JP3503126B2 - Air-drying adhesive resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for coating various base materials such as concrete and steel plate on site and on site, has a low odor, and has a good surface drying property. The present invention relates to a resin composition having excellent adhesion to a substrate. [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. [0004] A method of improving the adhesiveness, air permeability, water permeability, etc. by mixing a cement paste or a cement mortar synthetic polymer emulsion is also known. Kosho 44-
As disclosed in Japanese Patent No. 18757, there is a method in which a synthetic polymer emulsion is previously applied to a base to enhance the adhesiveness of mortar. However, the above technique has a problem in that the adhesiveness to concrete is not sufficient, and in order to maintain long-term durability, it is necessary to rely on periodic repainting and repair of the exterior. SUMMARY OF THE INVENTION The present invention relates to an air-drying adhesive resin composition having a low odor, a short surface drying time, and excellent adhesion to a substrate such as concrete. Hereinafter, referred to as a resin composition). [0006] 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 compound represented by the general formula (I): Wherein n is an integer of 1 or 2, R represents an aromatic group or an aliphatic group having 2 to 25 carbon atoms, and has an active hydrogen atom and an acryloyl group. A urethane compound obtained by reacting the compound is converted to a compound represented by the general formula (II): [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.
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 hydrogen or a methyl group]. A resin composition dissolved in a compound to be prepared. The polyfunctional isocyanate compound used in the present invention includes diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2
2,4-trimethylhexamethylene diisocyanate,
Cyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis (4
-Cyclohexyl isocyanate), hexamethylene diisocyanate, a burette of hexamethylene diisocyanate, a trimer of isophorone diisocyanate containing an isocyanurate ring, and a compound having two or more isocyanate groups such as polymethylene polyphenyl polyisocyanate. Examples of the polyhydric alcohol include ethylene glycol, 1,3-propanediol, 1,6-hexanediol, 1,2-propylene glycol, 1,3-butanediol, neopentyl glycol, and 1,4-butanediol. , Diethylene glycol, dipropylene glycol, hydrogenated bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, dipentaerythritol, polyethylene glycol, polypropylene glycol and the like. Among these polyhydric alcohols, those having an ether bond in the molecular skeleton such as diethylene glycol and dipropylene glycol are preferable from the viewpoint of surface drying properties,
From the viewpoint of surface drying properties and filler dispersibility, a molecular weight of 200
Particularly preferred are polypropylene glycols of from 1 to 10,000. In the present invention, 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 allyl glycidyl ether with a polyhydric alcohol or acid can be used. In the reaction, a small amount of Lewis acid or its ether, a complex with acetic acid is used, and after the reaction,
By neutralizing, washing and dehydrating, an allyl ether compound having an active hydrogen atom can be obtained. The hydroxyoxyalkyldicyclopentadiene represented by the above general formula (I) used in the present invention is an addition reaction product obtained by reacting a polyhydric alcohol with dicyclopentadiene in the presence of a strongly acidic catalyst. is there.
This reaction is known and is described, for example, in US Pat.
3,609 and in the Journal of the Chemical Society, 68.8, (1945), in the presence of a homogeneous strong acid catalyst such as a strong mineral acid catalyst or a Lewis acid catalyst. To give an addition reaction between glycol and dicyclopentadiene to obtain an addition reaction product represented by the above general formula (I). The polyhydric alcohol used in the reaction is not particularly limited as long as it has an aromatic group or an aliphatic group having 2 to 25 carbon atoms. Further, the aromatic group or the aliphatic group having 2 to 25 carbon atoms may contain oxygen. For example, ethylene glycol, 1,3-propanediol, 1,6
-Hexanediol, 1,2-propylene glycol,
1,3-butanediol, neopentyl glycol,
1,4-butanediol, diethylene glycol, dipropylene glycol, hydrogenated bisphenol A, propylene oxide adduct of bisphenol A, glycerin,
Trimethylolpropane, trimethylolethane and the like. Among these polyhydric alcohols, the number of carbon atoms of the aromatic group or the aliphatic group is 2 in terms of distillation purification of hydroxyoxyalkyldicyclopentadiene and physical properties of the coating film.
