KR102554888B1 - Non-yellowing organic-inorganic hybrid tile grout composition - Google Patents

Abstract

The present invention relates to a non-yellowing organic-inorganic hybrid joint agent composition, which is composed of hexamethylene-1,6-diisocyanate trimer (HDT), a non-yellowing urethane prepolymer, a silica sol and a plasticizer It consists of a main agent and a curing agent composed of polyaspartic acid (PAA), aminotrimethoxysilane and additives, and the hexamethylene-1,6-diisocyanate trimer and non-yellowing urethane prepolymer are 1:1 to a non-yellowing organic-inorganic hybrid joint agent composition that is mixed at a weight ratio of 6:1, exhibits an appropriate curing rate, has excellent manual workability, and suppresses yellowing.

Description

Non-yellowing organic-inorganic hybrid joint agent composition {NON-YELLOWING ORGANIC-INORGANIC HYBRID TILE GROUT COMPOSITION}

The present invention relates to a non-yellowing organic-inorganic hybrid joint agent composition, and more particularly, through an organic-inorganic hybrid joint material composition composed of polyaspartic polyurea and inorganic materials, it exhibits an appropriate curing speed during joint operation and has excellent manual workability It relates to a non-yellowing organic-inorganic hybrid joint agent composition that exhibits the effect of suppressing yellowing.

When a certain period of time elapses after construction, tiles installed on the wall or floor of a building need to be repaired due to problems such as penetration of contaminants, generation of mold, and deterioration of adhesive strength. White cement or epoxy-based joint agents are used as joint agents used for joint repair work, but in the case of water-based epoxy-based joints, construction conditions and hardening time are long, and in the case of solvent-free epoxy-based joints, yellowing occurs. There are problems such as long hardening time and poor workability.

For example, Korean Patent Registration No. 10-1115011 discloses yellowing by using a joint repair agent composed of a solvent-free epoxy resin and a curing agent to suppress workability, water resistance, durability, weather resistance, strength, adhesiveness, chemical resistance, resistance Although a joint composition with improved physical properties such as staining properties has been disclosed, there is a limit to shortening the curing time, which is a problem of epoxy-based repair agents, so that it is difficult to use depending on the working environment.

In order to solve this problem, Korean Patent Publication No. 10-2013-0064040 improves whitening and yellowing after joint work by using a joint composition for tiles composed of a main material made of polyurea, a curing agent and additives. In addition, Korean Patent Registration No. 10-1736583 improves manual workability and adhesive strength during joint repair work by using a joint repair agent composition in which a main material made of polyaspartic urea and a hardener are mixed.

From these prior arts, it can be seen that the joint agent composition containing polyurea can exhibit an advantageous effect in improving workability by shortening the curing time.

Republic of Korea Patent Registration No. 10-1115011 Republic of Korea Patent Publication No. 10-2013-0064040 Republic of Korea Patent Registration No. 10-1736583

The present invention was devised in view of the prior art as described above, and by securing sufficient pot life by exhibiting an appropriate curing speed during joint work through an organic-inorganic hybrid type joint composition containing polyaspartic polyurea and inorganic materials An object of the present invention is to provide a joint material composition capable of improving manual workability and suppressing yellowing.

The non-yellowing organic-inorganic hybrid joint agent composition of the present invention for solving the above problems is hexamethylene-1,6-diisocyanate trimer (HDT), non-yellowing urethane prepolymer, silica Consisting of a main component composed of sol and plasticizer and a curing agent composed of polyaspartic acid (PAA), aminotrimethoxysilane and additives, the hexamethylene-1,6-diisocyanate trimer and non-yellowing urethane The prepolymer is characterized in that it is mixed in a weight ratio of 1:1 to 6:1.

In this case, the hexamethylene-1,6-diisocyanate trimer has an NCO content of 20 to 25%, the non-yellowing urethane prepolymer has an NCO content of 7 to 15%, and the polyaspartic acid has an amine equivalent of 190 to 280 g/mol It is desirable to be

In addition, the silica sol is prepared by mixing an alkoxysilane, a silane coupling agent, an acid catalyst, and a co-solvent of water and alcohol and hydrolyzing the silica sol, and the alcohol may be removed by distillation under reduced pressure.

