JPS59163483A - Inorganic fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a thermosetting rod (fat and phosphorus) for inorganic fiber materials such as glass fiber and rock wool.
By treating with acids, inorganic fiber materials have heat resistance,
The present invention relates to a novel inorganic fiber that has good shape retention properties, heat insulation properties, and strength reduction prevention properties.

In general, heterocyclic ring/and aromatic thermosetting resin resin
When inorganic fiber materials such as glass fiber and rock wool that are molded and hardened with a binder are used at high temperatures, usually 400 to 500°C or higher, due to the lack of heat resistance of the binder, Combustion and decomposition cause significant thermal deterioration in high-temperature parts.
Inorganic #fiber compositions suffer from defects such as decreased shape retention, decreased heat insulation, increased costs due to thermal energy radiation, and decreased strength of the composition.

The present invention has been researched and completed in order to improve such defects, and because the binder has excellent carbonization persistence even at high temperatures of 400 to 600°C or higher, the inorganic material of the present invention This makes it possible to impart high heat resistance, heat insulation, good shape retention, and prevention of strength loss to fibrous materials.

That is, according to the present invention, a heterocyclic and/or aromatic thermosetting resin such as a triazine thermosetting resin and/or a phenolic thermosetting resin, and a phosphonic acid such as the general formula [Y]
R expressed as

The present invention provides inorganic fibers treated with phosphonic acids or the like.

The shape of the heterocyclic and/or aromatic thermosetting resin in the present invention may be water-soluble, water-dispersible, organic solvent-soluble, solvent-free, or non-water-dispersible; It is selected as appropriate depending on the embodiment and purpose. Specific examples of this heat-irradiating warlin fat are listed below (11 to (6)).
These can be used as weights or in combination of two or more types.

(11) Condensates of phenol derivatives such as phenol, nonylphenol, resorcinol, furesol, catechol, and hydroquinone with formaldehyde, and their alkylnyls (4) Phenolic thermosetting resins such as Tepi.

(2) Xylene-based thermosetting resins such as xylene and condensates of xylenes such as 1,2,3-xylenol and formaldehyde.

(3) Furfural-based thermosetting resin such as a condensate of furfural and formaldehyde.

(4) Triazine-based thermosetting resins such as adducts and condensates of triazine derivatives such as melamine, benzoguanamine, acetoguanamine, melon, and melam with formaldehyde, and alkyl etherified products thereof.

(triazine derivatives described in ffi+ +41,
A melamine-phenolic thermosetting resin is preferably a co-condensate of a mixture of melamine and a phenol derivative, preferably phenol, with formaldehyde.

(6) The triazine derivatives described in (4), preferably adducts and condensates of melamine and mixtures of amine compounds such as urea, thiourea, biuret, and dicyanthiae and formaldehyde, and alkyl etherified products thereof. A certain melamine-amino thermosetting resin.

Do the above (1) to (6) give good results?
In particular, economical efficiency, pre-existing production, scope of application, shape retention as an Iin process effect, heat resistance, heat insulation, and even 9<
From the point of +i degree drop prevention [I-, the four decoys of (4+ and (5)) are (2), f3) and (6)
Preferably, a triazine thermosetting resin or a phenolic thermosetting resin is used because it is superior to the above and can easily achieve the object of the present invention.

As the phosphonic acids of the present invention, compounds represented by the general formula [1] are preferably used.

: However, in the formula, R, HC, ~, represents an alkyl group, no\roalkylnok, 11, or a phenyl group.
11 R2 represents a hydrogen atom, a methyl group, an alkyl ester group consisting of C5~, an ester group containing a hydroxyl group or an epoxy group, or an ester group containing a phenyl group.

- 11 R3 represents a hydrogen atom or -CI(2-R,).
11 R4 and R5 may be the same or different, and represent a C1-5 11 1 alkyl ester group, a hydroxyl group or an epoxy group-containing ester group, or a phenyl group-containing ester group.
1() Further, specific examples of phosphonic acid compounds that can be used in the present invention are shown below.

