KR102594833B1 - A hybrid water-based binder for glass fiber with improved non-combustible performance and compressive strength - Google Patents

Abstract

The present invention relates to a hybrid water-based binder for glass fibers with improved non-flammable performance and compressive strength, which contains 0.01 to 0.01 parts by weight of an aziridine-based polymer per 100 parts by weight of a resin blend of phenol-formaldehyde resin and melamine-formaldehyde resin and 100 parts by weight of the resin blend. Contains 1 part by weight. It is characterized in that melamine-formaldehyde resin is added as a reinforcing material to phenol-formaldehyde resin to improve non-flammable performance, and aziridine-based polymer is added as a crosslinking agent to improve compressive strength.

Description

Hybrid water-based binder for glass fiber with improved non-combustible performance and compressive strength}

The present invention relates to an aqueous binder for glass fibers, in which melamine-formaldehyde resin is added as a reinforcing material to the phenol-formaldehyde resin used to bind glass fibers to improve non-flammable performance, and an aziridine-based polymer is used as a crosslinking agent. It relates to a water-based binder for glass fiber, characterized in that the compressive strength is improved by adding as.

Glass fiber refers to glass that is spun thin like fiber. Because glass fiber has excellent insulation, processability, and corrosion resistance, it is widely used as a substitute for asbestos as a building insulation material.

The method of using glass fiber is similar to reinforced concrete. Just as reinforced concrete improves its strength by pouring concrete over mesh-shaped rebars to compensate for each other's weak points, glass is made by applying a binder containing phenol-formaldehyde resin as the main ingredient to glass fibers and overlapping several layers of glass fibers. Use fiber.

Since glass fiber is used as a building insulation material, it is necessary to improve the non-flammable performance of the binder. The heat of combustion of phenol-formaldehyde resin, the main component of the binder, is 20~30MJ/kg, which is on the high side compared to the heat of combustion of resins that can be used as a binder.

US Patent Publication US 2014/0357787 A1 (2014.12.04.)

The purpose of the present invention is to improve the non-flammable performance of a water-based binder (or composition) for glass fiber.

The present invention is an aqueous binder for glass fiber and includes 100 parts by weight of a resin blend of phenol-formaldehyde resin and melamine-formaldehyde resin and 0.01 to 1 part by weight of an aziridine-based polymer based on 100 parts by weight of the resin blend.

Preferably, the mixing ratio of phenol-formaldehyde resin and melamine-formaldehyde resin may be 3:1 to 1.3:1.

Preferably, the aziridine-based polymer is Trimethylolpropane tris(2-methyl-1-aziridine propionate, Trimethylolpropane tris(β-N-aziridinyl) propionate, Pentaerythritol tris[3-(1-aziridinyl)propionate] or Pentaerythritol tris[2-methyl- 1-aziridinyl propionate].

Preferably, based on 100 parts by weight of the resin formulation, it may further include 0.01 to 10 parts by weight of an anti-vibration agent and 0.01 to 5 parts by weight of silane, the anti-vibration agent may be an anti-vibration oil, and the silane may be amino silane.

The present invention can improve the non-flammable performance of a water-based binder for glass fiber and improve the compressive strength of glass fiber.

Figure 1 shows the ring-opening reaction mechanism of aziridine.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited or limited by the exemplary embodiments. The purpose and effect of the present invention can be naturally understood or become clearer through the following description, and the purpose and effect of the present invention are not limited to the following description. Additionally, in describing the present invention, if it is determined that a detailed description of known technologies related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted.

The present invention relates to a hybrid water-based binder for glass fibers with improved non-flammable performance and compressive strength, which includes 100 parts by weight of the phenol-formaldehyde resin and melamine-formaldehyde resin blend and 0.01 to 1 part by weight of the aziridine-based polymer relative to 100 parts by weight of the resin blend. Includes. The present invention may further include additives such as dustproofing agents, silane, and crosslinking agents, and water.

