KR20060079552A - Two-component type room temperature curable polyurethane composition - Google Patents

Abstract

The present invention relates to a polyurethane composition, and more particularly, by modifying a diamine curing agent to monoepoxide, it is possible to secure sufficient pot life even in a high temperature and low temperature working environment without using a heavy metal catalyst, It is possible to form a coating film, and moreover, to satisfy various physical properties with excellent solvent-free workability without using 4,4'-methylenebis (2-chloroaniline), which is a carcinogenic substance generally used in polyurethane compositions. It is to provide a two-component polyurethane composition that can be.

Two-component polyurethane composition

Description

 Two-component type room temperature curable Polyurethane composition

The present invention relates to a polyurethane composition, the polyurethane composition has been used in various applications, such as the roof of the building, veranda, waterproofing of stairs and elastic flooring of sports facilities, flooring for outdoor parking, etc. due to the excellent weather resistance compared to the epoxy composition .

Conventionally, the polyurethane composition is composed of an isocyanate-terminated urethane prepolymer main body prepared from isocyanates such as TDI (toluene diisocyanate) and long chain polyols, and 4,4'-methylenebis (2-chloroaniline) which is an aromatic diamine as an isocyanate reaction component. Hereafter, abbreviated as 'MOCA') and a curing agent part containing a long chain polyol (addition of a catalyst such as organometallic and lead or a plasticizer as needed) at the construction site, and then It was prepared by hand coating after use and curing.

Prepolymer systems made from TDI and long chain polyols in polyurethane compositions are described in US Pat. Nos. 3,701,374, 3,963,681, 4,029,730, 4,089,822, 4,133,943, and 4,365,051. The isocyanate prepolymers described in these patents are prepolymers with high oligomer content as well as containing unreacted TDI.

Aromatic polyamines and aliphatic polyamines are commonly used as curing agents for curing such prepolymers. For example, US Pat. No. 4,182,825 describes a technique of using MOCA as a curing agent to prepare compositions with improved physical properties. However, there are many drawbacks and problems when using MOCA as a curing agent.

First, due to the high melting point of MOCA, it exists as a solid at room temperature and is difficult to use, such as being precipitated under polyol dissolution.

Secondly, since the aromatic diamine is used by heating and melting, not only the physical properties of the urethane composition are deteriorated, but also the color is severely changed by heating, and since the melting and heating are used, the manufacturing cost is increased by consuming a large amount of thermal energy.

Third, MOCA is a carcinogenic substance (A2), which is not only subject to legal regulations in storage, use, and transportation, but also has many shortcomings and problems as an extremely harmful substance for workers' health.

However, despite so many shortcomings and problems, it has been the only material as an aromatic amine crosslinker for urethane compositions such as excellent reactivity with isocyanate terminated prepolymers, sufficient pot life, and satisfactory physical properties after curing.

The inventors of the present invention overcome the shortcomings and problems of the conventional method, and develop and apply a curing agent for a polyurethane composition having excellent reactivity, sufficient pot life, and satisfactory physical properties after curing without using MOCA, which is an existing curing agent. Was completed. Accordingly, an object of the present invention is to provide a urethane composition having sufficient pot life and excellent physical properties.

The present invention relates to a method for producing a two-component polyurethane and a composition thereof, which can ensure proper pot life and satisfy basic properties such as hardness.

More specifically, a monoepoxide-modified diamine curing agent and diamine curing agent composed of a prepolymer having an isocyanate group at the terminal synthesized by reaction of aromatic or aliphatic diisocyanates with polyether polyols and / or low molecular glycols It relates to a method for producing a polyurethane composition excellent in physical properties by mixing and curing at room temperature using a curing agent portion composed of an additive such as a plasticizer.

The present invention is the main portion of the urethane prepolymer having an isocyanate group at the end and mono-epoxide modified diamine curing agent 1.0 to 5.0% by weight, diamine curing agent 1.0 to 5.0% by weight, pigment 40.0 to 60.0% by weight, plasticizer 25.0 to 45.0% by weight, dispersant, It is characterized by a two-component room temperature curable polyurethane resin composition comprising a curing agent portion containing 0.1 to 10.0% by weight of any one or more additives selected from a sedimentation inhibitor, an antifoaming agent, an ultraviolet stabilizer, and a moisture absorbent. It is preferable that the said main part and a hardening | curing agent part consist of 1: 1 to 3 weight ratio.                     