The joint material composition according to the present invention is an organic-inorganic hybrid type joint composition containing polyaspartic polyurea and an inorganic material, and exhibits an appropriate curing speed during joint work to secure sufficient pot life, thereby improving manual workability. It can show the effect of suppressing the yellowing phenomenon after joint work.

Hereinafter, the present invention will be described in detail.

The non-yellowing organic-inorganic hybrid joint agent composition according to the present invention includes a subject consisting of hexamethylene-1,6-diisocyanate trimer (HDT), a non-yellowing urethane prepolymer, silica sol, and a plasticizer, and It is composed of a curing agent composed of polyaspartic acid (PAA), aminotrimethoxysilane and additives, and the hexamethylene-1,6-diisocyanate trimer and the non-yellowing urethane prepolymer are 1: 1 to 6: 1 It is characterized in that it is mixed in a weight ratio.

The polyurea-based joint composition is prepared through a process of forming polyurea by the reaction of an isocyanate compound and an amine-based curing agent. In order to prepare a polyaspartic polyurea joint composition, as in Korean Patent Registration No. Similarly, a polyaspartic polyurea grout composition is obtained through a process of reacting a base material containing an isocyanate compound with a curing agent containing aspartic amine. However, the isocyanate compound and the aspartic amine have a fast curing rate, so that after forming the composition, they are cured before construction.

In order to improve this, it is possible to prepare a polyaspartic polyurea joint composition by reacting HDT with PAA instead of reacting with aliphatic isocyanate and aspartic amine, but it is difficult to control the curing speed. can't

In order to solve this problem, in the present invention, a urethane prepolymer is mixed with hexamethylene-1,6-diisocyanate trimer constituting the main component. When the urethane prepolymer is mixed, the hexamethylene-1,6-diisocyanate trimer is stabilized and the reactivity is slightly lowered, so it was found that the curing speed is too fast to solve the problem that curing occurs before joint construction.

To this end, it was found that the hexamethylene-1,6-diisocyanate trimer and the urethane prepolymer are preferably mixed in a weight ratio of 1:1 to 6:1. When the HDT and the non-yellowing urethane prepolymer are mixed in the above range, the workable time after mixing the main agent and the curing agent, that is, the pot life can be increased, so that it is possible to work without being restricted by the working time during joint repair work. That is, the hexamethylene-1,6-diisocyanate trimer and the non-yellowing urethane prepolymer have NCO contents of 20 to 25% and 7 to 15%, respectively. Due to the combination of two components having different NCO contents, the curing agent and It has been shown that the rate of reaction can be controlled.

As described above, the hexamethylene-1,6-diisocyanate trimer is preferably mixed with the urethane prepolymer in a weight ratio of 1: 1 to 6: 1, specifically 35 to 55 parts by weight It is preferable to use do. If the content of the HDT is too small, it is difficult to form a coating film and mechanical properties are deteriorated.

In addition, the non-yellowing urethane prepolymer is produced by the reaction of isocyanate and polyol, and a hydroxyl group of polyol reacts with an isocyanate group of isocyanate to form a urethane bond. Since the non-yellowing urethane prepolymer also exhibits the effect of improving the elongation and flexibility of the joint composition by being blended with the curing agent, the physical properties of the joint composition can be improved through combination with hexamethylene-1,6-diisocyanate trimer. there is. In addition, it is possible to reduce the amount of expensive hexamethylene-1,6-diisocyanate trimer, thereby reducing the manufacturing cost of the joint agent composition.

The isocyanate group formed at the end of the non-yellowing urethane prepolymer preferably has a residual rate of 5 to 15%. If the terminal isocyanate group is less than 5%, the abrasion resistance and hardness of the joint agent composition may be reduced, and if it exceeds 15%, the bending resistance may be reduced and the reaction rate may be increased, thereby reducing joint repair work efficiency. In addition, the non-yellowing urethane prepolymer preferably has a molecular weight of 2,000 to 3,000 g/mol. This is because if the molecular weight is too small, the flexibility and impact resistance of the joint work area may be reduced, and if the molecular weight is too large, the viscosity of the joint agent composition may be too high and workability may be reduced.

As described above, the non-yellowing urethane prepolymer is preferably mixed with hexamethylene-1,6-diisocyanate trimer in a weight ratio of 1: 1 to 6: 1, specifically used in the range of 10 to 35 parts by weight It is desirable to do If the content of the non-yellowing urethane prepolymer is too small, a problem in that elongation and flexibility cannot be sufficiently secured, and if the content is too large, mechanical properties may be deteriorated.