“Hybrid” means a mixture of two or more types of resin among phenol-formaldehyde resin, urea-formaldehyde resin, melamine-formaldehyde resin, polyester resin, unsaturated polyester resin, epoxy resin, silicone resin, and PVA resin. , More specifically, in the above resins, it means that phenol-formaldehyde resin and at least one type of resin are mixed.

Resins suitable for hybridization with phenol-formaldehyde resin include urea-formaldehyde resin, melamine-formaldehyde resin, silicone resin, etc. Among these, the suitable resin is melamine-formaldehyde resin.

The heat of combustion of phenol-formaldehyde resin is 20~30MJ/kg, and the heat of combustion of melamine-formaldehyde resin is 15~20MJ/kg, which is lower than the heat of combustion of phenol-formaldehyde resin. Therefore, the addition of melamine-formaldehyde resin can contribute to improving non-combustible performance. Melamine-formaldehyde resin is a polymer of melamine and formaldehyde and has a number average molecular weight ranging from 300 to 3,000. The smaller the number average molecular weight, the better the storage stability. The larger the number average molecular weight, the better the mechanical properties, but the lower the storage stability.

The resin blend of phenol-formaldehyde resin and melamine-formaldehyde resin may have a blending ratio of 99:1 to 1:99 (based on weight, the same hereinafter) based on a total of 100 parts by weight of the resin blend, and preferably 80:20. It can have a mixing ratio of ~55:45. The mixing ratio is preferably about 24:1 to 1:1, and preferably about 3:1 to 1:1 or 3:1 to 1.31:1. It is desirable to mix the melamine-formaldehyde resin at a content between the minimum content to improve non-combustible performance and the maximum content that does not cause an increase in viscosity or a decrease in compatibility.

A dustproofing agent is added to lower the dust rate of glass fiber. The dustproofing agent can be added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the resin mixture. If the content of the dustproofing agent is less than the lower limit, dust from the glass fiber may scatter and cause problems during work. If the content of the dustproofing agent exceeds the upper limit, the surface of the glass fiber itself becomes slippery, which may cause problems in the post-process (attachment to the substrate).

Silane is added to improve the strength and water-repellent performance of glass fiber. The silane may be one or more of epoxy silane, amino silane, vinyl silane, methacrylic silane, methoxy silane, and ethoxy silane, with epoxy silane and amino silane being suitable. Silane can be added in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the resin mixture. If the silane content is less than the lower limit, the effect of improving the bonding strength and water repellent performance of glass fiber may not appear, and if the silane content exceeds the upper limit, the problem of price increase may occur.

Aziridine-based polymer is added as a crosslinking agent to increase the bonding force between fibers and improve compressive strength. The aziridine-based polymer can be added in an amount of 0.01 to 1 part by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the resin mixture. If the content of the aziridine-based polymer is less than the lower limit, the compressive strength may not be improved, and if the content of the aziridine-based polymer exceeds the upper limit, the curing time of the glass fiber may be shortened due to excessive crosslinking, which may cause a precure phenomenon. The precure phenomenon refers to a phenomenon in which the entire fiber is not cured during a certain residence time, but only a portion of the fiber is quickly cured.

The aziridine-based polymer will be further explained with reference to FIG. 1. Figure 1 shows the ring-opening reaction mechanism of aziridine. Referring to FIG. 1, aziridine can be cross-linked after a ring-opening reaction with a hydroxy group (-OH) or carboxyl group (-COOH) due to external heat to improve fiber bonding strength (adhesion). Here, the hydroxy group (-OH) or carboxyl group (-COOH) refers to the functional group of phenol-formaldehyde resin and melamine-formaldehyde resin. If the aziridine-based polymer is multifunctional, water resistance can also be improved. Aziridine-based polymer types include Trimethylolpropane tris(2-methyl-1-aziridine propionate, Trimethylolpropane tris(β-N-aziridinyl) propionate, Pentaerythritol tris[3-(1-aziridinyl)propionate] or Pentaerythritol tris[2-methyl-1- aziridinyl propionate]. Below, experimental examples of the present invention will be described.

