KR101341156B1 - Resin impregnant and manufacturing method of the same - Google Patents

Abstract

The present invention relates to a resin impregnation agent, and aims to reduce sludge and COD by using three or more different vinyl-based acrylic monomers, and to shorten the time of generating a fume.

Description

Resin impregnant and manufacturing method thereof

The present invention relates to a resin impregnating agent and a method for manufacturing the same, and more particularly, to a resin impregnating agent which reduces the amount of residual impregnant and the amount of fume remaining on the surface when the impregnating agent is sealed by using a selected vinyl-based acrylic monomer, and a method of manufacturing the same. It is about. In addition, the present invention relates to an environmentally friendly resin impregnation agent and a method for manufacturing the same, which can reduce the generation of COD of the washing waste liquid generated when the resin impregnation agent is washed.

Impregnation agent improves the surface of product smoothly and minimizes the defect rate by sealing a number of pores generated in various forms in the casting due to the gas generated during casting such as die casting, ceramic, cast iron, sintered metal. By lowering leakage defects due to the pores generated during die casting of metals such as aluminum used in the automotive industry, it lowers the defect rate of the product, improves the strength, durability, stability and processing of the surface, and improves productivity and production cost. Brings savings.

Conventional impregnants have a silicate as a main component and the inorganic (water glass), and the epoxy-based and the organic such as acrylic-based binary. However, the inorganic impregnant has a long curing time and a high viscosity and low permeability, so that it takes a long time to inject it at a forced pressure.

In addition, it is not applicable to relatively large pores due to the large volume reduction after curing and low boiling point material. On the other hand, anaerobic acrylic resins and thermosetting unsaturated polyester resins, which are organic impregnants, have a shorter curing time and a higher penetration rate of the impregnating composition than the inorganic impregnants, but the process is complicated. However, the thermosetting impregnant can be washed with water due to its relatively low surface tension, and it can shorten working time and shorten curing time by treating at high vacuum.

Currently, the impregnant market has commercialized thermosetting acrylic resin, which is one of organic vinyl compounds having a short curing time, low viscosity, high penetration rate and high work efficiency. However, after the pore impregnation of the material, it can be washed with water in the surface cleaning process, but the cleaning power is low, causing imperfections due to residual impregnated components on the surface of the material or causing problems of process cost and environmental pollution for waste liquid treatment after cleaning. .

On the other hand, there was an example of highlighting the effective improvement in the environmental problems and economics sector by reusing the water-insoluble impregnation agent, but in this case it is improved by adding additional substances to the impregnation agent in use. At this time, the manufacturing process is more complicated, and the situation has a problem causing heat resistance and discoloration of the cured product.

The present applicant has also solved the above problems in Korean Patent Registration No. 10-0980230. In addition, the cleaning power of the impregnating agent has been enhanced (Korean Patent Registration No. 10-0998866), and a resin impregnation agent that can visually check the degree of sealing of micropores after impregnation has been developed (Korea Patent Registration No. 10-0998867).

However, in recent years, the development of environmentally friendly resin impregnation agents for environmental regulation and improvement of the working environment is required.

In other words, the use of the impregnant is intended to reduce the chemical oxygen demand (COD) of the wastewater inevitably generated, to suppress sludge generation, and to improve the amount of fume generated from the impregnant remaining on the surface of the impregnated agent.

The present invention reduces the affinity with water at the time of washing by using a vinyl acryl monomer, thereby facilitating waste liquid treatment and at the same time without affecting the physical properties of conventional resin impregnants, the chemical oxygen demand of the waste washing water generated during the washing process. To reduce COD and to reduce sludge formation to improve impregnation workability.

In addition, the use of vinyl acryl monomer impregnant reduces the amount of impregnant remaining on the surface of the material after curing of the impregnating agent, thereby shortening the generation time of the fume of the impregnant remaining in the impregnating agent for a long time after curing. We want to promote convenience.

In addition, the degree of sealing of the impregnating agent in the pores of the impregnating agent can be improved by preventing the oxidation of the cured product of the resin impregnation, heat resistance, stability, chemical resistance, chemical resistance, increase in mechanical strength, high penetration due to low viscosity, and cleaning and adding fluorescent material after curing. Make it visible to the naked eye.

