JPH06293821A - One pack-type urethane resin composition - Google Patents

Abstract

PURPOSE:To obtain a one pack-type urethane resin composition resistant to separation and precipitation during storage, relatively rapidly curable in air and giving a coating film free from blister defect. CONSTITUTION:This urethane composition is produced by compounding (A) 100 pts.wt. of a prepolymer having free isocyanate terminal and obtained by reacting a polyisocyanate compound with an N-2hydroxyalkyl-oxazolidine at an NCO/OH equivalent ratio of 1.2-10 with (B) 5-200 pts.wt. of an inorganic filler treated with an organic material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component urethane resin composition having excellent storage stability.

[0002]

2. Description of the Related Art As a conventional one-pack urethane resin composition, for example, a moisture-curable coating in which a urethane prepolymer having a terminal isocyanate group (NCO group) is mixed with an inorganic filler is used. Waterproof material (see Japanese Patent Application Laid-Open No. 57-94056, hereinafter referred to as "Prior Art I")
However, in the conventional technique I, carbon dioxide may be generated by the reaction of moisture in the air or the ground with the NCO group. This carbon dioxide gas often causes "blister" when the coating film is thick. Also, Japanese Patent Publication No. 48-20639 (hereinafter referred to as "Prior Art II") and Japanese Patent Laid-Open No. 2-5.
In Japanese Patent No. 5715 (hereinafter referred to as "prior art III"),
Oxazolidine-isocyanate compositions are described. In this conventional technology II and conventional technology III, although carbon dioxide gas is not generated during curing, when the oxazolidine-isocyanate composition is blended with an inorganic filler and stored for a long period of time, the inorganic filler precipitates to form a hard cake. So
Despite being a one-part coating material, it is necessary to stir it well before use and to use it after the composition becomes uniform. One-component coating materials have the value of one-component materials if they can be used without modification before use, and two-component materials are sufficient if they are stirred before use. Use one-component materials. There is no merit.

Further, it is known that an organic / inorganic anti-sedimentation agent is used in combination for the purpose of preventing the sedimentation of the inorganic filler. Delay or worsen storage stability.

The present invention has been made in view of the above problems of the prior art, and its object is to cure relatively quickly in air without separation / sedimentation during storage. It is intended to provide a one-component urethane resin composition in which the coating film has no blistering.

[0005]

To achieve the above object, the gist of the present invention is to provide a polyisocyanate compound and N-2.
-Hydroxyalkyl-oxazolidine with NCO / O
One-part urethane resin composition obtained by mixing 5 to 200 parts by weight of an organic-treated inorganic filler with 100 parts by weight of a terminal free isocyanate-containing prepolymer obtained by reacting at an H equivalent ratio of 1.2 to 10 It is in things.

The polyisocyanate compound of the present invention is
A reaction product of an ethylene oxide adduct of methanol or ethanol with a polyisocyanate, a compound having a free isocyanate group obtained by the reaction of a compound having two or more active hydrogens in one molecule with a polyisocyanate, or a polyisocyanate alone Say. Examples of such a compound having active hydrogen include "ethylene glycol,
Propylene glycol, diethylene glycol, polyhydric alcohols such as trimethylolpropane and malonic acid, succinic acid, adipic acid, polybasic acids such as phthalic acid are condensed, polyester polyol having a hydroxyl group at the end ",
"Ethylene glycol, propylene glycol, 1,4
-Low molecular weight polyols such as butanediol, 1,6-hexanediol and trimethylolpropane "," Polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol and sorbitol Ethylene oxide, propylene oxide, butylene oxide added polyether polyol "," polybutadiene glycol, polyisoprene glycol, lactone ring-opening polymer, tetrahydrofuran ring-opening polymer, castor oil, a hydroxyl group-containing compound such as polyol ", etc., Those having an average molecular weight of 30 to 100,000 per active hydrogen are preferable, and they are used alone or as a mixture. As the polyisocyanate, compounds having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, 1,6-hexamethylene diisocyanate, tolidine Examples thereof include diisocyanate, isophorone diisocyanate or a water additive thereof, a crude product, a buret body, an isocyanurate body, or a carbodiimide modified product.