In addition, the silica sol constitutes an organic-inorganic hybrid joint agent by silane-modifying hexamethylene-1,6-diisocyanate trimer or urethane prepolymer constituting the main component. When such an organic-inorganic hybrid joint composition is used, an effect of improving physical properties such as surface cracking after joint work, adhesion, water resistance, and weather resistance is obtained.

Korean Patent Registration No. 10-1736583, which is a prior art, also reacts an alkoxysilane with an isocyanate to form a silane-modified isocyanate. Without doing so, a silica sol is prepared separately and mixed to form a main material.

The silica sol may be prepared by hydrolyzing an alkoxysilane, a silane coupling agent, and an acid catalyst in the presence of a co-solvent in which water and alcohol are mixed. However, when alcohol remains in the prepared silica sol, the alcohol causes a side reaction with isocyanate, which is a factor in degrading the physical properties of the joint agent composition. Therefore, the silica sol is used after removing all alcohol components through vacuum distillation.

The silica sol may be used in the range of 10 to 25 parts by weight. If the silica sol content is too small, the hardness of the coating film cannot be sufficiently increased, and if the silica sol content is too large, the elongation rate decreases and the possibility of cracking in the coating film increases.

In addition, the plasticizer contained in the subject is used to control the viscosity of the subject and increase the stability of the reaction. In general, phthalate-based compounds are used as plasticizers, but in the present invention, non-phthalate-based plasticizers are used. The non-phthalate plasticizer includes dioctyl terephthalate (DOTP), butyl 2-ethylhexyl terephthalate (BOTP) or di (2-ethylhexyl) terephthalate (di (2-ethylhexyl )terephthalate, DEHT) can be used.

The plasticizer is preferably used in the range of 1 to 5 parts by weight. If the content of the plasticizer is too small, the viscosity control effect cannot be obtained, and if the amount is too large, tensile strength and mechanical properties may be deteriorated.

The curing agent mixed with the main agent may be composed of polyaspartic acid (PAA), aminosilane, and a thickening agent.

Since the polyaspartic acid contains an amine group, it can react with isocyanate to form polyurea. An appropriate amine equivalent weight of polyaspartic acid is an important factor in forming a polyurea structure through reaction with hexamethylene-1,6-diisocyanate trimer and urethane prepolymer constituting the main component.

In particular, the polyaspartic acid of the present invention has an amine equivalent of 190 to 280 g/mol. For example, in a conventional production method for producing polyaspartic acid by reacting polyether diamine and diethyl maleate in an equivalent of 1:1, polyaspartic acid having an amine equivalent of 46 g/mol is obtained. Since polyaspartic acid having an amine equivalent weight of 190 to 280 g/mol can be prepared by reacting an alkoxyamine with a dicarboxylic acid selected from maleic acid or fumaric acid to increase the amine equivalent weight.

If the amine equivalent is too low or too high, curing is insufficient and the physical properties of the coating film are deteriorated. properties such as durability.

The polyaspartic acid is preferably used in the range of 65 to 80 parts by weight, and the curing reaction with the main agent is stably achieved within the amine equivalent and content range, and if the content of the polyaspartic acid is too small, the relative An increase in the amount may decrease the durability of the coating film, and if it is too large, an excessive amount of amine is included, resulting in a decrease in curability and easy yellowing.

In addition, aminotrimethoxysilane, a component of the curing agent, is a component added to promote a gel reaction to the unreacted silanol group of the silica sol contained in the main material, and through this, the hardness and durability of the coating film formed using the joint agent composition will improve The aminotrimethoxysilane may be used in the range of 5 to 10 parts by weight. If the content of the aminotrimethoxysilane is too small, unreacted silica sol may remain, and if the content is too large, unreacted silane compounds may remain. It is preferable to use it within the above range because it can impair the hardness and durability of the coating film.

In addition, additives such as pigments or pearls, fillers, antifoaming agents, leveling agents, dispersing agents, UV stabilizers, and UV absorbers may be added to the curing agent.

By adding the pigment or pearl, it is possible to impart color to the joint repaired part, and the required color can be imparted by being contained in the range of 5 to 10 parts by weight.

In addition, ceramic powders such as alumina, silica, mica, zeolite, ocher, jade, titanium dioxide, etc. may be used as the filler, and far-infrared ray emission and antibacterial effects may be obtained by adding such a filler. The filler may be contained in the range of 1 to 5 parts by weight.