One aspect of the present invention is a vinyl-based acrylic monomer comprising a first acrylic monomer for the softness of the cured impregnant, a second acrylic monomer for the hardness of the impregnated cured product, and a third acrylic monomer for enhancing the bonding strength between monomers ;

Antioxidants; And

Non-ionic surfactants,

The second acrylic monomer is included in 30 to 40 parts by weight based on 100 parts by weight of the first acrylic monomer, the third acrylic monomer is included in 1 to 5 parts by weight relative to 100 parts by weight of the first acrylic monomer.

At this time, the first acrylic monomer may be a vinyl-based acrylic monomer represented by the following formula (1).

[Chemical Formula 1]

(Wherein R represents a hydrocarbon residue of 6 to 8 carbon atoms).

At this time, the first acrylic monomer is preferably selected from the group consisting of Hexyl methacrylate, 2-Ethylhexyl acrylate, 2-Ethylhexyl methacrylate, Heptyl methacrylate, Octyl methacrylate and mixtures thereof.

In addition, the second acrylic monomer uses a vinyl-based acrylic monomer represented by the following formula (2).

(2)

(In this case, n in Chemical Formula 2 has a value of 2 to 4.)

The second acrylic monomer is preferably at least one selected from the group consisting of Hydroxypropyl methacrylate, Hydroxyethyl methacrylate, Hydroxybutyl methacrylate and mixtures thereof.

In addition, the third acrylic monomer is a vinyl-based acrylic monomer represented by the formula (3).

(3)

At this time, the third acrylic monomer is preferably selected from the group consisting of Ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, Triethylolpropane dimethacrylate, Triethylolpropane trimethacrylate and mixtures thereof.

The nonionic surfactant may be included in an amount of 2 to 7 parts by weight based on 100 parts by weight of the first acrylic monomer, and the antioxidant may include 0.2 to 0.6 parts by weight based on 100 parts by weight of the first acrylic monomer.

In addition, the antioxidant is preferably a phosphorus-based and phenol-based is mixed.

In addition, it is preferable to further include a fluorescent agent which can emit light upon UV irradiation, wherein the fluorescent agent is included 0.001 to 0.003 parts by weight relative to 100 parts by weight of the first acrylic monomer.

In addition, the fluorescent agent is 4-methyl-7- (diethylamino) coumarin, 2,2 '-(2,5-thiophenediyl) bis [5- (1,1-dimethylethyl)]-benzoxazole, 2,2'-( It is preferable to include at least one substance selected from the group consisting of 4,4'diphenolvinyl) di-benzoxazole.

In addition, a light stabilizer is further included to protect the impregnating agent from heat or ultraviolet rays, and the light stabilizer is preferably included in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the first acrylic monomer.

In addition, the light stabilizer is 2-Cyano-3,3-diphenylacryloxy alkylene acrylic acid esters, 1,3-Bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2- cyano-3,3diphenyl-acryloyl) oxy] methyI] propane preferably includes at least one material selected from the group consisting of.

The other aspect of the present invention,

The first acryl monomer for the softness of the cured product and the rigidity of the cured product and imparting a bonding force between the acryl monomer and the second acrylic monomer contained in 30 to 40 parts by weight relative to 100 parts by weight of the first acrylic monomer A first step of mixing a third acrylic monomer contained in 2 to 7 parts by weight based on 100 parts by weight of 1 acrylic monomer; And

It provides a method for producing a resin impregnating agent comprising a second step of putting a nonionic surfactant, a light stabilizer and an antioxidant in the acrylic monomer mixture solution.

First, the resin impregnating agent according to the present invention can improve the worker environment by reducing the amount of impregnant remaining on the surface of the sealing product and increasing the temperature drop rate of the substrate to reduce the time of generating a fume. Second, the COD can be reduced by 40% by replacing the component with an organic material having a function similar to the existing impregnant component material. Third, the impregnation agent used for casting impregnation has a specific gravity lower than that of water to facilitate waste liquid treatment, and wastewater treatment cost can be reduced.

Impregnation agents according to the present invention include vinyl-based acrylic monomers, surfactants, antioxidants, light stabilizers, and fluorescent agents.