Thus, the present invention will be described in detail for each component.

First, the urethane prepolymer is prepared by reacting an isocyanate with a polyol as a resin composition applied to a conventional two-component resin.

Examples of the isocyanate include aromatic isocyanate and alicyclic isocyanate, and examples of the aromatic isocyanate include, for example, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,6-xylene diisocyanate, para-phenylene diisocyanate, 3,3'-tolidene-4,4'-diisocyanate, 3,3 -Dimethyl-diphenylmethane-4,4'-diisocyanate can be used, and examples of the alicyclic diisocyanate include 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, Bis (isocyanatomethyl) cyclohexane, tetramethyl styrene diisocyanate, etc. are mentioned, One or more of these is mixed and used.

The polyol may be a polyether polyol having a number average molecular weight of 500 to 5000 having 2 to 3 activated hydrogens, specifically, polybutadiene diol, polytetramethylene ether glycol, polypropylene oxide glycol and triol, polybutylene Oxide glycol and triol, and low molecular glycols are characterized by 1,6-hexanediol, neopentyl glycol, 1,4 and 1,3 butanediol, ethylene propylene glycol, diethylene glycol, dipropylene glycol, etc. One or more of these may be mixed and used, and appropriately adjusted and selected according to the physical properties and properties to be finally expressed within the above-described conditions.                     

The isocyanate and polyol may be used in an equivalence ratio of isocyanate group (NCO) and hydroxyl group (OH) in the range of 1.0 to 5.0: 1, preferably 1.5 to 2.5: 1, and if the equivalent ratio is less than 1.0, the viscosity may be high. If it exceeds 5.0, the storage stability of the urethane prepolymer becomes poor.

Next, the curing agent portion may include a mono epoxide-modified diamine curing agent, a diamine curing agent, a plasticizer, a pigment, a dispersant, an antifoaming agent, a moisture absorbent, an ultraviolet stabilizer, and a precipitation inhibitor as a curing agent mixture.

The mono epoxide-modified diamine curing agent is used to improve the disadvantage of poor workability due to fast pot life when using diamine curing agent alone, the effect of delaying the reaction with NCO due to the steric hindrance effect of the mono-epoxide modified group and Due to two or more functional groups per molecule, there is an effect of increasing the crosslinking density after curing.

The monoepoxide-modified diamine curing agent may include neodecanoic acid oxiranylmethyl ester and / or epichlorohydrin, and the monoepoxide and diamine may be 80 to 150 degrees. Synthesis at to prepare a monoepoxide modified diamine. Such diamines include isophorone diamine, diethylene diamine, ethyldiamine, 1,2-bis- (2-amino-phenyldioethane), 1,1'-isopropylidine-bis- (para-phenylene-oxy ) -Di-2-ethanol, diethyltoluenediamine, dimethylthiotoluenediamine, 1,3-trimethylene glycol-bis (para-aminobenzoate), methylene-bis-N, N'-dibutylaniline, and the like. Can be mentioned.

The monoepoxide-modified diamine curing agent is used in an amount of 1.0 to 5.0% by weight, preferably 1.5 to 3.0% in the curing agent mixture. When the amount is less than 1.0% by weight, the reaction rate between the curing accelerator diamine and the prepolymer cannot be slowed down. If the time is faster, more than 5.0% by weight, there is a disadvantage that the tensile strength, tear strength, hardness, and the like fall.

As the diamine curing agent, isophorone diamine, diethylene diamine, ethyldiamine, 1,2-bis- (2-amino-phenyldioethane), 1,1'-isopropylidine-bis- (para-phenylene-oxy ) -Di-2-ethanol, diethyltoluenediamine, dimethylthiotoluenediamine, 1,3-trimethylene glycol-bis (para-aminobenzoate), methylene-bis-N, N'-dibutylaniline and the like It is characterized in that it can be used by mixing one or more of these. Among them, it is preferable to use DETDA (diethyltoluenediamine) in terms of mechanical properties.

If the content of the diamine curing agent in the curing agent mixture is high, the tensile strength, tear strength, elongation, and hardness are good, but the reaction is fast and the pot life does not come out. Therefore, 1.0 to 5.0% by weight, preferably 2.0 to 4.0% by weight of the curing agent mixture is used, but when the amount is less than 1.0% by weight, the physical properties deteriorate, and when it exceeds 5.0% by weight, the pot life is shortened and workability becomes poor.

