JPH08882B2 - Non-flammable inorganic fiber binder - Google Patents

Description

TECHNICAL FIELD The present invention relates to a binder for inorganic fibers, in particular, a short glass fiber having excellent nonflammability.

[Conventional technology]

Inorganic fiber heat insulating materials such as glass fibers are widely used as various building and vehicle constituent materials due to their excellent sound absorbing and heat insulating properties. When a heat insulating material is manufactured using inorganic fibers such as glass fibers, the mat is sprayed with an uncured binder immediately after the glass is fiberized, and the mat is cured while passing through a heating furnace.

As a general binder that has been used conventionally, an aqueous binder obtained by adding or reacting urea to a resol type phenol resin is widely used. The use of urea as a binder for mineral fiber insulation is known in the art and is widely used as commercially acceptable. The reason is that urea acts as a bulking agent and easily reacts with free formaldehyde in the resol-type phenolic resin under weak alkaline or neutral pH conditions to form methylol urea, which is used in the inorganic fiber insulation material manufacturing process. The role of urea is to reduce the free formaldehyde content in the resol-type phenolic resin, and thereby to release formaldehyde from the resol-type phenolic resin, because it easily polymerizes to form a urea-formaldehyde resin binder at the curing temperature. And also greatly reduce the emission of other volatile components. By reducing the volatile components in this way, the amount of the binder deposited on the glass fibers at high temperature during use and during the curing process increases, and the binder efficiency improves. In addition, urea is currently one-fifth the price of resol-type phenolic resins, so it is also useful as an economical extender.

[Problems to be Solved by the Invention]

When an inorganic fiber heat insulating material is prepared using the above binder, the inorganic fiber itself is nonflammable, but as the density of the binder increases, the higher the density and the strength of the product, the lower the nonflammability of the heat insulating material produced. Come on. That is, although the base material test of the noncombustible material test according to the Ministry of Construction Notification No. 1828 passes, it approaches the judgment standard value. That is, in the base material test, when the heating furnace temperature is 750 ± 10 ° C, the reference temperature of the furnace rise temperature after inserting the test specimen is 50 ° C or less, 44
It approaches the judgment standard at ~ 49 ° C. Therefore, there is only a margin of 5 ° C. for the criterion value. Therefore, in order to increase the non-combustibility, higher flame retardancy than phenolic resin, containing nitrogen in the molecular structure, and increasing the addition amount ratio of urea that has been used for economic effects from the past, the non-combustibility is better. However, since the ratio of the urinary resin contained in the cured binder is high, there is a defect that water resistance is deteriorated.

Therefore, the present invention aims to provide a binder for glass fibers which does not have such defects, that is, has excellent nonflammability and water resistance.

[Means for solving the problem]

That is, the present invention provides (A) a resol type phenolic resin, (B) at least one guanidine salt selected from the group consisting of guanidine carbonate, guanidine hydrochloride, guanidine phosphate and guanidine sulfamate, and optionally (C) A non-flammable inorganic fiber binder comprising urea.

 Hereinafter, the present invention will be described in more detail.

In the present invention, the non-combustible inorganic fiber to which the binder of the present invention can be applied is not particularly limited, but glass fiber and rock wool are typical, and glass short fiber is particularly suitable.

The binder of the present invention comprises a resol type phenolic resin (A) and at least one guanidine salt (B) as essential components, and optionally an aqueous binder to which urea (C) is added. An aqueous binder obtained by reacting the phenol resin (A) with one or more kinds of guanidine salts (B) or (B) and urea (C) in advance and modifying them, and then adding urea may be used.

Here, the resol type phenol resin is referred to as a water-soluble initial condensate of phenols and formaldehyde.
As the phenols, conventional ones such as phenol, cresol, xylenol, butylcresol and bisphenol are used (hereinafter represented by phenol). Phenol and formaldehyde molar ratio 1.0
It is suitable to react under a basic catalyst in a proportion of ~ 4.2 mol, and a mixture of phenol and formaldehyde is heated at about 40 to 70 ° C for 10 hours to obtain a water-soluble initial condensate, which is treated with a suitable acid. Neutralization may be performed. After reacting phenol and formaldehyde, 5-100% of the total amount of phenol and formaldehyde
The urea-modified phenol / formaldehyde resin condensed by adding a certain degree of urine can be used in place of the non-modified phenol / formaldehyde resin. The resol-type phenol resin as the main component in the present invention is such a urea-modified phenol resin. It contains a phenolic resin.