Impregnating agent to be prepared in the present invention is prepared by mixing a total of three kinds of vinyl-based acrylic monomers having different physical properties that can constitute a stable bond between the hard and monomer based on the softness of the cured product, as follows: .

The first acrylic monomer is a main component used in the preparation of the impregnating agent in the present invention is water-insoluble, close to odorless, low specific gravity, and has a soft monomer characteristics, such as the formula (1) that can be given to the pores of the casting and softness of the cured product A monomer having an alkyl methacrylate as the basic structural formula is selected.

[Chemical Formula 1]

(Wherein R represents a hydrocarbon residue of 6 to 8 carbon atoms).

In addition, the organic component having an alkyl group in Chemical Formula 1 may be selected as the first acrylic monomer, and at least one or more of the monomers listed below without limitation may be used.

Primary acrylic monomers: Hexyl methacrylate, 2-Ethylhexyl acrylate, 2-Ethyl hexyl methacrylate, 2-Ethylhexyl methacrylate, Heptyl methacrylate, Octyl methacrylate

The second acrylic monomer uses a hydroxyalkyl methacrylate (Hydroxy alkyl methacrylate) to give a hardened material of the impregnated cured product and has a structure as shown in the following formula (2).

(2)

At least one or more of monomers having a value of n = 2 to 4 in Formula 2 and listed below without limitation may be used.

It is preferable that 30-40 weight part is included with respect to 100 weight part of 1st acryl monomers. If it is less than 30, the hardening time is not hardened, so that a hardening time is long, and the specific gravity increases, making it difficult to separate oil and water from water. In addition, if it exceeds 40, the hardness of the impregnant increases, thereby decreasing the elasticity and flexibility of the impregnant and reacting sensitively to temperature, and cracks of the cured product occur due to hardening.

Second Acrylic Monomer: Hydroxypropyl methacrylate, Hydroxyethyl methacrylate, Hydroxybutyl methacrylate

The third acryl monomer is included to impart hardness of the cured product and to shorten the curing time and to increase the bonding strength between monomers included in the impregnating agent, and the ethylene dimethacrylate represented by the following Chemical Formula 3 is basically used. Choose a material that has a structure. For reference, at least one or more of the monomers listed below without limitation may be used.

(3)

It is preferable that 1-5 weight part is included with respect to 100 weight part of 1st acryl monomers. If it is less than 1, the heat resistance is lowered. If it is more than 5, discoloration and cracking of the cured product may be caused, thereby impairing the impregnant properties.

Tertiary Acrylic Monomers: Ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, Triethyl propane dimethacryl Triethylolpropane dimethacrylate, Triethylolpropane trimethacrylate

On the other hand, the surfactant is to add a nonionic surfactant that can increase the affinity with water for the removal and cleaning power of the impregnated components remaining on the surface of the impregnated material.

Nonionic surfactants include, but are not limited to, non-ionic higher alcohol surfactants such as methanol ethoxylate, ethanol ethoxylate, lauryl alcohol ethoxylate, lauryl alcohol alkoxylate or nonionic fatty acid ester surfactants. Latex, sorbitan fatty acid esters, polyoxylethylene sorbitan fatty acid esters, polyoxy alkylrentals can be used

The content of the surfactant is not dissolved in the wash water and suitable for 2 to 7 parts by weight compared to 100 parts by weight of the first acrylic monomer, which does not change the physical properties in use for a long time, but if less than 2, it has a low affinity for water When the 7 or more is added, low intermolecular affinity between the non-aqueous monomer and the washing water is increased, thereby increasing the intermolecular affinity, which may cause emulsification of the washing water.

The light stabilizer is included to impart a function for protecting the impregnating agent from heat or ultraviolet rays, and includes 0.01 to 0.1 parts by weight relative to 100 parts by weight of the first acrylic monomer. The light stabilizer used at this time is preferably cyan acrylate ester. 2-Cyano-3,3-diphenylacryloxy acrylic acid esters, 1,3-Bis [(2-cyano-3,3-diphenyl acryloyl) oxy] -2,2-bis [[(2-cyano- 3,3diphenyl-acryloyl) oxy] methyI] propane can be used.