The plasticizer is DOP (dioctylphthalate), DINP (diosonylyl phthalate), DOA (dioctyl adipate), TOTM (trioctyl trimellitate), DBP (dibutyl phthalate), DIDP (diisodecyl phthalate) ), DOM (dioctyl methacrylate), DINA (diisononyl adipate) and the like can be used, most preferably DBP.

The plasticizer is used in 25.0 to 45.0% by weight, preferably 35.0 to 40.0% by weight of the curing agent mixture, when the amount is less than 25.0%, the viscosity is high and the workability is poor, and when the used amount is more than 45.0% by weight, the workability is good but it is precipitated during storage. This can lead to poor storage stability and low hardness.

The pigment may be a sieving pigment or a coloring pigment, and the sieving pigment may be a sieving pigment commonly used, such as calcium carbonate, talc, silicon dioxide, or dolomite, and as a coloring pigment, carbon black, iron oxide, disaccharide, cyanine You can use what is chosen from organic-based pigments, such as green. The amount of such pigment used is 40.0 to 60.0% by weight in the curing agent mixture. If it is less than 40 weight%, the hardness of a coating film will become low, and if it exceeds 60.0 weight%, a viscosity will become high and workability will be inferior and coating property will be weak.

In addition, one or more additives selected from a dispersant, a UV stabilizer, an antifoaming agent, a sedimentation inhibitor, a moisture absorbent, and the like may be used, and the amount thereof is 0.1 to 10.0 wt% in the curing agent mixture.

The present invention will be explained in more detail with reference to the following examples and comparative examples.

 The present invention will be described in detail through the following examples. This example does not limit the scope of the invention.

The raw material used by a present Example is as follows.

TDI: Toluene Diisocyanate

PP-2000: Polypropylene Glycol (Molecular Weight: 2000) (Polyol Korea)

PP-3000: Polypropylene Glycol (Molecular Weight: 3000) (Polyol Korea)                     

GP-3000: Polypropylene Glycol (Molecular Weight: 3000) (Polyol Korea)

MOCA: 4,4'-methylenebis (2-chloroaniline)

DETDA: diethyltoluenediamine (ALBEMARLE)

DBP: Dibutyl Phthalate

NAOE: neodecanoic acid oxiranylmethyl ester (RESOLUTION)

ECH: epichlorohydrin

DEG: diethylene glycol

Metallic dryer: Pb-Octoate 24%

BYK-066: Silicone antifoaming agent, BYK

Sieving Pigments: Calcium Carbonate

Recipe of the subject

According to the formulation table of the following Examples and Comparative Examples, TDI having a weight ratio of 2,4-isomer / 2,6-isomer is 80/20 into a 2 l glass flask, and PP-2000, GP-3000, and DEG were respectively added under a nitrogen stream. After the completion of the reaction of the para-position NCO group at 60 ℃ or less at 90 ~ 105 ℃ heated for 4 to 8 hours, the reaction was completed. In this way, a urethane prepolymer, which is an isocyanate terminated prepolymer, was prepared.

Preparation of hardener

MOCA, PP-3000, NAOE-modified diamine, ECH-modified diamine, DETDA, DBP, sieving pigment (CaCO ₃ ), antifoaming agent (BYK-066) and metallic dryer were added to a 2L cylinder container according to the formulation table of Examples and Comparative Examples below. And stirred for 25 minutes at room temperature to prepare each curing agent.

[Examples 1-3]

TDI, PP-2000, and GP-3000 having a weight ratio of 2,4-isomer / 2,6-isomer of 80/20 were combined in the equivalent ratios in Table 1 below, and then synthesized by the formulation of the subject matter.

In preparing the curing agent, a curing accelerator diamine DETDA and NAOE modified diamine or ECH modified diamine for retardation of reactivity were mixed and prepared in the weight ratio in Table 1 below.

Examples 1 and 3 were NAOE, and Example 2 was DETDA modified with ECH.

Comparative Example 1

TDI, PP-2000, GP-3000, and DEG having a weight ratio of 2,4-isomer / 2,6-isomer by weight of 80/20 in the prior art were synthesized in the formulation of the subject after compounding in the equivalent ratio in Table 2 below.