~ 25. Ethylene glycol, 1,2-
Preferred are propylene glycol, diethylene glycol, dipropylene glycol, glycerin and the like, which have a low melting point and are liquid at room temperature. The number of aromatic groups is usually two or less. 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 above-mentioned polyfunctional isocyanate compounds, polyhydric alcohols, allyl ether compounds having an active hydrogen atom, hydroxyoxyalkyldicyclopentadiene represented by the general formula (I) and compounds having an active hydrogen atom and an acryloyl group Are reacted to obtain a urethane compound, the reaction temperature is usually 0 to 120
° C, preferably 20 to 80 ° C, and the reaction time is usually 1 to 50 hours, preferably 3 to 10 hours. In the reaction, a urethane reaction catalyst such as dibutyltin dilaurate and a polymerization inhibitor such as hydroquinone, methylhydroquinone and N-nitrosophenylhydroxylamine aluminum salt may be present. All of these materials may be reacted at the same time, or any compound may be reacted with the polyfunctional isocyanate compound, and then the other compound may be reacted. The total amount of active hydrogen atoms of the above four compounds is preferably in the range of 0.8 to 1.5 equivalents with respect to the isocyanate group. The polyhydric alcohol, the allyl ether compound having an active hydrogen atom, the hydroxyoxyalkyldicyclopentadiene represented by the general formula (I), and the compound having an active hydrogen atom and an acryloyl group are optional assuming that the total amount of the active hydrogen atoms is 100 equivalent%. The compounding ratio of each compound may be changed,
% Of an allyl ether compound, 1 to 29 equivalent% of a compound represented by the above general formula (I), and 97% of a compound having an active hydrogen atom and an acryloyl group.
It is preferably used in the range of 1 to 1 equivalent%. In order to prevent a decrease in stirring efficiency due to an increase in the viscosity of the compound during the reaction, this reaction can be performed in the presence of the compound represented by the above general formula (II). The resin composition of the present invention contains the urethane compound obtained as described above dissolved in the compound represented by the general formula (II). Examples of the compound represented by the general formula (II) include compounds in which a terminal hydroxyl group of the compound represented by the general formula (I) is added with an acryloyl group by esterification. For example, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl Oxyisopropyl methacrylate, dicyclopentenyloxy isopropyl acrylate, dicyclopentenyl oxyneopentyl methacrylate, dicyclopentenyl oxyneopentyl acrylate and the like can be mentioned. In the resin composition of the present invention, the amount of the compound represented by the general formula (II) 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 preferably carried out by adding a photoinitiator, for example, benzophenone, benzyl, Michler's ketone, thioxanthone, anthraquinone, benzoin ether, methoxyacetophenone, to the resin composition in an amount of 0.1 to 5% by weight based on the resin composition. And irradiation with light using a sunlight, an ultraviolet lamp or the like. The resin composition of the present invention may contain conventional low molecular weight polymerizable monomers such as styrene, chlorostyrene, divinylbenzene, tert-butylstyrene, styrene bromide, diallyl phthalate, methacrylic acid, if necessary. 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 preferable to use a methacrylic acid ester, a methacrylic acid ester having a long-chain alkyl group, or a compound obtained by esterifying a part or all of the hydroxyl groups of a long-chain polyhydric alcohol such as polyethylene glycol dimethacrylate with acrylic acid or methacrylic acid. . Further, a low contraction agent can be used. For example, methyl methacrylate, ethyl methacrylate,
Examples thereof include lower alkyl esters of acrylic acid or methacrylic acid such as methyl acrylate and ethyl acrylate, homopolymers or copolymers such as styrene and vinyl acetate, polyethylene, and polypropylene. It can be used in the range of ５０50% by weight. Furthermore, a filler and a reinforcing material can be added to the resin composition of the present invention, if necessary. Fillers include glass beads, silica powder, barium sulfate,
Calcium carbonate, talc, silica sand, aluminum hydroxide and the like can be used. Examples of the reinforcing material include cloths, mats, and nonwoven fabrics made of organic fibers such as glass fiber, polyester, aramid, vinylon, and phenol.
