KR100497288B1 - 1-component urethane sealant - Google Patents

Abstract

The present invention relates to a one-component urethane sealing material composition, wherein a polyol having a divalent or higher OH group and having a number average molecular weight of 400 to 8,000 and a compound having a divalent or higher isocyanate group at its terminal is reacted between NCO / OH 1.5 and 2.0 in a chemical equivalent ratio. The urethane prepolymer having an unreacted isocyanate group at the produced terminal is characterized by mixing a viscosity-providing compound.

This sealing material composition not only satisfies the required properties such as adhesiveness, elasticity, strength and watertightness as an adhesive for automobile glass, but also has high moisture and hardening and high viscosity as a sealing material. Since the attachment process can be eliminated, there is an advantage that the productivity can be improved compared to the existing sealing material.

Description

One-component urethane sealing material composition

The present invention relates to a one-component urethane sealing material composition, and more particularly, to a one-component urethane sealing material composition which can be applied mainly for direct grazing of automotive glass, side molding, board joints, and bonding or sealing around a bonnet. will be.

Existing one-component urethane sealing material has excellent physical properties such as adhesiveness, high elasticity, high strength, weather resistance, thixotropic and moisture hardening, and can be used for sealing work for the above purposes, but the viscosity of the sealing material is 15000-20000PS (20 ℃) and the hardening time of the sealing material has a long problem such as the need to attach a tape to prevent the sliding of the glass during the automobile glass work, as well as to prevent the device from sticking out (Rubber Dam).

And, in order to improve this, in order to shorten the curing time by adding an excessive amount of catalyst, as a one-component urethane sealing material, curing of the coating film is fast, but it is difficult to use due to poor storage stability. Viscosity can be increased, but in this case, there are many difficulties in mixing and dispersing and inferior physical properties of the sealing material.

In addition, while the preheating type containing latent curing agents such as kechimin, aldimine, and oxazolidine is highly viscous and fast to cure, high temperature hot box equipment must be used before the pressure pump is used, A lot of losses occur.

After all, the object of the present invention is to work without the use of taping and rubber dams when bonding the car window and meet all the physical properties of the automotive direct grazing adhesion, such as adhesiveness, high elasticity, watertightness and high weatherability improved workability and productivity 1 It is to provide a liquid urethane sealing material composition.

The one-component urethane sealing material composition for achieving the object of the present invention is based on a prepolymer (prepolymer) which is hardened quickly and has a high storage stability even without excessive catalyst input at room temperature, and can provide not only thixotropy but also viscosity to it. It is prepared using additives.

Specifically, unreacted at the terminal, produced by reacting a polyol having a divalent or higher OH group with a number average molecular weight of 400 to 8,000 and a compound having a divalent or higher isocyanate group at the terminal such that NCO / OH is between 1.5 and 2.0 in a chemical equivalent ratio The urethane prepolymer having an isocyanate group is prepared based on a high viscosity prepolymer mixture formed by mixing a viscosity-providing compound.

The one-component urethane sealing material composition of the present invention forms an elastic sealing material due to crosslinking generated by moisture or moisture in the air, and the components thereof are as follows.

First, the preparation of the prepolymer mixture is described.

In preparing the urethane prepolymer, polyols include polyoxypropylene glycol having an OH group at the terminal, polyoxypropylene glycol added with ethylene oxide (EO), polyoxytetramethyl glycol, polycaprolactone, polycaprolactam, polybutadiene, and the like. However, in order to achieve the rapid moisture hardening required in the present invention, at least polyoxypropylene to which ethylene oxide (EO) is added must be contained alone or in a mixture of polyols contained in the urethane prepolymer. The added polypropylene glycol is a polyol having 2 to 6 functional groups with a number average molecular weight of 500 to 7000 and an EO content of 5 to 80%, more preferably a EO content of 10 to 40%, and 2 to 4 It is preferable to use polypropylene glycol with EO addition whose functional group number and number average molecular weight are 1000-5000.