In addition, as the antifoaming agent, a non-silicone antifoaming agent such as BYK-011, BYK-012, or BYK-066N may be used. The antifoaming agent may be contained in the range of 0.1 to 0.3 parts by weight.

In addition, the leveling agent may be added to increase surface flatness, and BYK-333 or BYK-378 may be used. The leveling agent may be contained in the range of 0.5 to 3 parts by weight.

In addition, by adding BYK-182 as a dispersant, it is possible to obtain effects of preventing settling of additive components such as pigments, pearls, and fillers and increasing gloss. The dispersant may be contained in the range of 0.5 to 3 parts by weight.

In addition, a UV stabilizer and a UV absorber may be contained in the range of 0.5 to 3 parts by weight, respectively. TINUVIN 292 or Irganox 1010 may be used as the UV stabilizer, and TINUVIN 1130 may be used as the UV absorber.

The joint agent composition is used for joint repair construction after preparing the main agent and the curing agent, respectively, in a weight ratio of 1:1. After preparing a non-yellowing urethane prepolymer and a silica sol, respectively, the subject is prepared by mixing hexamethylene-1,6-diisocyanate trimer and a plasticizer with the prepared non-yellowing urethane prepolymer and silica sol and stirring for 0.5 to 1 hour can do.

The effects of the joint composition of the present invention will be described through the following examples.

[Production Example]

fabrication of the subject

The non-yellowing urethane prepolymer constituting the main material was prepared by adding DBTDL as a catalyst to polyether polyol (molecular weight 2,000-3,000 g/mol) and isophorone diisocyanate (IPDL) and reacting at 80-100 ° C for 4 hours. manufactured.

In addition, in order to prepare a silica sol, 3-aminopropyltrimethoxysilane and a silane coupling agent (Silquest A-171) are hydrolyzed by adding 1N hydrochloric acid as an acid catalyst to a 9:1 co-solvent of water and ethanol, thereby hydrolyzing the sol. was obtained. Silica sol was obtained by distilling the obtained sol under reduced pressure to remove the ethanol component.

The prepared non-yellowing urethane prepolymer was prepared by adding hexamethylene-1,6-diisocyanate trimer and di(2-ethylhexyl)terephthalate to polyether polyol and silica sol and stirring at room temperature for 1 hour to prepare a main agent.

Preparation of curing agent

Polyaspartic acid constituting the curing agent was prepared as follows.

3-(2-[2-(3-aminopropoxy)ethoxy]ethoxy)propylamine (3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propylamine) and diethyl maleate 1: Polyaspartic acid (PAA-1) having an amine equivalent of 197.5 g/mol was prepared by reacting at 1 equivalent at 60° C. for 10 hours.

In addition, 2- [2- (2-aminoethoxy) ethoxy] ethylamine (2- [2- (2-aminoethoxy) ethoxy] ethylamine) and diethyl maleate at 1: 1 equivalent at 60 ℃ for 10 hours By reaction, polyaspartic acid (PAA-2) having an amine equivalent weight of 227.2 g/mol was prepared.

In addition, 3-[2-(3-aminopropoxy)ethoxy]propylamine (3-[2-(3-aminopropoxy)ethoxy]propylamine) and diethyl maleate were mixed at 1:1 equivalent at 60°C for 10 hours. By reaction, polyaspartic acid (PAA-3) having an amine equivalent weight of 212.8 g/mol was prepared.

In addition, for comparison, polyetherdiamine having a molecular weight of 2,500 and diethyl maleate were reacted in an equivalent ratio of 1:1 at 60° C. for 10 hours to prepare polyaspartic acid (PAA-4) having an amine equivalent of 47.6 g/mol.

Aminotrimethoxysilane, pearl, mica, antifoaming agent (BYK-011), leveling agent (BYK-333), dispersing agent (BYK-182), UV stabilizer (TINUVIN 292) and UV absorber (TINUVIN 1130) ) was mixed and stirred at room temperature for 1 hour to prepare a curing agent.