fa) Ro-(dimethylphosphono)propionic acid methyl ester, Ro-(dimethylphosphono)propionic acid ethyl ester, 3-(dimethylphosphono)propionic acid butyl ester, 6-(dimethylphosphono)propionic acid pentyl ester, Ro-(dimethylphosphono)propionic acid (2-chloroethyl) ester, 3-(dimethylphosphono)propionic acid phenyl ester, 3-(di(
2-chloroethyl)phosphono1propionic acid methyl ester, 5-[di(2-chloroethyl)phosphonocopropionic acid diethyl ester, 3-(dibutylphosphono)propionic acid ethyl ester, 3-(dibutylphosphono)
Propion r acid pentyl ester 1.5-(dibutylphosphono)propionic acid (2-chloroethyl) ester,
Ro-(dibutylphosphono)propionic acid phenyl ester, 2-methyl ester to 3-(diphenylphosphono)cropion, 3-(diphenylphosphono)propionic acid phenyl ester, Ro-(dimethylphosphono)-2-methyl-propion Saka methyl ester, 6-(dimethylphosphono)-2-methyl-propionic acid butyl ester,
6-(dimethylphosphono)-2-methyl-propionic acid phenyl ester, 3-(diphenylphosphono)-2-
Methyl-propionic acid phenyl ester, dimethylphosphonoconocono-phosphoric acid dimethyl ester, dimethylphosphonocono-phosphoric acid diethyl ester, dimethylphosphonocono-conocono-phosphate
dibutyl phosphoric acid diester, dimethylphosphonosuccinic acid diphenyl ester, di(2-chloroethyl)phosphonocono-mono-mono-mono-mono-diphenyl phosphate, di(2-chloroethyl)phosphono-cono-mono-phosphate diphenyl ester, diethylphosphono-cono-mono-di(3),' (2-chloroethyl)ester,
Diethylphosphonosuccinic acid diphenyl ester, diphenylphosphonosuccinic acid dimethyl ester, diphenylphosphonosuccinic acid diphenyl ester, 1,2-di(carboxymethyl)-ro-dimethylphosphonopronol, 1,
2-di(carboxydiethyl)-3-diethylphosphonoconokun, L2-di(carboxyphenyl)-6-cyphenylphosphonoproban, 1,2-di(carboxyphenyl)-3-di(2- chloroethyl)phosphonopropane,
3-(dimethyl)phosphono-2-methyl-propion v
-N,N-dinothyladnoethyl ester, 3-(diphenyl)phosphonopropionte-N,N-diethylamine ethyl ester, ethylo, sulfonic acid diphenyl ester, phenylphosphone ff) c) thyl ester, phenylphosponic acid diphenyl ester , vinyl phosphophone r2 cyclo(2-chloroethyl)ester, ethane-
1127 Phosponic acid tetra(2-chloroethyl) ester, 2-dimethylposhoptan-1,2,4-tricarboxylic acid trinotyl ester, bis(2-hydroxyethyl) methylphosphonic acid trinotyl ester, 2-
Phosphonobutane-i, 2.4-tricarboxylic acid, 1-hydroquinethane-1, todiphosphonic acid, nido-1-norotrinonarenephosphonic acid, phenylphosphonic acid, phenylphosphon fb) Ro-(diethylphosphono)propionic acid (2- hydroxyethyl) ester, 3-, (diethylphosphono)propion M (2-hydroxyethyl) ester, ro-[di(2-chloroethyl)phosphonocopropionic acid (2-hydroxyethyl) ester, 3-(diphenylphosphono) )-,40 Pionic acid (1,2-hydroxyethyl) ester, Ro-(dimethylphosphono)-2
-Methylpropionic acid (2-hydroxyethyl) ester 3-(diisopropylphosphono)-2-methylpropionic acid (2-hydroxyethyl) ester,
1-methyltrimethylenephosphono)propionic acid (2-
(C) 6-(dimethylphosphono)propionate glycidyl ester, 6-(dimethylphosphono)propionate glycidyl ester, 3-A Diisopropylphosphono)propionic acid glycidyl ester, 3-(di(2-
chloroethyl)phosphono]propionate glycidyl ester, ro-diphenylphosphonopropionate glycidyl ester, ro-(dimethylphosphono)-2-methylpropionic acid glycidyl ester, ro-(diphenylphosphono)-2-methyl-propionate glycidyl ester ester,
and epoxy group-containing phosphonic acid compound ζ; any of these compounds can be used for the purpose of the present invention, but those that exhibit the effects of removal, brightness, and gu + I: jh IJ azine thermosetting A combination of a phenolic thermosetting resin and a phosphonic acid represented by the general formula [[]].