One-dimensional fabrics and the like can be used. It is preferable that each of the filler and the reinforcing material is used in a range of 10 to 500% by weight based on the resin composition. Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples. Synthesis Example 1 Synthesis of hydroxyethyl monoether dicyclopentadiene 0.5 equipped with a stirrer, a cooler, a thermometer and a dropping funnel.
Ethylene glycol 12 in a 4-liter four-necked flask
4 g and 19.4 g of paratoluenesulfonic acid were charged and the temperature was raised to 120 ° C., and 264 g of dicyclopentadiene was added to 1 g.
It was dropped over time. After completion of the dropwise addition, the mixture was further kept at 120 ° C. for 2 hours, and then neutralized with 20 g of sodium methylate. The neutralized solution was distilled at 120 ° C./2 mmHg to obtain hydroxyethyl monoether dicyclopentadiene 200
g was collected. Synthesis Example 2 Synthesis of dicyclopentenyloxyethyl methacrylate In a 1-liter four-necked flask equipped with a stirrer, a condenser, a rectification tube, a thermometer and a dropping funnel, 60 g of dicyclopentadiene, 160 g of ethylene glycol and After reacting 4 g of p-toluenesulfonic acid at 120 ° C. for 4 hours, the temperature was lowered to 80 ° C., and 430 g of methacrylic acid and 4 g of p-toluenesulfonic acid were added. The mixture was reacted at 100 ° C. for 5 hours while distilling water. The obtained reaction product was neutralized with magnesium oxide. After the reaction product was washed with water, it was purified by distillation under reduced pressure. Example 1 In a 1-liter four-necked flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 550 g of the dicyclopentenyloxyethyl methacrylate synthesized in Synthesis Example 2 was added.
Millionate MR-100 (Nippon Polyurethane Industry Co., Ltd.)
132 g of polymethylene polyphenyl polyisocyanate having an NCO content of 31.0%), 2 g of dibutyltin dilaurate was added, and the mixture was heated to 60 ° C. Next, 200 g of polypropylene glycol PPG-2000 (manufactured by Sanyo Chemical Industries, Ltd .; molecular weight: about 2,000) and 30 g of neoallyl P-30 (manufactured by Daiso Corporation; pentaerythritol triallyl ether) were placed in the flask. A mixed solution of 30 g of hydroxyethyl monoether dicyclopentadiene synthesized in 1 and 120 g of 2-hydroxyethyl methacrylate was added dropwise over about 3 hours. The determination of the synthesis end point was performed by tracking the reaction every time using an infrared spectrophotometer (manufactured by Hitachi, Ltd .; model 270-30). That is, the point at which the absorption peak near 2240 cm ^-1 attributed to the isocyanate group disappeared was regarded as the synthesis end point. In this example, it was confirmed that the absorption peak had disappeared two hours after the completion of the dropwise addition of the mixed solution, and thus the synthesis was terminated, and a urethane compound (1) was obtained. 100 g of the obtained urethane compound (1)
Then, 50 g of dicyclopentenyloxyethyl methacrylate was added thereto to obtain a resin composition (I). The viscosity was measured at 25 ° C. using a BL viscometer, and it was 2.5 poise. Comparative Example 1 Dicyclopentenyloxyethyl methacrylate 550 was prepared in the same manner as in Example 1 using the same synthesis apparatus as in Example 1.
g, Millionate MR-100 232 g and dibutyltin dilaurate 2 g were further added and heated to 60 ° C. Then, neoallyl P-3053 g, hydroxyethyl monoether dicyclopentadiene 33 were placed in the flask.
g and 185 g of 2-hydroxyethyl methacrylate
Was added dropwise over about 3 hours. The synthesis was completed in the same manner as in Example 1. The synthesis was completed 2 hours after the completion of the dropwise addition, and a urethane compound (2) was obtained. 100 g of the obtained urethane compound (2)
And dicyclopentenyloxyethyl methacrylate 5
0 g was added to obtain a resin composition (II), and its viscosity was measured using a BL viscometer. As a result, it was 2.0 poise at 25 ° C. <Test Example 1>-Mechanical strength-Each resin composition obtained by adding 0.5 g of cobalt octylate and 1.0 g of 80% cumene hydroperoxide to 50 g of the resin composition (I) and the resin composition (II). The product was poured into a casting mold to obtain a cured resin having a width of 12 mm, a thickness of 5 mm, and a length of 120 mm. Measure the mechanical strength of the cured product of each resin composition according to JIS
It measured based on -K-7203. As a result, the cured product of the resin composition (I) had a flexural strength of 1.0 kgf / mm ² , a flexural modulus of 30 kgf / mm ² , and the flexural strength of the resin composition (II) of 2.