The guanidine salt used in the present invention is selected from the group consisting of guanidine carbonate, guanidine hydrochloride, guanidine phosphate and guanidine sulfamate. As the guanidine salt, a commercially available product is sufficient, and they may be used alone or in combination of two or more. The guanidine salt may be added to the resol-type phenol resin as it is, but may be used by reacting both in advance. In some cases, the urea-modified phenolic resin may be used by replacing all or part of the urea with one or more guanidine salts. The composition ratio of guanidine salt and urea at that time was 99/1 to 1/99 (weight ratio,
The same shall apply hereinafter), and the composition ratio of the resol type phenolic resin and the guanidine salt is 99/1 to 50/50 (resin content conversion) used together. Further, urea may be optionally added or reacted. The amount of urea added is based on the total of the former two.
It is 10-5: 0-5.

Next, when the guanidine salt and urea are added to the resol type phenol resin (including urea modified resol type phenol resin, the same applies below), the composition ratio of the guanidine salt and urea is 99/1 to 1/99 together. However, it may be added. The composition ratio of the resol-type phenol resin, the guanidine salt, and the total amount of urea is 99/1 to 50/50 (resin content conversion).

The strength characteristics and flame retardancy of the obtained inorganic fiber heat insulating material can be adjusted by changing the addition method or the addition amount and modification amount of the guanidine salt, so it is possible to easily respond to the required characteristics. You can Preferably, the proportion of the resole type phenolic resin (A), guanidine salt (B) and urea (C) in the binder is (A) :( B) :( C) = 90-50: 1-60: 1- It is desirable to use within the range of 50 from the balance of strength characteristics and flame retardancy / water resistance.

Non-combustible inorganic fiber heat insulating material created using this binder, the temperature rise in the furnace in the base material test of the non-combustible material test can significantly suppress the temperature rise in the furnace as 10 ~ 30 ℃,
The non-combustible grade can be improved. The binder obtained by adding or reacting the resol type phenol resin of the present invention with a highly flame-retardant guanidine salt is more difficult than the binder used by adding or reacting urea to the resol type phenol resin which has been conventionally used. In addition to being flammable, it was possible to improve the moisture resistance and water resistance defects of the urea-formaldehyde resin by using a guanidine salt copolymerizable with urea or a urea resin.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” or “%” means “parts by weight” or “% by weight” unless otherwise specified.

Example 1 100 parts of phenol and 300 parts of 40% formalin are thermometers,
Put in a flask equipped with a condenser and stirrer, mix evenly, and then add 6 parts of 48% sodium hydroxide aqueous solution to 50 ° C.
The temperature is raised to 50 ° C and the reaction is performed for 10 hours. Immediately after completion of reaction 30
The mixture was cooled to ℃ and neutralized with an acid to obtain a phenol resin A having a resin content of 40%, a pH of 7.5 and an infinite water dilutability. Next, 60 parts by weight of phenol resin A (converted to resin content), 5 parts by weight of guanidine sulfamate, 35 parts by weight of urea and water, and 30 parts of 25% ammonia water for each of the binder main components, which are usually used auxiliary components, Ammonium sulfate (3 parts), silane coupling agent (0.2 parts), and oil (3 parts) were added and mixed to prepare a binder having a concentration of 15%. The binder was sprayed immediately after the glass was made into fibers, and cotton was collected to form a mat. The binder was cured by passing through a heating furnace at 250 ° C. to prepare a glass fiber heat insulating material having a density of 64 kg / m ³ , a thickness of 25 mm, and a binder adhesion amount of 9%. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance was measured by the method according to Ministry of Construction Notification No. 1828. I.e. 40 x 40
Put a sample of × 50mm in an electric furnace adjusted to be stable at 750 ° C for 20 minutes or more, and set the temperature before sample insertion and
The maximum temperature after insertion was measured, and if the difference was within 50 ° C, it was regarded as acceptable. The results are shown in Table 1.