Moreover, as a compound which has a bivalent or more isocyanate group at the terminal, 2, 4- toluene diisocyanate, 4, 4- diphenylmethane diisocyanate, 1, 6- hexamethylene diisocyanate, isophorone diisocyanate, a xylene diisocyanate, 1, Aromatic or aliphatic isocyanates such as 5-naphthalene diisocyanate, 3,3-dimethoxy 4,4-biphenyl diisocyanate, 3,3-dimethyl 4,4-biphenyl diisocyanate, phenylenedi isocyanate alone or in combination The most suitable of these compounds is preferably 4,4-diphenylmethane diisocyanate alone or mixed with 2,4-toluene diisocyanate. The mixing ratio thereof is preferably in the range of 8: 2 to 2: 8, and more preferably 7: 3 to 5: 5 in terms of chemosugar.

The method for preparing a prepolymer using the above-described raw material includes a polyol containing EO-containing polypropylene glycol alone or a part thereof within 0.05% of water (more preferred, as mentioned above in the dihydric polyol or more hydroxylated at the terminal). Dehydrated at less than 0.01%) and react with divalent or more aromatic or aliphatic isocyanate with NCO / OH 1.5-2.0 (more preferably 1.7-1.9) in a chemical equivalent ratio and react the temperature at 60-100 ° C. for at least 10 hours. The urethane prepolymer having an unreacted isocyanate group is obtained. As such, the urethane prepolymer having an isocyanate group at the end is a moisture curing type in which the NCO group reacts with moisture in the air to cure.

A viscosity imparting compound is added to the urethane prepolymer obtained as described above to increase the viscosity, and these compounds have an excellent effect on the viscosity increase in the stationary state after mixing with the urethane prepolymer, so that not only the urethane prepolymer but also the urethane sealant are manufactured. It is possible to solve the problem of dispersion that may be caused by the excessive input of the powder filler for high viscosity in the manufacture of the sealing material. Viscosity-imparting compounds that can be used include high molecular compounds such as castor oil wax, amide wax, plant polymer oil, castor wax and amide wax mixture, castor wax and cray mixture, and polymeric urea-urethane compound. The amount is 1 to 10 parts by weight based on 100 parts by weight of the prepolymer, and a high viscosity urethane prepolymer mixture is stirred at high speed until the temperature of the prepolymer is charged between 50 and 60 ° C. until the viscosity-comprising compound is completely dissolved in the prepolymer. To prepare.

The prepolymer mixture obtained by the present invention has a viscosity of 5000 to 10000 PS at room temperature (20 ° C.), and a prepolymer mixture which is not affected by moisture in order to prepare a continuous one-component moisture hardening sealing material (storage temperature: 40 to 50). ℃). In addition, the temperature is maintained at 50 to 60 ° C. for easy transportation of the urethane prepolymer mixture.

And the viscosity giving compound used herein is defined in the Examples and claims.

In order to prepare a one-component urethane sealant having a urethane prepolymer mixture prepared by the above method, the raw materials are stored and transported by a sealed device so as not to affect the moisture. That is, in addition to the urethane prepolymer mixture storage tank, the liquid raw material storage tank (e.g., plasticizer, etc.), powder raw material storage tank (e.g., carbon black, calcium carbonate fillers), and additive storage tank (e.g. thixotropic agents, catalysts, etc.) Moisture and curing in the air is fast to obtain a sealing material composition having a high viscosity of 30000 PS or more at room temperature (20 ℃).

In the present invention, in the production of a one-component urethane sealant, the curing catalyst is an organometallic catalyst such as dibutyl tin dilaurate (DBTDL), tetrabutyl titanate, dibutyl tin butyl malonate, stanners octate, and dimethyl cyclohexyl. Amine, tetramethylguanidine (TMG), tetramethylethylenediamine (TMEDA), triethylenediamine (DABCO), dimethylpiperazine, trimethylpiperazine, 1,4-bis (2-hydroxypropyl) -2-methylpiperazine Although amine catalysts such as (DHPMP) may be used alone, it is more preferable to mix and use an organometallic catalyst and an amine catalyst to promote curing.