In this case, it has a high absorption in the 300 ~ 370nm wavelength range of ultraviolet damage, and at the same time can be obtained the antioxidant effect of the phenol-based and the thermal stability of the advantage of the hindered amine.

In addition, the light stabilizer is easy to dissolve in the liquid form and strong heat resistance can be ensured that the stability does not cure even in strong sunlight does not drop to half level when the heat loss.

Antioxidants include impregnants to prevent changes in physical properties from the external environment (air, moisture, heat or light, etc.), 0.2 to 0.6 parts by weight relative to 100 parts by weight of the first acrylic monomer, and phenolic and phosphorus antioxidants. Use in combination. Addition of antioxidants can enhance chemical and physical stability by preventing discoloration and increasing heat resistance. However, the use of antioxidants such as sulfur-based or amine-based is not limited, but discoloration should be taken into account during use during processing.

Phosphorous acid may be used as the phosphorus antioxidant, and as the phenolic antioxidant, BHT (Butylhydroxytoluene), TBHQ (tert-Butylhydroquinone), BHA (Butylated hydroxyanisole) and the like may be used.

As the fluorescent agent, a substance capable of emitting light upon UV irradiation is added to the pores of the impregnant to check the sealing state of the impregnant, and includes 0.001 to 0.003 parts by weight relative to 100 parts by weight of the first acrylic monomer, 4-methyl-7- group consisting of (diethylamino) coumarin, 2,2 '-(2,5-thiophenediyl) Bis [5- (1,1-dimethylethyl)]-benzoxazole, and 2,2'-(4,4'diphenolvinyl) di-benzoxazole It is preferable to select at least one.

In addition, the polymerization initiator may be added to the stability of the impregnating agent for curing, heat resistance, sealing effect. The polymerization initiator is a water-insoluble azo compound and is included in an amount of 0.1 to 1 parts by weight based on the total weight of the impregnant. Polymerization initiators that can be used include Azobisisobutyronitrile, 2,2'-azobis-2-isobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis-2,4'-dimethyl valeronitrile, dimethyl-2,2 '-azobisisobutylate can be used. However, without limitation, peroxide-based and redox-based polymers may be used as curing initiators for curing the impregnating agent.

  (Example)

≪ Example 1 >

The impregnating agent of the present invention was added by stirring the first acrylic monomer Hexyl methacrylate 65wt%, the second acrylic monomer Hydroxyethyl methacrylate 27wt% and the third acrylic monomer Triethylene glycol methacrylate 3.2wt%, so that each sealing agent was dispersed in solution. To be done. Within 0.008wt% of cyan acrylate-based liquid light stabilizer for additional functions, less than 0.2wt% of phosphorus and phenolic antioxidants, 4.59wt% of nonionic surfactant and 4-methyl-7- (diethylamino) fluorescent 0.002wt% of coumarin is mixed in the sealing solution to completely dissolve to prepare a sealing impregnating agent.

≪ Example 2 >

The impregnating agent of the present invention was added by stirring the first acrylic monomer 2-Ethylhexyl methacrylate 72wt%, the second acrylic monomer Hydroxypropyl methacrylate 21wt% and the third acrylic monomer Diethyleneglycol dimethacrylate sequentially, each sealing agent was dispersed in the solution Let this be done. Within 0.008wt% of cyan acrylate liquid light stabilizer, less than 0.2wt% of phosphorus and phenolic antioxidants, 3.89wt% of nonionic surfactant and fluorescent agent 4-methyl-7- (diethylamino) 0.002wt% of coumarin is mixed in the sealing solution to completely dissolve to prepare a sealing impregnating agent.

≪ Comparative Example 1 &

45 wt% of Isotridecylmetacrylate, 45 wt% of Benzyl methacrylate, and 8 wt% of diethylene glycol dimethacrylate were used as the sealing acrylic monomer, and 0.2 g of the phenolic antioxidant BHT was completely dissolved in the acrylic monomer mixture. The light stabilizer is sufficiently stirred after adding 0.8 g of powdered bentriazole (Benzotriazole). 1 g of surfactant ISC-100 ^TM (Ilshin Chemical) was added to dissolve to prepare an impregnating agent.