Example 2 100 parts of phenol and 300 parts of 40% formalin are thermometers,
Put in a flask equipped with a condenser and stirrer, mix evenly, and then add 6 parts of 48% sodium hydroxide aqueous solution to 50 ° C.
The temperature was raised to 50 ° C and the reaction was continued for 9 hours at 60 ° C.
React on time. Immediately after completion of the reaction, the mixture was cooled to 30 ° C. and neutralized with an acid to obtain a phenol resin B having a resin content of 50%, pH 7.5, and infinite water dilutability. Next, 60 parts by weight of phenol resin B (converted to resin content), 5 parts by weight of guanidine sulfamate, urea
35 parts by weight and water, and 25% ammonia water for each of the binder main components for the commonly used subcomponents
30 parts, ammonium sulfate 3 parts, silane coupling agent 0.2 parts, oil 3 parts were added and mixed to prepare a binder having a concentration of 15%, and the density was adjusted.
A glass fiber heat insulating material having a weight of 64 kg / m ³ , a thickness of 25 mm, and a binder attached amount of 9% was prepared. This heat insulating material also has a high nonflammability in addition to the excellent sound absorption and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 3 100 parts of phenol and 300 parts of 40% formalin are thermometers,
Put in a flask equipped with a condenser and stirrer, mix evenly, and then add 6 parts of 48% sodium hydroxide aqueous solution to 50 ° C.
The mixture is heated to 50 ° C. and reacted at 50 ° C. for 9 hours, 10 parts of guanidine sulfamate and 50 parts of urea are added, and the reaction is continued for another hour. Immediately after completion of the reaction, cool to 30 ° C, neutralize with acid, resin content 50%
A phenol resin C having a pH of 7.5 and an infinite water dilutability was obtained. Next, 60 parts by weight of phenolic resin C (converted to resin content), 40 parts by weight of urea, and water, and 25% ammonia water 30% for each of the binder main components for the commonly used subcomponents.
Parts, ammonium sulfate 3 parts, silane coupling agent 0.2 parts, oil 3
Parts and mix to prepare a binder with a concentration of 15% and a density of 64
A glass fiber heat insulating material having a kg / m ³ , a thickness of 25 mm and a binder adhesion amount of 9% was prepared. This heat insulating material also has a high nonflammability in addition to the excellent sound absorption and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 4 100 parts of phenol and 300 parts of 40% formalin are thermometers,
Put in a flask equipped with a condenser and stirrer, mix evenly, and then add 6 parts of 48% sodium hydroxide aqueous solution to 50 ° C.
The temperature is raised to 50 ° C. and the reaction is carried out at 50 ° C. for 9 hours, 50 parts of guanidine sulfamate and 10 parts of guanidine phosphate are added and the reaction is continued for another 1 hour. Immediately after completion of the reaction, it was cooled to 30 ° C and neutralized with an acid.
A phenol resin C having a resin content of 50%, a pH of 7.5 and an infinite water dilutability was obtained. Next, phenol resin D 60 parts by weight (converted to resin content), urea 40 parts by weight and water, and for the commonly used auxiliary components, 25% ammonia water 30 parts, ammonium sulphate 3 parts, silane coupling for the binder main component, respectively. Agent 0.2
Parts and 3 parts of oil are added and mixed to prepare a binder with a concentration of 15%, a density of 64 kg / m ³ , a thickness of 25 mm, and a binder adhesion amount of 9%.
Created a glass fiber insulation material. This heat insulating material also has a high nonflammability in addition to the excellent sound absorption and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 5 60 parts by weight of the resol-type phenolic resin A (resin content conversion) obtained in Example 1, 5 parts by weight of guanidine carbonate, 35 urea
30 parts by weight of water and 25% ammonia water for each of the binder and the main components of the commonly used subcomponents.
Parts, ammonium sulfate 3 parts, silane coupling agent 0.2 parts, oil 3
Parts and mix to prepare a binder with a concentration of 15% and a density of 64
A glass fiber heat insulating material having a kg / m ³ , a thickness of 25 mm and a binder adhesion amount of 9% was prepared. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 6 60 parts by weight of the resol-type phenolic resin A (resin content) obtained from Example 1, 5 parts by weight of guanidine hydrochloride, 35 parts by weight of urea, and water, and other commonly used subcomponents with respect to the binder main component 25% ammonia water 30 each
Parts, ammonium sulfate 3 parts, silane coupling agent 0.2 parts, oil 3
Parts and mix to prepare a binder with a concentration of 15% and a density of 64
A glass fiber heat insulating material having a kg / m ³ , a thickness of 25 mm and a binder adhesion amount of 9% was prepared. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 7 60 parts by weight of resol type phenolic resin A (resin content) obtained in Example 1, 5 parts by weight of guanidine phosphate, 35 urea
30 parts by weight of water and 25% ammonia water for each of the binder and the main components of the commonly used subcomponents.
Parts, ammonium sulfate 3 parts, silane coupling agent 0.2 parts, oil 3
Parts and mix to prepare a binder with a concentration of 15% and a density of 64
A glass fiber heat insulating material having a kg / m ³ , a thickness of 25 mm and a binder adhesion amount of 9% was prepared. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 8 60 parts by weight of the resol-type phenol resin A obtained in Example 1 (converted to resin content), 10 parts by weight of guanidine sulfamate, 30 parts by weight of urea and water, and other commonly used subcomponents relative to the binder main component. 25% ammonia water 30 parts, ammonium sulfate 3 parts, silane coupling agent 0.2
Parts and 3 parts of oil are added and mixed to prepare a binder with a concentration of 15%, a density of 64 kg / m ³ , a thickness of 25 mm, and a binder adhesion amount of 9%.
Created a glass fiber insulation material. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 9 60 parts by weight of the resol-type phenol resin A obtained in Example 1 (converted into resin content), 20 parts by weight of guanidine sulfamate, 20 parts by weight of urea and water, and other commonly used subcomponents with respect to the binder main component 25% ammonia water 30 parts, ammonium sulfate 3 parts, silane coupling agent 0.2
Parts and 3 parts of oil are added and mixed to prepare a binder with a concentration of 15%, a density of 64 kg / m ³ , a thickness of 25 mm, and a binder adhesion amount of 9%.
Created a glass fiber insulation material. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 10 60 parts by weight of the resol-type phenol resin A obtained in Example 1 (converted to a resin content), 30 parts by weight of guanidine sulfamate, 10 parts by weight of urea and water, and usually used subcomponents with respect to the binder main component. 25% ammonia water 30 parts, ammonium sulfate 3 parts, silane coupling agent 0.2
Parts and 3 parts of oil are added and mixed to prepare a binder with a concentration of 15%, a density of 64 kg / m ³ , a thickness of 25 mm, and a binder adhesion amount of 9%.
Created a glass fiber insulation material. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Example 11 60 parts by weight of the resol-type phenol resin A obtained in Example 1 (converted into resin content), 40 parts by weight of guanidine sulfamate and water, and 25% ammonia for each of the binder main components with respect to commonly used auxiliary components 30 parts of water,
Ammonium sulfate 3 parts, silane coupling agent 0.2 parts, oil 3 parts were added and mixed to prepare a binder having a concentration of 15%, and a density of 64 kg / m.
^3. A glass fiber heat insulating material having a thickness of 25 mm and a binder attachment amount of 9% was prepared. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Comparative Example 1 100 parts phenol and 280 parts 40% formalin thermometer,
Put in a flask equipped with a condenser and a stirrer, mix evenly, then add 7 parts of 48% sodium hydroxide aqueous solution, and add to 50 ° C.
The temperature is raised to 50 ° C and the reaction is performed for 10 hours. Immediately after completion of reaction 30
The mixture was cooled to ℃ and neutralized with an acid to obtain a phenol resin D having a resin content of 40%, a pH of 7.5, and an infinite water dilutability. Next 70 parts by weight of this resol type phenol resin D (resin equivalent), urea 30
30 parts by weight of water and 25% ammonia water for each of the binder and the main components of the commonly used subcomponents.
Parts, ammonium sulfate 3 parts, silane coupling agent 0.2 parts, oil 3
Parts and mix to prepare a binder with a concentration of 15% and a density of 64
A glass fiber heat insulating material having a kg / m ³ , a thickness of 25 mm and a binder adhesion amount of 9% was prepared. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