Examples of inorganic fibers included in the present invention include glass fibers, kasuri, asbestos, rock wool, and ceramic fibers.

Glass*fiber, asbestos, rock i++ treated according to the present invention
The confectionery field to which inorganic fiber compositions such as I can be applied include Δ%, shape retention at temperature, high heat resistance,
For each fi g field that requires heat resistance and prevention of strength deterioration, 1fij heat shields such as pipelines are available.

In addition, the treatment method in the present invention includes room temperature or fd
After pouring and mixing at high temperature, and further containing by applying pressure or pressure (a) and reducing pressure, heat curing at high temperature or room temperature curing with a curing medium is employed.

In the present invention, the heterocyclic and/or aromatic thermosetting resins shown in (1) to (6) above can be converted into 100
The mixing ratio of the phosphonic acids shown in (a) to (c) above to Shigetabe or the charged weight ratio when reacting should be 01 to 10%, preferably 05 to 5% in terms of jd phosphorus. Next, based on 100 parts by weight of the molten fiber, 0.1 to 40 parts by weight, preferably 1 part by weight of this phosphonic acid-containing heterocyclic ring/and aromatic thermosetting resin in terms of solid content are added. ~20
It is best to mix the two so that they become heavy.

Heterocyclic cylindrical resin used in the present invention/and aromatic thermosetting resin alone or with ammonium, etc.! F! ：Machine・
〉Used phosphorus such as acid salts or triphenyl phosphate;
Inorganic fibers treated with dredged ester-containing A-node cyclic splicing/and aromatic thermosetting resin exhibit good shape retention, heat resistance, and heat insulation properties in the temperature range up to about 300°C.
However, when it comes into contact with a high-temperature body of 400° C. to 900° C., the temperature decreases rapidly, causing the above-mentioned problems of 7 Jl.

However, inorganic fibers treated with the method of the present invention are loose.

It is possible to maintain good shape, high heat resistance, heat insulation, and elasticity even when in contact with a high-temperature body of ~900°C, and the present invention has remarkable characteristics that are unmatched in the past. has become clear.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Examples 1-6 Phenol 15 o3i (,42% formaldehyde 3
While stirring 2'5 parts of the mixture, 48
Gradually add 70 parts of % caustic soda. Next, the outer width was increased to 65"C and stirring was performed. Formaldehyde reaction rate 7
When it reached 0% or higher, it was immediately cooled down.

This resin liquid is solid! The U content was 461%, the water capacity was infinite, and the free formaldehyde was 71%.

10 parts of this phenolic resin (1% phosphonic acids as listed in Table 1) was added and mixed thoroughly. The composition thus obtained was heated for 1 hour at 135°C Cured under certain conditions.

The cured product was subjected to thermobalance differential thermal analysis measurement to examine the weight retention rate. The results are shown in Table-1.

Comparative Examples 1 to 4 Tests were conducted in exactly the same manner as in Example 1, except that a phenol resin alone or a phosphorus compound other than the uninvented one was used in place of the phosphonic acids, and the results are shown in Table 1.

] , --) c ~ -7- / Table ~ 1 j ll 2'3-(diphenylphosphocafropionic acid phenyl ester 1 /〆 4 phenylphosphonic acid dimethyl ester □ 2,7 1
96.81 7/5 1 Dimethylmethylphosphonate 1.8 1
96.31 Comparative Example 1 ----1
-- 876) 2 (Diammonium phosphate 2.0
89.9-// 3 1) Butyl phosphate 5,5, 91.
4:zz4',) butyl phosphate
・ , i. (Note 1) Thermobalance/Differential Thermal Analysis Measurement Conditions/Atmosphere: In air 0 Temperature rising rate: 10°C/min. Chart speed: 1 -/min (Note 2) Structural formula of compound A % Formula % 76 parts of dimethylphosphonosuccinate dimethyl ester was added to 100 parts of the phenol resin used in Example 1, and the mixture was thoroughly mixed. A phenolic resin binder was prepared.

To 100 parts of rock wool, add 65 parts of this pheno-A ink fat binder and mix well.
0 * m, inner diameter 300 mm, weight 200 kg/m" was molded and cured into a cylindrical shape. The outside of this cylindrical cured product was +1
1. Surface with iron plate! It was used as a heat insulating material for waste gas pipes. (Waste waste temperature 600°C) Outside the insulation material (til1
Surface IC heat? (H1!7 where temperature was measured by setting up a steel plate ↓
,+! ．． The surface temperature of t41 rose only to a maximum of 230''C, demonstrating good IC insulation and heat resistance.