In the present invention, since the amount of the catalyst input during the production of the sealing material is used in an appropriate amount of 0.05 parts by weight or less in the total weight of the sealing material composition, rather than an excessive amount, the storage stability of the sealing material is obtained. When 0.1 weight part or more of catalysts are added, since the storage property is extremely poor, there exists a possibility that a sealing agent composition may gelatinize.

Also, as plasticizers, phthalates such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate, diisododecyl phthalate, butylbenzyl phthalate, dioctyl adipate, diisooctyl adipate, and diisononyl adipate Adipates such as or trioctyl trimellitate, trimellitates such as triisooctyl trimellitate and mesamol can be used alone or in combination.

A description with reference to the following Examples.

Preparation of Urethane Prepolymer Mixtures

Preparation Example 1

Polypropylene glycol triol having an average molecular weight of 3100 and an EO content of 20% (trade name: Polygon Co., Ltd. SC-3314) 3305 parts by weight and 800 parts by weight of polypropylene diol having an average molecular weight of 2000 were mixed / stirred to 100 ° C. The water is dehydrated for 5 hours or more until the water content of the polyol is 0.01% or less under vacuum decompression while maintaining the temperature at elevated temperature. Next, 895 parts by weight of 4,4-diphenylmethane diisocyanate is added to maintain the reaction temperature at 75 ° C until the free isocyanate of the prepolymer becomes 2.5%.

Then, 150 parts by weight of a hydrogenated castor oil wax-based viscosity imparting compound (trade name: Kusumoto Chemical Co., Ltd. Disparon 305) was added to the ebipolymer cooled to 55 ° C., and then dissolved in a high-speed stirring urethane prepolymer having a viscosity of 7500 PS (20 ° C.). A mixture was prepared.

Preparation Example 2

A mixture of 178 parts by weight of 2,4-toluene diisocyanate and 382 parts by weight of 4,4-diphenylmethyl diisocyanate in 4440 parts by weight of polypropylene glycol triol (Konics SC-3513) having an average molecular weight of 5100 and an EO content of 15%. After the reaction was carried out until the free isocyanate of the prepolymer became 2.0%, a urethane prepolymer mixture having a viscosity of 7000 PS (20 ° C.) was added by adding 175 parts by weight of a polyamide wax-based viscosity imparting compound (trade name: Disparon 6500). Was prepared. At this time, the manufacturing method is the same as that of Preparation Example 1.

Preparation Example 3

To the polyol, a mixture of 3830 parts by weight of polypropylene glycol triol having an average molecular weight of 5000 and 720 parts by weight of polypropylene diol having an average molecular weight of 3000 was added 450 parts by weight of 2,4-toluene diisocyanate. A urethane prepolymer of 420 PS (20 ° C.) was obtained.

Preparation Example 4

To the prepolymer of Preparation Example 3, 175 parts by weight of the viscous compound (disparon 6500) was added to obtain a prepolymer mixture having a viscosity of 7500 PS (20 ° C.).

Preparation Example 5

825 parts by weight of 4,4-diphenylmethyldiisocyanate was added to 4175 parts by weight of polypropylene glycol triol having an average molecular weight of 3500 and an EO content of 15% to give a free isocyanate of 2.5 and a viscosity of 510 PS (20 ° C.). A mixture was obtained.

Preparation of 1-component urethane sealing material composition

Example 1

480 parts by weight of the urethane prepolymer mixture prepared in Preparation Example 1 with 300 parts by weight of carbon black, 6 parts by weight of calcium carbonate, dehydrated plasticizer (DOP) and 1.5 parts by weight of thixotropic agent Additives consisting of 0.03 parts by weight of catalyst (0.01 parts by weight of DBTDL and 0.02 parts by weight of DABCO), and a small amount of raw materials such as dispersants are added and added to the mixers in each reservoir to uniformly mix and dehydrate under reduced pressure to obtain high viscosity and moisture. The one-component urethane sealant composition having a rapid curing with was prepared.