Comparative Example 2 Resol-type phenol resin D6 obtained in Comparative Example 1
0 parts by weight (converted to resin content), 40 parts by weight of urea and water, and 30 parts of 25% ammonia water, 3 parts of ammonium sulfate, 0.2 parts of silane coupling agent for the binder main component for each of the normally used subcomponents. Add 3 parts of oil and mix to a concentration of 1
A binder of 5% was prepared to prepare a glass fiber heat insulating material having a density of 64 kg / m ³ , a thickness of 25 mm, and a binder adhesion amount of 9%. This heat insulating material has a high non-combustibility in addition to the excellent sound absorbing and heat insulating properties that have been provided conventionally. The non-combustible performance is as shown in Table 1.

[Effects of the Invention] As described in detail above, the non-combustible inorganic fiber heat insulating material prepared by using the binder of the present invention is capable of improving the non-combustible grade in addition to the excellent sound absorbing and heat insulating properties provided conventionally. You can The inorganic fiber heat insulating material that has a conventional commonly used main component with a resole-type phenol resin or urea-modified phenol resin and uses a binder to which urea is added or reacted has a margin of 5 ° C against the judgment standard. Although the inorganic fiber heat insulating material prepared by using the binder of the present invention has a margin of 10 to 30 ° C., a high quality, non-combustible inorganic fiber heat insulating material can be obtained. Further, this binder is an excellent binder that can be applied to all binders that have been used for glass heat insulating materials.

Claims (2)

[Claims] 1. A resol type phenolic resin, (B) at least one guanidine salt selected from the group consisting of guanidine carbonate, guanidine hydrochloride, guanidine phosphate and guanidine sulfamate, and optionally (C). Non-flammable inorganic fiber binder made of urea. 2. The ratio of (A) :( B) :( C) is 90 to 50: 1.
The binder for inorganic fibers according to claim 1, wherein the binder is -60: 1-50.