≪ Comparative Example 2 &

As a sealing acrylic monomer, 50 wt% of isodecyl methacrylate, 40 wt% of hydropropyl methacrylate, 5 wt% of trimethylol propane methacrylate, and 3 wt% of alkyl methacrylate are sequentially mixed, and 0.4 g of phenolic antioxidant BHT is completely dissolved in the acrylic monomer mixture. In addition, 0.8 g of powdered bentriazole (Benzotriazole) is mixed with the light stabilizer, and after sufficiently stirring, 1 g of the surfactant ISC-100 ^TM (ILC) is dissolved to prepare an impregnating agent.

≪ Comparative Example 3 &

Sealing acrylic monomer 2-Hydroxyethyl methacrylate 58wt%, Triethylene glycol dimethacrylate 24wt%, Alkyl methacrylate 13wt%, Lauryl methacrylate 2wt% are mixed sequentially, and 2wt% R-methacryloxypropyl trimethoxysilane and 1wt% surfactant are dissolved and stirred To prepare an impregnating agent.

[Experimental Example]

Comparing the performance of the impregnating agent prepared through the Example and Comparative Example is as follows.

<Experimental Example 1>

COD  content

This COD content is the result of request for analysis from KTR. As a result of the COD analysis of the sample diluted with stock COD and 10% tap water as Example 2 and Comparative Example 1, the sample for analysis was compared with Comparative Example 1 to confirm that Example 2 reduced COD by 40%. Can be. The analysis results are shown in Table 1 below.

sample Results unit Test Methods Comparative Example 1-100% 668000 mg / L Water Pollution Process Test Criteria
(2010) Example 2-100% 267000 Comparative Example 1-10% 67800 Example 2-10% 27100

For reference, the COD of a third-party product (Ultrasela, PC504), currently distributed in the impregnant market, represents 17800 ppm in the 1% solution of the impregnant. Through this indirect comparison with Example 2, it can be seen that the amount of COD generated less than the product that is commercialized in the impregnant prepared in Example 2.

 Fume Fume ) Shorten occurrence time

After the impregnating agent is cured due to the use of the water-insoluble monomer, the fume is generated due to the impregnation agent remaining on the surface of the material to be impregnated. Thus, the amount of fume generated was indirectly compared through the temperature of the material to be impregnated. The temperature of the material to be impregnated according to the elapsed time after impregnation is shown in Table 2.

Impregnation material temperature Comparative Example 2 Example 2 Elapsed time 15 minutes 50 ° C (1 ~ 2 ° C) 48 ° C (1 ~ 2 ° C) 20 minutes 40 degrees Celsius (1-2 degrees Celsius) 37 ℃ (1 ~ 2 ℃)

The amount of fume generation of the impregnant remaining on the surface of the material after curing is the same, but inversely proportional to the rapid temperature drop rate of the material surface in terms of the duration of the fume generation. When looking at the convenience of the operator, the falling rate of the impregnant remaining on the surface of the impregnating material with time after curing is higher than the conventional impregnating agent (Comparative Example 2) the falling speed of Example 1. Therefore, the duration of fume generation is shorter, which is more effective than conventional impregnants.

Sludge ( Sludge Captain

After the impregnation of the impregnated material, sludge is generated in the washing step due to the chemical reaction between the impregnant and the wash water. Thus, 20 vol% of the impregnant was mixed with 80 vol% of tap water and heated in a water bath at 90 ° C. for 20 minutes to measure the amount of sludge generated at this time. Table 1 shows the results of sludge generation of tap water and impregnant solution. For reference, the other company applied as a comparative example is Ultraseal's PC504 product.