Examples of 2-hydroxyalkyl-oxazolidine include 2- (2-ethyl-1 / 3-oxazolidin-3-yl) -ethanol and 3- (2-ethyl-5-methyl-1 / 3-oxazolidine-3. -Yl) -2-propanol, 2- (2-hepta-3-yl-1 / 3-oxazolidin-3-yl) -ethanol, 2- (2-propyl-1 / 3-oxazolidin-3-yl)- Examples thereof include ethanol, 3- (2-propyl-5-methyl-1,3-oxazolidin-3-yl) -2-propanol, and aldehydes such as formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, and benzaldehyde. Obtained by condensation reaction with di (hydroxyalkyl) amines such as diethanolamine and dipropanolamine Than it is.

Examples of the organic-treated inorganic filler include fatty acid-treated calcium carbonate, fatty acid metal salt-treated calcium carbonate,
Fatty acid ester treated calcium carbonate, rosin acid treated calcium carbonate, fatty acid treated talc, fatty acid metal salt treated talc, fatty acid ester treated talc, fatty acid treated bentonite, fatty acid ester treated bentonite, silane treated calcium carbonate, titanium treated calcium carbonate, polyacrylic acid treated Examples thereof include calcium carbonate and surfactant-treated calcium carbonate.

The urethane resin composition may contain, if necessary,
Solvent, catalyst, viscosity reducer, plasticizer, pigment, colorant, extender,
A stabilizer, a flame retardant, a thixotropic agent, a surfactant, an inorganic filler, etc. may be used in combination.

The urethane resin composition comprises concrete,
Waterproof by applying to a structure such as stone, tile, brick, glass, wood, plastic, metal, steel, rubber, etc. with a trowel, roller, rubber rake, spraying, or pouring / filling with a pump. It can be used as a material. Further, at the time of coating, spraying, pouring and filling, a primer such as a urethane primer, an epoxy primer or a silicone primer can be used for the purpose of adjusting the groundwork and improving the adhesiveness.

Further, for the purpose of improving weather resistance and abrasion resistance, a top coat of acrylic urethane, acryl, silicone, acryl silicon, fluorine type or the like may be applied.

The urethane resin composition is a nonwoven fabric,
A woven cloth, a mesh cloth, a net, a paper, or a bitumen-processed material of these materials may be used as a core material and flow-coated to perform waterproofing by a membrane method.

[0013]

The prepolymer containing terminal free isocyanate (hereinafter also referred to as "prepolymer A") of the present invention has a structure as shown in FIG.
As shown in Fig. 1, the oxazolidine ring is hydrolyzed by the water in the air to form an amine polyol, and further reacts with the terminal free isocyanate in the prepolymer A as shown in Fig. 1 (b) (c). By this, a urethane cross-linked polymer is obtained. The structure of the prepolymer A affects the flexibility / elasticity of the urethane crosslinked polymer and produces an elastic polymer.

However, the polyisocyanate compound and N-
2-hydroxyalkyl oxazolidine and NCO / O
If the reaction is carried out at an H equivalent ratio of less than 1.2, the resulting coating film will be soft and the water resistance will be poor. On the other hand, this equivalence ratio is 1
When it exceeds 0, carbon dioxide gas is generated at the time of curing the coating film, and the coating film tends to blister.

When the amount of the inorganic filler treated with an organic substance is less than 5 parts by weight based on 100 parts by weight of the prepolymer A,
There is no reinforcing effect on the coating and the inorganic filler settles during storage, forming a hard cake at the bottom of the storage container. On the other hand, when the compounding amount of the organic-treated inorganic filler exceeds 200 parts by weight, the viscosity of the urethane resin composition obtained becomes too high, and it becomes difficult to apply, spray, inject, and fill the urethane resin composition. Therefore, by mixing 5 to 200 parts by weight of an organic-treated inorganic filler with 100 parts by weight of prepolymer A, the urethane resin composition of the present invention does not separate even during long-term storage, and coating, spraying, pouring and filling. Sometimes the material runs out,
Workability is good because there is no so-called stringing. By using such an organic substance-treated inorganic filler, curing of the urethane resin composition is accelerated and the coating film is reinforced. The reason why the curing is accelerated seems to be that the organic substance used for the treatment has a function of promoting the ring opening of the oxazolidine ring.