Preparation of joint composition

The joint composition as shown in Table 1 was prepared by mixing the subject and the curing agent in a weight ratio of 1:1. In Table 1, the unit of content is parts by weight.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 subject HDT 45 50 45 50 30 70 prepolymer 20 15 20 15 35 - silica sol 15 15 15 15 15 15 plasticizer 2 2 2 2 2 2 curing agent PAA-1 70 - - - 70 70 PAA-2 - 70 - - - - PAA-3 - - 70 - - - PAA-4 - - - 70 - - aminosilane 8 8 8 8 8 8 pigment 5 5 5 5 5 5 filler 2 2 2 2 2 2 antifoam 0.2 0.2 0.2 0.2 0.2 0.2 leveling agent 0.8 0.8 0.8 0.8 0.8 0.8 dispersant One One One One One One UV stabilizer 0.5 0.5 0.5 0.5 0.5 0.5 UV absorber 0.5 0.5 0.5 0.5 0.5 0.5

After applying the joint composition according to Examples and Comparative Examples to a polyethylene plate to a thickness of 0.8 ± 0.2 mm, the pot life was measured. In addition, the coating film properties were measured after curing the coating film at 25° C. and 60% for 5 days. The results are shown in Table 2. In Table 2, the pot life was measured according to KS M ISO 10364, and the available time after mixing the main material and the hardener. Tensile strength was measured using a universal tensile tester according to KS F 4922. Hardness was measured with a SHORE D durometer according to ASTM D2240. Adhesive strength was measured according to KS L 1592. In addition, discoloration stability is the result of observing yellowing while repeatedly exposed to ultraviolet rays for 1,000 hours using a UVA-340 lamp according to ASTM G154-12.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pot life (minutes) 50 52 48 26 15 0.5 Tensile strength (N/㎟) 19.5 19.8 18.6 18.2 19.4 19.6 Hardness 52 53 50 50 48 45 Adhesive strength (N/㎟) 10.2 9.8 10.3 9.0 8.5 9.2 discoloration stability Great Great Great Great discoloration discoloration

Looking at the results of Table 2, the joint compositions of Examples 1 to 3 had a pot life of 48 to 52 minutes, and showed a significantly longer pot life than the joint compositions of Comparative Examples 1 to 3 or the conventional joint composition. This is a result of a significant increase in pot life compared to the commonly used epoxy joint, which has a pot life of only 40 minutes at 23℃ and 50% temperature and humidity conditions. It was confirmed that the efficiency could be increased.

Examples 1 to 3 and Comparative Examples 1 to 3 showed similar results in physical properties such as tensile strength, hardness, and adhesive strength of the formed coating film, but in the case of Comparative Examples 2 and 3, discoloration stability was found to be low, preventing yellowing. turned out to be difficult. This is believed to be due to the difference in the mixing ratio of the non-yellowing polyurethane prepolymer and the hexamethylene-1,6-diisocyanate trimer used in Comparative Examples 2 and 3. In particular, in the case of Comparative Example 3, which does not contain the non-yellowing polyurethane prepolymer, the pot life is only 0.5 minutes, so if the curing speed is not controlled by the addition of the urethane prepolymer, sufficient pot life can be used as a joint composition. was difficult to ascertain.

Although the present invention has been described through preferred embodiments as described above, it is not limited to the above embodiments, and various modifications and modifications can be made by those skilled in the art within the scope of not departing from the spirit of the present invention. Change is possible. Such modifications and variations are intended to fall within the scope of this invention and the appended claims.

Claims (3)

a subject consisting of hexamethylene-1,6-diisocyanate trimer (HDT), a non-yellowing urethane prepolymer, a silica sol and a plasticizer; and
A curing agent composed of polyaspartic acid (PAA), aminotrimethoxysilane and additives;
is made up of
The hexamethylene-1,6-diisocyanate trimer and the non-yellowing urethane prepolymer are mixed in a weight ratio of 1: 1 to 6: 1. Non-yellowing organic-inorganic hybrid joint agent composition.
The method of claim 1,
The hexamethylene-1,6-diisocyanate trimer has an NCO content of 20 to 25%, the non-yellowing urethane prepolymer has an NCO content of 7 to 15%, and the polyaspartic acid has an amine equivalent of 190 to 280 g/mol Non-yellowing organic-inorganic hybrid joint agent composition, characterized in that.
The method of claim 1,
The silica sol is prepared by mixing an alkoxysilane, a silane coupling agent, an acid catalyst, and a co-solvent of water and alcohol and hydrolyzing it, wherein the alcohol is removed by vacuum distillation. composition.