Example 2

The urethane prepolymer mixture prepared in Preparation Example 2 was used to prepare a one-component urethane sealing material composition having high viscosity and rapid curing with moisture by the same composition and preparation method as in Example 1.

Comparative Examples 1-3

With each prepolymer mixture prepared in Preparation Examples 3, 4, and 5, a one-component urethane sealing material composition was prepared in the same manner and composition as in Example 1.

Comparative Example 4

A one-component urethane sealant preparation was prepared in the same manner and composition as in Example 1 with the prepolymer mixture prepared in Preparation Example 4. However, only 0.15 parts by weight of the catalyst input was added in excess to Comparative Example 2.

The compositions of the prepolymers or prepolymer mixtures prepared in Preparation Examples 1 to 5 are shown in Table 1 below, and the properties and physical properties of the one-component urethane sealing material compositions prepared in Examples 1 and 2 and Comparative Examples 1 to 4 are shown in Table 2 below. Indicated.

TABLE 1

TABLE 2

In addition, the measurement method of the physical property was carried out in accordance with the standard of the automobile manufacturer, the physical properties of the production examples, examples and comparative examples were values satisfying the standard, and all other physical properties items were satisfactory level.

However, as shown in Tables 1 and 2, the one-component urethane sealing material composition (Examples 1 and 2) prepared by the urethane prepolymer mixture of Preparation Examples 1 and 2 was prepared as the prepolymers of Preparation Examples 3 and 4 and 5. It can be seen that it is a highly viscous urethane sealing material composition having excellent storage stability and quick curing with moisture than the one-component urethane sealing material composition (Comparative Examples 1 to 4) prepared with the prepolymer mixture.

As described in detail above, the sealing material composition of the present invention not only satisfies the required properties such as adhesiveness, elasticity, strength and watertightness, especially as an adhesive for automobile glass, but also has high moisture and curing as a sealing material and has high viscosity, and thus, glass upon initial curing. Since the taping work and the rubber dam attachment process for the support of the can be eliminated, there is an advantage that can bring productivity improvement compared to the existing sealing material.

Claims (6)

Unreacted at the terminal, produced by reacting a polyol containing polyoxypropylene glycol added with ethylene oxide (EO) as an essential component and a compound having a divalent or higher isocyanate group at the terminal such that NCO / OH is 1.5 to 2.0 in a chemical equivalent ratio 100 parts by weight of a urethane prepolymer having an isocyanate group; One or more viscosity giving compounds selected from castor oil wax system, amide wax system, plant polymerization oil system, castor oil wax system and amide wax system, castor oil wax system and cray mixture system, and polymeric urea-urethane compound system1 A one-component urethane sealing material composition based on a urethane prepolymer mixture formed by adding ˜10 parts by weight. The one-component urethane sealing material composition according to claim 1, wherein the polyoxyflofilene glycol to which ethylene oxide (EO) contained in the polyol is added has an EO content of 5 to 80%. The polyol according to any one of claims 1 and 2, wherein the polyol is selected from polyoxypropylene glycol added with ethylene oxide and polyoxypropylene glycol, polyoxytetramethylene glycol, polycaprolactone, polycaprolactam and polybutadiene. A one-component urethane sealing material composition, characterized in that at least one species is mixed composition. The one-component urethane sealing material composition according to any one of claims 1 and 2, wherein the polyoxypropylene glycol added with ethylene oxide has 2 to 6 functional groups and a number average molecular weight of 500 to 7000. The compound according to claim 1, wherein the compound having a divalent or higher isocyanate group at its terminal is 2,4-toluene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate 1,5 At least one member selected from the group consisting of naphthalene diisocyanate, 3,3-dimethoxy 4,4-biphenyl diisocyanate, 3,3-dimethyl 4,4-biphenyl diisocyanate and phenylene diisocyanate One-component urethane sealing material composition. The one-component urethane sealing material composition of any one of claims 1 to 2, 4 to 5 and 7 is bonded or sealed to automotive glass adhesives, side moldings, bonnets and trunks, plastics, and steel plate joints. Use for purposes.