[0016]

EXAMPLES Examples of the present invention will be described below. [Example 1] A planetary mixer was charged with 100 parts by weight of lauric acid-treated calcium carbonate as an organic-treated inorganic filler, 30 parts by weight of dioctyl phthalate, 20 parts by weight of titanium oxide, and 0.1 part by weight of carbon. Then, the mixture was kneaded at room temperature for 15 minutes, and subsequently, while being kneaded at 100 ° C., dehydration operation was performed for 1 hour in vacuum. Next, 100 parts by weight of polyoxypropylene triol (average molecular weight 4000) / tolylene diisocyanate prepolymer (terminal NCO group content = 3.7% by weight) and 2- (2-ethyl-1)
-3-oxazolidin-3-yl) -ethanol 4.4
Reaction product with parts by weight (hereinafter referred to as "prepolymer I") 1
00 parts by weight and 10 parts by weight of xylene were mixed in the kneaded product in the planetary mixer and kneaded at room temperature for 15 minutes to obtain a one-pack waterproofing material (equivalent ratio of NCO / OH =
3.0).

Next, in order to investigate the storage stability, 25
After leaving for 1 month at ℃ and 50 ℃, separation of waterproof material and tack free time according to JIS-A5758,
The viscosity was measured. Furthermore, when left at 25 ° C. for 1 month, the foaming state and the mechanical properties (hardness, tensile strength, elongation) according to JIS-K6301 were investigated. The results are shown in Table 1 below.

The measurement of the separation of the waterproof material is as follows: "Put a waterproof material in a 1 liter metal container and seal it with nitrogen.
It is carried out at 25 ° C. and 50 ° C. for 1 month, and then it is judged whether or not the inorganic filler is separated by sedimentation ”. The foaming state was as follows: "The one-component waterproof material produced as described above was poured onto a slate plate preheated to 50 ° C so that the coating film thickness was 2.0 mm, and the temperature was kept in a constant temperature chamber at 50 ° C. After standing, it is visually evaluated whether or not the cured coating film foams. "

[Example 2] Calcium carbonate treated with rosin acid was used as an organic-treated inorganic filler, and polyoxypropylene glycol (average molecular weight 2000) / diphenylmethane diisocyanate prepolymer (instead of prepolymer I of Example 1) was used. Terminal NCO group content = 2.2
% By weight) and 100 parts by weight of 2- (2-propyl-1,3-)
A one-pack waterproof material was obtained under the same conditions as in Example 1 except that a reaction product with oxazolidin-3-yl) -ethanol (5.6 parts by weight) (hereinafter referred to as "prepolymer II") was used (NC).
O / OH equivalent ratio = 1.5).

Further, in the same manner as in Example 1, various properties relating to storage stability and mechanical properties were investigated. The results are shown in Table 1.

Comparative Example 1 A one-component waterproof material was obtained in the same manner as in Example 1 except that untreated calcium carbonate was used in place of lauric acid-treated calcium carbonate. In addition, in the same manner as in Example 1, various properties related to storage stability and mechanical properties were investigated. The results are shown in Table 1.

[0022]

[Table 1]

As is clear from Table 1, the one-pack waterproofing materials according to Examples 1 and 2 do not separate or settle the inorganic filler even after being left at 25 ° C. and 50 ° C. for 1 month, and the It cures relatively quickly and there is no foaming in the coating.
However, since the untreated calcium carbonate was blended in Comparative Example 1, separation and sedimentation of this inorganic filler was observed after standing at 25 ° C for 1 month, and complete separation after standing at 50 ° C for 1 month. It gelled and became unusable.

[Example 3] 180 parts by weight of dioctyl phthalate, 200 parts by weight of lauric acid-treated calcium carbonate, and 50 parts by weight of titanium oxide were added to a planetary mixer.
0.3 parts by weight of carbon and 10 parts by weight of an antioxidant were charged, and the mixture was kneaded at room temperature for 10 minutes, and subsequently, at 100 ° C., dehydration operation was performed for 1 hour under vacuum.