Table 1 shows the compositions of Examples 1 to 6, and Table 2 shows the compositions of Comparative Examples 1 to 5. The aqueous binder of Example 1 was prepared by mixing phenol-formaldehyde resin and melamine-formaldehyde resin at room temperature, adding additives and water in that order, and then stirring. The mixture was sprayed or applied to the glass fiber material and then heat cured and bound. Thermal curing was carried out at 150~200℃. Examples 2 to 6 and Comparative Examples 1 to 5 were also prepared in the same manner as Example 1.

ingredient
(part by weight) Example
One Example
2 Example
3 Example
4 Example
5 Example
6 Phenol-formaldehyde resin 180.25 180.25 130.2 130.2 110 110 Melamine-formaldehyde
Resin (reinforcement agent) 60.08 60.08 98.3 98.3 115.08 115.08 aminosilane 0.5 0.5 0.5 0.5 0.5 0.5 Aziridine-based polymer One 0.5 One 0.5 One 0.5 Anti-vibration oil 9 9 9 9 9 9 water 749.17 749.17 761 761 764.42 764.42 Total 1000 1000 1000 1000 1000 1000 Solid content (% by weight) 10 10 10 10 10 10 binder status Good Good Good Good Good Good

ingredient
(part by weight) Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 Phenol-formaldehyde resin 244 - 250 230.5 235.2 Melamine-formaldehyde resin (reinforcement agent) - 192 - - - PVA water solution (reinforcer) - - 20.2 - - Water dispersion Polyester (reinforcement agent) - - - 41.1 - Silica sol (reinforcement agent) - - - - 41.1 aminosilane 0.5 0.5 0.5 0.5 0.5 Aziridine-based polymer - - - - - Anti-vibration oil 9 9 9 9 9 water 746.5 798.5 720.3 718.9 714.2 Total 1000 1000 1000 1000 1000 Solid content (% by weight) 10 10 10 10 10 binder status Good Good Good agglomeration agglomeration

designation Heat of combustion (MJ/kg) Phenol-formaldehyde resin 23.5 Melamine-formaldehyde resin 18.7 PVA water solution 23.8 Water dispersion Polyester 35.8 Silica sol < 1.0

Table 3 shows the results of combustion heat measurement. The measurement targets are phenol-formaldehyde resin, melamine-formaldehyde resin, PVA aqueous solution, water-dispersed polyester, and silica sol. The heat of combustion was heat treated in an oven at 135°C for 1 hour, the resin solid content was collected, and the higher calorific value (MJ/kg) of the resin solid content was measured using a bomb calorimeter.

division compatibility save
stability compression
robbery
(N/㎜) as
temperature difference
(℃) Non-combustible performance passed or not cut
Processability Example 1 ◎ ◎ 28.5 2.7 ○ 5 Example 2 ◎ ◎ 26.4 2.5 ○ 5 Example 3 ◎ ◎ 29.7 1.9 ○ 4 Example 4 ◎ ◎ 27.1 2.1 ○ 4 Example 5 ◎ ○ 29.7 1.3 ○ 4 Example 6 ◎ ○ 27.3 1.7 ○ 4 Comparative Example 1 ◎ ◎ 23.9 7.9 ○ 5 Comparative Example 2 ◎ ◎ 21.8 0.9 ○ 4 Comparative Example 3 ◎ ○ 22.6 6.3 ○ 3 Comparative Example 4 X X NG NG X NG Comparative Example 5 X X NG NG X NG

Table 4 shows the physical property evaluation results of Examples 1 to 6 and Comparative Examples 1 to 5. The physical properties subject to evaluation are compatibility, storage stability, compressive strength, furnace temperature difference, non-combustibility performance based on furnace temperature difference, and cutting processability. Below, the evaluation method for each evaluation target physical property will be described.