Example 2 Comparative Example 3 Comparative Example (Third Party) Sludge geometry Create a clear cured product Create a white clay-like hardener Pale yellow cured product

Sludge Production (%) 10.92 32.09 22.70

Claims (14)

Vinyl-based acrylic comprising a first acrylic monomer represented by the following formula (1) for the softness of the impregnated cured product, a second acrylic monomer for hardness in the impregnated cured product, and a third acrylic monomer for enhancing the bonding strength between monomers Monomers;
Antioxidants; And
Non-ionic surfactants,
The second acrylic monomer is included in 30 to 40 parts by weight relative to 100 parts by weight of the first acrylic monomer, the third acrylic monomer comprises 1 to 5 parts by weight relative to 100 parts by weight of the first acrylic monomer,
The nonionic surfactant is a resin impregnating agent is included in 2 to 7 parts by weight relative to 100 parts by weight of the first acrylic monomer.
[Chemical Formula 1]

(Wherein R represents a hydrocarbon residue of 6 to 8 carbon atoms).
delete The method of claim 1,
The first acrylic monomer is hexyl methacrylate (Hexyl methacrylate), 2-ethylhexyl acrylate (2-Ethylhexyl acrylate), 2-ethylhexyl methacrylate (2-Ethylhexyl methacrylate), heptyl methacrylate (Heptyl methacrylate) , Octyl methacrylate (Octyl methacrylate) and a resin impregnating agent selected from at least one selected from the group consisting of. The method of claim 1,
The second acrylic monomer is a resin impregnating agent is a vinyl-based acrylic monomer represented by the following formula (2).
(2)

(In the above, the alkyl group of n = 2-4 is represented.) 5. The method of claim 4,
The second acrylic monomer is selected from the group consisting of hydroxypropyl methacrylate (Hydroxypropyl methacrylate), hydroxyethyl methacrylate (Hydroxyethyl methacrylate), hydroxybutyl methacrylate (Hydroxybutyl methacrylate) and mixtures thereof Resin impregnant. The method of claim 1,
The third acrylic monomer is a resin impregnating agent is a vinyl-based acrylic monomer represented by the following formula (3).
(3)

The method according to claim 6,
The third acrylic monomer is ethylene glycol dimethacrylate (Ethylene glycol dimethacrylate), diethylene glycol dimethacrylate (Diethylene glycol dimethacrylate), triethylene glycol dimethacrylate (triethylene glycol dimethacrylate), triethyl propane dimethacrylate Resin impregnating agent selected from the group consisting of triethylolpropane dimethacrylate, triethylolpropane trimethacrylate and mixtures thereof. The method of claim 1,
The antioxidant is a resin impregnating agent containing 0.2 to 0.6 parts by weight relative to 100 parts by weight of the first acrylic monomer. The method of claim 8,
The antioxidant is a resin impregnating agent mixed with phosphorus and phenolic. The method of claim 1,
A fluorescent agent capable of emitting light upon UV irradiation is further included, and the fluorescent agent is a resin impregnating agent containing 0.001 to 0.003 parts by weight relative to 100 parts by weight of the first acrylic monomer. The method of claim 10,
The fluorescent agent is 4-methyl-7- (diethylamino) coumarin, 2,2 '-(2,5-thiophenediyl) Bis [5- (1,1-dimethylethyl)]-benzoxazole, 2,2'-(4, A resin impregnating agent comprising at least one substance selected from the group consisting of 4'diphenolvinyl) di-benzoxazole. The method of claim 10,
A light stabilizer is further included to protect the impregnating agent from heat or ultraviolet rays, and the light stabilizer is contained in an amount of 0.01 to 0.1 parts by weight based on 100 parts by weight of the first acrylic monomer. 13. The method of claim 12,
The light stabilizer is 2-Cyano-3,3-diphenylacryloxy alkylene acrylic acid esters, 1,3-Bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano- 3,3diphenyl-acryloyl) oxy] methyI] propane A resin impregnating agent comprising at least one substance selected from the group consisting of. Between the first acryl monomer represented by the following formula (1) for the softness of the cured product and the second acryl monomer imparting hardness of the cured product and included in an amount of 30 to 40 parts by weight relative to 100 parts by weight of the first acrylic monomer, and an acrylic monomer A first step of imparting a bonding force and mixing a third acrylic monomer contained in 2 to 7 parts by weight based on 100 parts by weight of the first acrylic monomer; And
A method of producing a resin impregnating agent comprising a second step of adding a nonionic surfactant, a light stabilizer and an antioxidant to the acrylic monomer mixture solution.
[Chemical Formula 1]

(Wherein R represents a hydrocarbon residue of 6 to 8 carbon atoms).