Next, polyoxypropylene glycol (average molecular weight 2000) and polyoxypropylene triol (average molecular weight 3000) were mixed in a ratio of 2: 1,
This mixture was mixed with 2,4-tolylene diisocyanate and NC.
The reaction was carried out at an O / OH equivalent ratio = 1.7 to obtain a terminal N
CO group-containing prepolymer (Terminal NCO group content = 2.5
% By weight) and 100 parts by weight of a reaction product of 100 parts by weight of 2- (2-ethyl-1 / 3-oxazolidin-3-yl) -ethanol and 3.5 parts by weight of the mixture are mixed into the kneaded product in the planetary mixer. Then, the mixture was kneaded in a vacuum at room temperature for 15 minutes to obtain a one-component sealing material. (NCO / OH equivalent ratio =
2.5) Then, tack-free time according to JIS-A5758, foaming state, and penetration degree according to JIS-K2808,
The mechanical properties (100% modulus, tensile strength, elongation) according to JIS-K6301 were investigated. The results are shown in Table 2 below.

Comparative Example 2 200 parts by weight of untreated calcium carbonate was used in place of 200 parts by weight of lauric acid-treated calcium carbonate of Example 3, and a hydrophobic silica “#” produced by Japan Aerosil Co., Ltd. was used as a thixotropic agent. R-97
A one-component sealing material was obtained under the same conditions as in Example 3 except that 5 parts by weight of "2" were blended. Also in Comparative Example 2, the same characteristics as in Example 3 were investigated. The results are shown in Table 2 below.

[0027]

[Table 2]

As is apparent from Table 2, the one-part sealing material of Example 3 had excellent curability, no foaming was observed in the cured product, and the result of the viscosity examination by the penetration was 50 ° C./30. The viscosity after day is practically good, and there is no problem in mechanical properties. However, the resin of Comparative Example 2 was difficult to cure, foaming was observed in the cured product, and the result of the viscosity investigation by the penetration was 50.
The viscosity increased after 30 ° C./30 days and was unusable.

Example 4 A primer (moisture-curing urethane primer) was added to the roof of a concrete building in an amount of 0.2.
kg / m ^{2 was} applied, and after 3 hours, the one-component urethane resin composition obtained by the method of Example 1 was applied by a roller at 0.3 kg / cm ² ,
Immediately, a polyester non-woven fabric reinforcing agent (weight per unit area: 50 g / m ² ) was applied. And after 5 hours, it was possible to get on,
Further, the urethane resin composition of Example 1 (1.5 kg / cm ²⁾ was iron coated. The next day, an acrylic urethane topcoat was sprayed on. The thus obtained waterproof layer was free from blistering, peeling and water leakage even after 1.5 years from coating, and was sufficiently usable as a roof waterproofing material.

[Embodiment 5] 0.15 of a primer (moisture curing type urethane primer) was applied to the wall of a concrete building.
The composition was prepared by blending 10 parts by weight of xylol with 100 parts by weight of the urethane resin composition obtained by the method of Example 3 after 1 hour of coating with kg / m ² by air spraying on the above wall surface.
It was sprayed with 0 kg / m ² . The next day, 0.20 kg of acrylic urethane top coat was air sprayed on this wall.
/ M ^{2 was} sprayed.

The waterproof layer thus obtained is 1.5 after painting.
Even after a lapse of years, there was no blistering, peeling, or water leakage, and it could withstand use as a wall waterproofing material.

[0032]

Since the present invention is configured as described above, it has the following effects. Since it is a one-pack type, there is no need for compounding and mixing work as in the two-pack type, work efficiency is good, and pot life is not restricted. The composition does not separate and does not harden in the closed container, and has excellent storage stability. It cures quickly in air. The cured coating film does not foam and has excellent mechanical properties. By adjusting the blending amount of inorganic fillers and selecting the prepolymer skeleton, it can be used as a waterproofing material, sealing material, wall material, paving material, flooring material, paint, etc., depending on each purpose of use. You can

[Brief description of drawings]

FIG. 1 is an explanatory view of the operation of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // C09K 3/10 D

Claims (1)

[Claims] 1. A polyisocyanate compound and N-2-hydroxyalkyl-oxazolidine are reacted at an NCO / OH equivalent ratio = 1.2 to 10 to 100 parts by weight of a prepolymer containing a terminal free isocyanate.
A one-pack urethane resin composition containing 5 to 200 parts by weight of an inorganic filler treated with an organic substance.