(1) Compatibility

In order to evaluate the compatibility of phenol-formaldehyde resin with each reinforcing agent, they were mixed in a pre-designed mixing ratio and evaluated based on the following criteria.

◎: Each component mixes well to form a very uniform mixture.

○: Each component is mixed well to form a somewhat uniform mixture.

×: Most of the ingredients are not mixed with each other

(2) Storage stability

The mixture was stored at room temperature for one week and evaluated based on the following criteria.

◎: Each ingredient is mixed well and maintains a very uniform mixing state.

○: Each component maintains a certain degree of uniform mixing.

×: Each component does not maintain a uniform mixing state, and layer separation, agglomeration, or crystals occur.

(3) Compressive strength

When the manufactured specimen was cut to 300 mm mm) was calculated.

Compressive strength (N/㎜) = H1 ÷ H2

H1: Force measured at 50% compression (N)

H2: 50% compression height (mm)

(4) Non-combustible performance

To confirm the non-flammability performance of the manufactured specimen, it was measured using the method specified in KS F ISO 1182. Non-combustible performance is judged by the temperature difference inside the heating furnace (maximum temperature - final temperature), and if the temperature difference is less than 20℃, it is judged as passing. The smaller the temperature difference, the higher the non-flammability performance.

(5) Cutting processability

In order to evaluate the processability of the glass fiber insulation material, when it was cut using a cutter, the cut surface was observed to evaluate the cutting processability. At this time, the closer it is to 0, the worse the appearance is due to the occurrence of fiber bundles and lint on the cut surface, and the closer it is to 5, the smoother the cut surface is, indicating excellent cutting processability.

Referring to Table 4, the physical property evaluation results are explained.

Examples 1-6 include both phenol-formaldehyde resin and melamine-formaldehyde resin. In Examples 1 to 6, the minimum and maximum furnace temperature differences were 1.3°C (Example 5) and 2.7°C (Example 1), respectively. Comparative Examples 1 and 3 do not contain melamine-formaldehyde resin. The furnace temperature differences of Comparative Examples 1 and 3 were 7.9°C and 6.3°C, respectively, which is higher than the above-mentioned maximum furnace temperature difference of 2.7°C in Example 1. Therefore, it can be evaluated that the improvement in non-combustible performance comes from the addition of melamine-formaldehyde resin.

Comparative Example 2 includes only melamine-formaldehyde resin. In other words, Comparative Example 2 does not contain phenol-formaldehyde resin. The furnace temperature difference of Comparative Example 2 was 0.9°C, which was lower than the above-mentioned minimum furnace temperature difference of 1.3°C in Example 5. Therefore, the non-flammable performance of Comparative Example 2 can be considered to be superior to that of Examples 1 to 6. However, Comparative Example 2 has a problem with compressive strength. This is because Comparative Example 2 showed the lowest compressive strength (21.8 N/mm) among Examples 1 to 6 and Comparative Examples 1 to 5. Although it is a resin with high surface hardness, it can be evaluated that the bonding strength of glass fibers is the lowest.

Examples 1 to 6 include aziridine-based polymers. In Examples 1 to 6, the minimum/maximum compressive strengths were 26.4 N/mm (Example 3) and 29.7 N/mm (Example 5), respectively. Comparative Examples 1 to 3 do not contain melamine-formaldehyde resin. Comparative Examples 1 to 3 do not contain an aziridine-based polymer. Comparative Example 1 showed the highest compressive strength (23.9N/mm) among Comparative Examples 1 to 3. However, the compressive strength of Comparative Example 1 is lower than that of Example 3. Therefore, it can be evaluated that the improvement in compressive strength results from the addition of the aziridine-based polymer.

Elaborate on compressive strength. The composition of Examples 1 and 2 differs only in the content of the aziridine-based polymer, but the content of the remaining components (excluding water) is the same. The same applies when the configurations of Examples 3 and 4 are compared with each other, and the same applies when the configurations of Examples 5 and 6 are compared with each other. The compressive strengths of Examples 1, 3 and 5 are higher than those of Examples 2, 4 and 6. Therefore, it can be evaluated that the improvement in compressive strength results from the addition of the aziridine-based polymer.