The flexural modulus was 5 kgf / mm ² and the flexural modulus was 150 kgf / mm ² . Test Example 2 -Surface Drying of Coating Film- 100 g each of resin composition (I) and resin composition (II)
And paraffin wax (manufactured by Nippon Seiro Co., Ltd .; melting point: about 50
C) was added after dissolving the wax in an amount of 1.0 g each. Further, 100 g of silica sand No. 6 and 150 g of silica sand powder were added to each resin composition, and 1.0 g of cobalt octylate was added.
And 2.0 g of 80% cumene hydroperoxide were added and mixed well using a high-speed stirrer. This mixture was coated on a concrete sidewalk board with a trowel to a thickness of 3 mm. When observed in a room controlled at 25 ° C, it was about 2
In 0 minutes, the inside of the coating film was cured, and in about 1 to 1.5 hours, each of the resin compositions was brought into a touch-dry state. <Test Example 3> -Fluidity- As in Test Example 2, 100 g of silica sand No. 6 and 150 g of silica sand powder were added to the resin composition (I) and the resin composition (II) and mixed well. Above, a concrete pavement installed at an inclination angle of 30 ° was poured at once at the upper end, and the time required for the mixture to reach the lower end was measured. As a result, it took about 10 seconds for the mixture of the resin composition (I) and about 20 seconds for the mixture of the resin composition (II). <Test Example 4>-Impact Resistance-Using a concrete sidewalk board of each resin composition of which surface dryness was evaluated in Test Example 2, after holding at -40 ° C for 6 hours, immediately take out and weigh. An iron ball of about 1 kg was dropped from a height of about 1 m. Impact resistance was measured, which was expressed as the relationship between the number of drops of an iron ball and the occurrence of cracks. As a result, no crack was observed even when the coating film of the resin composition (I) was dropped five times, but cracks occurred in the resin composition (II) three times. <Test Example 5> -Adhesiveness- In the same manner as in Test Example 2, a mixture of the resin composition (I), the resin composition (II), the aggregate, and the hardener was applied to a concrete sidewalk board with a thickness of 3 mm. Was applied with a trowel so that 24 at room temperature
After standing for a time, a jig was attached to the surface of the composition with an epoxy adhesive, and a Kenken-type tensile test was performed. The test was carried out at n = 5, and all the test pieces showed cohesive failure of the concrete sidewalk board, and the adhesive strength was 33 kgf / mm ² . Test Example 6 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 90 minutes, the odor sensitivity value was measured. As the sensor, Naoi Sensor XP329 type manufactured by Shin 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, and contributes to shortening the application time for coating the substrate. Further, the obtained coating film has excellent adhesiveness to various base materials such as concrete, and also has toughness, so that occurrence of cracks and peeling after construction can be suppressed.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-8-283357 (JP, A) JP-A-3-100069 (JP, A) JP-A-7-216050 (JP, A) JP-A-60-1985 163911 (JP, A) JP-A-6-145275 (JP, A) JP-A-57-165416 (JP, A) JP-A-2-142808 (JP, A) JP-A 8-193108 (JP, A) JP-A-8-193109 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 C08G 18/00-18 / 87 C09D 1/00-201/10

Claims (1)

(57) [Claim 1] Polyfunctional isocyanate compound, polyhydric alcohol, allyl ether compound having an active hydrogen atom, general formula (I) Wherein n is an integer of 1 or 2, R represents an aromatic group or an aliphatic group having 2 to 25 carbon atoms, and has an active hydrogen atom and an acryloyl group. A urethane compound obtained by reacting the compound is converted to a compound represented by the general formula (II): [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.
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 hydrogen or a methyl group]. An air-drying resin composition obtained by dissolving in a compound to be obtained.