In preparing the curing agent, MOCA and the long-chain polyol were prepared after mixing in a weight ratio in Table 2 below. MOCA was used after being dissolved in polyol because it was solid at room temperature.

At this time the isocyanate jockeys ratio of NCO / (OH + NH ₂₎ of the total non-amino group and a chapter of the curing agent diamine plus the hydroxyl nose of a chain polyol of the urethane prepolymer is 1.09: unreacted isocyanate of a first isocyanate composition group prepolymer Compared to 2.5% by weight.

[Comparative Examples 2 and 3]

Comparative Examples 2 and 3 compared the change in mechanical properties and pot life when used alone without mixing DETDA and mono epoxide-modified DETDA when mixing the curing agent.

After mixing the main material prepared as described above and the curing agent according to the weight ratio, the pot life and gelation time are measured with a Brookfield viscometer. The physical properties of the specimens were measured 7 days after the coating of the mixed solution mixed in the weight ratio to a glass plate 2mm thickness, the coating film properties are measured by UTM.

The test lists listed in Tables 1, 2 and 3 in connection with Examples and Comparative Examples are as follows.

<Housework time and curability>

Pot life: The time from mixing the master and the hardener to working (the time until the viscosity of the mixture reaches 25,000 cps at Brookfield Viscometer Spindle # 6, 10 rpm).

Gelation time: The time after mixing of the main material and the curing agent and starting to lose fluidity (the time until the viscosity of the mixture reaches 100,000 cps at Brookfield Viscometer Spindle # 6, 10 rpm.

-No adhesion time: The time elapsed until the adhesion of the mixed solution disappears from the surface of the coating film.

TABLE 1

TABLE 2

As can be seen from the results, Examples 1, 2, and 3 have sufficient effect due to the delayed reaction with NCO due to the steric hindrance effect of the mono-epoxide modified group and the crosslinking density after curing due to more than 2.3 functional groups per molecule. It showed time and excellent mechanical properties.                     

Comparative Example 1 has a disadvantage in that mechanical properties are excellent but MOCA is a carcinogenic substance.

In addition, as a result of applying DETDA alone as in Comparative Example 2, the mechanical properties were excellent, but the pot life was very short.As a result of applying mono epoxide-modified DETDA alone as in Comparative Example 3, the pot life was sufficiently secured but the mechanical properties were weak. Indicated.

Therefore, the polyurethane two-component composition of the present invention is capable of ensuring sufficient pot life even in high and low temperature working environments without heavy metal catalysts by using a diamine curing agent as a monoepoxide and increasing the crosslinking density after curing. The coating film can be formed, and it is used in the polyurethane composition, which is a conventional carcinogenic substance, and can satisfy various physical properties with excellent solvent-free workability without using 4,4'-methylenebis (2-chloroaniline). It was possible to provide a two-part polyurethane composition.

Claims (4)

Urethane prepolymer main part having an isocyanate group at the terminal and monoepoxide modified diamine curing agent 1.0 to 5.0% by weight, diamine curing agent 1.0 to 5.0% by weight, pigment 40.0 to 60.0% by weight, plasticizer 25.0 to 45.0% by weight, dispersant, antisettling agent, A two-component room temperature curable polyurethane resin composition comprising a curing agent portion containing 0.1 to 10.0 wt% of at least one additive selected from an antifoaming agent, an ultraviolet stabilizer, and a water absorbent. The method of claim 1, A two-component room temperature curable polyurethane resin composition comprising the main portion and the curing agent portion in a ratio of 1: 1 to 3 weight. The method of claim 1, The diamine curing agent isophorone diamine, diethylene diamine, ethyldiamine, 1,2-bis- (2-amino-phenyldioethane), 1,1'-isopropylidine-bis- (para-phenylene-oxy) 1 selected from di-2-ethanol, diethyltoluenediamine, dimethylthiotoluenediamine, 1,3-trimethylene glycol-bis (para-aminobenzoate), methylene-bis-N, N'-dibutylaniline, and the like. A two-component room temperature curable polyurethane resin composition characterized by using more than one component. The method of claim 1, The monoepoxide modified diamine curing agent is prepared by reacting neodecanoic acid oxyrenylmethyl ester or epichlorohydrin or a mixture thereof with diamine.