When comparing the contents of melamine-formaldehyde resin in Examples 1, 3, and 5, the content of Example 1 was the lowest and the content of Example 5 was the highest. Comparing the compressive strengths of Examples 1, 3, and 5, the compressive strength of Example 3 is higher than that of Example 1, and the compressive strength of Example 3 is the same as that of Example 5. Meanwhile, the storage stability of Example 5 is lower than that of Examples 1 and 3. Therefore, as the content of melamine-formaldehyde resin increases, the compressive strength improves, but if the content of melamine-formaldehyde resin exceeds the appropriate level, the compressive strength is maintained without improvement and the problem of reduced storage stability occurs. can see.

When comparing the contents of melamine-formaldehyde resin in Examples 2, 4, and 6, the content of Example 2 is the lowest and the content of Example 6 is the highest. Comparing the compressive strengths of Examples 2, 4, and 6, the compressive strength of Example 4 is higher than that of Example 2, and the compressive strength of Example 6 is higher than that of Example 4.

However, the difference in compressive strength between Examples 2 and 4 is 0.7N/mm, while the difference in compressive strength between Examples 4 and 6 is 0.2N/mm. Meanwhile, the storage stability of Example 6 is lower than that of Examples 2 and 4. Therefore, as the content of melamine-formaldehyde resin increases, the compressive strength improves, but if the content of melamine-formaldehyde resin exceeds the appropriate level, the rate of increase in compressive strength decreases and the problem of reduced storage stability occurs. You can.

Examples 1, 3, and 5 are the same as Examples 2, 4, and 6, except that they contain 0.5 parts by weight more aziridine-based polymer. While the compressive strength of Example 5 results in the so-called upper limit being reached, the compressive strength of Example 6 does not. Therefore, it can be seen that the additional addition of 0.5 parts by weight of aziridine-based polymer affected the rate of increase in compressive strength.

Comparative Examples 4 and 5 included water-dispersed polyester and silica sol as reinforcing agents for phenol-formaldehyde. Comparative Examples 4 and 5 were not hybridizable due to poor compatibility with phenol-formaldehyde resin.

ingredient
(part by weight) Example
7 Example
8 Example
9 Example
10 Example
11 Comparative example
6 Comparative example
7 phenolic resin 243.9 218.48 180.25 130.2 110 85.04 52.63 melamine resin 10 30 60.08 98.3 115.08 135 160.5 Mixing ratio 24:1 7.3:1 3:1 1.3:1 0.96:1 0.63:1 0.33:1 Viscosity (cps) 18.0 24.1 33.7 47.3 53.3 61.0 71.6 compatibility ◎ ◎ ◎ ◎ ○ X X Heat of combustion (MJ/kg) 23.4 22.7 21.5 21.1 20.7 20.4 19.8

Table 5 shows experimental results regarding the mixing ratio of phenol-formaldehyde resin and melamine-formaldehyde resin. The mixing ratio was evaluated based on viscosity, compatibility, and heat of combustion. The mixing ratios of Examples 7 to 11 and Comparative Examples 6 to 7 were about 24:1, about 7.3:1, about 3:1, about 1.3:1, about 0.96:1, about 0.63:1, and about 0.33:1, respectively. am.

Referring to Table 5, as the content of melamine-formaldehyde resin increases, the viscosity increases. As viscosity increases, the pump dispensing the binder may be overloaded. In addition, the lower the viscosity of the binder, the more uniformly the binder can be sprayed. However, as the viscosity increases, the binder becomes non-uniform, which may deteriorate the physical properties of glass fibers that have completed the heat curing process.

As the content of melamine-formaldehyde resin increases, miscibility decreases. Decreased miscibility means that the phenol-formaldehyde resin and the melamine-formaldehyde resin are not mixed uniformly. The glass fibers have completed the heat curing process by spraying the phenol-formaldehyde resin and melamine-formaldehyde resin unevenly. The physical properties of the fiber may deteriorate.

