred in the film on the polypropylene film when the low temperature side was set to 0 ° C. and returned to room temperature. Test Example 1 An odor sensor having an intake pipe and an exhaust pipe was attached to a closed container having a capacity of 20 liters, and 5 g of the resin composition (I) produced in Example 1 was left at the bottom of the container. After a minute, the odor sensitivity value was measured. As the sensor, an odor sensor XP329 type manufactured by New Cosmos Electric Co., Ltd. was used. The results are shown in Table 1 together with the odor sensitivity values of other resins, monomers, solvents and the like. [Table 1] As the odor sensitivity value of the sensor is larger, the odor is stronger. In Table 1, the resin composition (I) showed the lowest odor sensitivity value. The resin composition of the present invention has low odor and excellent surface drying properties, reaches a surface dried state in a short time, and has excellent adhesion to various substrates. further,
The physical properties of the cured product are improved, the toughness is improved, and there is no fear of cracking of the coating film (cured product) when applied to a portion where a large temperature difference occurs.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-237048 (JP, A) JP-A-7-216050 (JP, A) JP-A-2-142808 (JP, A) JP-A 8- 59761 (JP, A) JP-A-8-193108 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08G 18/67

Claims (1)

(57) [Claim 1] A polyfunctional isocyanate compound, a polyhydric alcohol, an allyl ether compound having an active hydrogen atom, and a urethane compound obtained by reacting an active hydrogen atom with a compound having an acryloyl group With the general formula (I) [Wherein, R ₁ represents an alkylene group having 2 to 12 carbon atoms or at least 2 alkylene groups bonded by at least one oxygen atom.
And each alkylene chain has at least 2 carbon atoms, and represents an oxaalkylene group having a total of 4 to 12 carbon atoms, and R ₂ represents a hydrogen atom or a methyl group. ] The air-drying resin composition melt | dissolved in the compound shown by these.