On the other hand, the lower the mixing ratio of melamine-formaldehyde resin, the closer it gets to the composition of the binder containing only phenol-formaldehyde resin. Accordingly, despite the mixing of the melamine-formaldehyde resin, the non-flammable performance may not be improved or may be slightly improved even if it is improved. Therefore, it is desirable to lower the heat of combustion and improve non-flammable performance by mixing the melamine-formaldehyde resin at an appropriate level. Therefore, considering viscosity, compatibility and heat of combustion, it is preferable to set the mixing ratio of phenol-formaldehyde resin and melamine-formaldehyde resin to 24:1 to 0.96:1, as in Examples 7 to 11, and 3 :1~ 1.3:1 is more desirable.

ingredient
(part by weight) Example
12 Example
13 Example
14 Example
15 Comparative example
8 Comparative example
9 Phenol:melamine 3:1 mixture 100 100 100 100 100 100 Aziridine-based polymer 0.01 0.05 0.1 One 3 5 Curing time (sec) 240 237 230 213 195 180 Pretty Cure Status doesn't exist doesn't exist doesn't exist doesn't exist has exist has exist Binder condition (MJ/kg) Good Good Good Good Good Good

Table 6 shows the precure state and binder state according to the content of aziridine-based polymer. Examples 12 to 15 and Comparative Examples 8 to 9 included a total of 100 parts by weight of the resin blend, which was prepared by mixing phenol-formaldehyde resin and melamine-formaldehyde resin at a weight ratio of 3:1.

Referring to Table 6, as the content of aziridine-based polymer increases, the curing time tends to decrease. However, a precure phenomenon occurred in Comparative Examples 8 to 9. The curing time of Examples 12 to 15 is in the range of 200 to 250 seconds, and the curing time of 200 to 250 seconds can be considered effective as a curing time in which the precure phenomenon does not occur. On the other hand, if the precure phenomenon occurs, it may lead to defects in the glass fiber, and the production cost of the glass fiber may increase due to supplementation or reproduction of the glass fiber. Increasing the content of aziridine-based polymer contributes to improving compressive strength, but when considering curing time and whether precure phenomenon occurs, 0.01 to 1 part by weight is appropriate per 100 parts by weight of the resin mixture.

Although the present invention has been described in detail through representative embodiments above, those skilled in the art will understand that various modifications can be made to the above-described embodiments without departing from the scope of the present invention. will be. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims described later, but also by all changes or modified forms derived from the claims and the concept of equivalents.

Claims (5)

With respect to 100 parts by weight of the resin blend of phenol-formaldehyde resin and melamine-formaldehyde resin and 100 parts by weight of the resin blend,
0.01 to 1 part by weight of aziridine-based polymer;
0.01 to 10 parts by weight of anti-vibration oil; and
Contains 0.01 to 5 parts by weight of amino silane,
The heat of combustion of the melamine-formaldehyde resin is lower than the heat of combustion of the phenol-formaldehyde resin,
A hybrid water-based binder for glass fiber with improved non-flammable performance and compressive strength, wherein the mixing ratio of the phenol-formaldehyde resin and the melamine-formaldehyde resin is 24:1 to 0.96:1.
According to paragraph 1,
A hybrid water-based binder for glass fiber with improved non-flammable performance and compressive strength, wherein the mixing ratio of the phenol-formaldehyde resin and the melamine-formaldehyde resin is 3:1 to 1.3:1.
According to paragraph 2,
The aziridine-based polymer is Trimethylolpropane tris (2-methyl-1-aziridine propionate, Trimethylolpropane tris (-N-aziridinyl) propionate, Pentaerythritol tris [3- (1-aziridinyl) propionate] or Pentaerythritol tris [2-methyl-1-aziridinyl propionate], a hybrid water-based binder for glass fibers with improved non-flammable performance and compressive strength.
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