After 6 months, I tried removing the iron plate on the surface, but the cured product retained its initial shape.

Example 8 In Example 7, a completely different test was carried out except that 76 parts of CBr4-Cl ((゛.' As a result, the temperature of the outer surface of the insulation material was a maximum of 240°C, and it maintained its initial shape well even after being heated.
Ta.

Actual example 1 Example 9 In Example 7, 4 parts of ethane-1,2-diphosphonic acid tetra(2-chloroethyl) ester was used instead of 76 parts of dimethylphosphonic acid dimethyl ester. A completely similar test was conducted except for the following. As a result, the temperature of the outer surface of the insulation material was 480°C, and the initial three forms were well maintained even after two months.

Comparative Example 5 In Example 7, a similar test was conducted using phenol resin alone without using 76 parts of dimethylphosphonosuccinic acid dimethyl ester.

Temperature l-1 of the external surface of the insulation material: rose to a maximum of 810°C, and the outer iron plate turned red. Moreover, it was not possible to maintain the initial shape for one month.

Examples 10 to 14 A mixture of 252 parts of melamine and 486 parts of 37.2% formalin was adjusted to pH 106 with an aqueous sodium hydroxide solution, and then heated and reacted to obtain a homogeneous transparent liquid. pH 4. Lower OK,
684 parts of methanol was added and methyl etherification was carried out by heating under reflux. Approximately 700 parts of a water-soluble methylated methylolmelamine resin having a homogeneous scarcity of 70% was obtained by concentration under reduced pressure. (Yield 95%) Table 2 was added to 100 parts of this melamine resin.
Add 1% of phosphonic acids as described in , calculated as phosphorus amount,
Mix well. The composition thus obtained was heated at 150°C
It was cured under curing conditions of 1 hour. The cured product was subjected to thermobalance differential thermal analysis 1111 to determine the weight retention rate, and the results are shown in Table 2.

Schif/′ ′−)! , +/' (Note 3) The thermobalance/differential thermal analysis measurement conditions are as in Clone-1 (Note 1)
) = 2 94.1 1 F36.6 1 81 Roshi 4.9
165.2 1 52.4 1 Ro21: 26A
;91.4172.11.7.0.5165.3 , 5
9.4150.3'6.29.6195.1:
88.2' 82.4 1 75.1':
69.3'56.2', 40.3
', 35.2 19 nails 75.1159.8
; 55.2153.2 4B, 6125.4 '25
．． 3 B4.6 69.1 146.8 U7.
8, 21, 8 14.8 114.8 14.8
;□□□□□□□□□□ 960 72.4: tq, 7 ro5.7
17,0 21.6 19,4 19.4 Comparative Examples 6 to 7 In Examples 10 to 14, water-soluble methylated methylolmelamine resin was used alone or in place of phosphonic acids, secondary ammonium phosphate was used. The same test was conducted except for the following, and the results are shown in Table 2.

Examples 15-1 5 parts of the melamine resin and phosphonic acid composition used in Example 10.11.1 were added to 100 parts of Noroc wool, and +! <After mixing, it was molded into a cylindrical shape and hardened so that the outside (T2'JJDmnr, inner diameter 120 mm, weight 150 kg/n2) was obtained.

This cured product is installed in high pressure steam piping (inner temperature 500℃),
The surface was covered with an iron plate, and the heat insulation properties and shape retention of the rock wool insulation material were tested. Within 6 months from the start of the test, the rock wool insulation material retained its initial shape, and its insulation effect was also excellent.

In addition, in this test, when the composition of Example 10 is used, Example 15 corresponds to Example 11, Example 16 corresponds to Example 17, and Example 16 corresponds to Example 17.

Example 18 A flask is charged with 140 parts of 67.2% formalin, and 5 [] parts of concentrated sulfuric acid is slowly added dropwise so that the internal temperature does not exceed 60''C.

Next, 106 parts of mixed xylene was added, and when the internal temperature was raised to 95°C, reflux started, and the reflux reaction was continued for 5 hours.

After the reaction was completed, the internal temperature was lowered to 80°C, and toluene was added at 80°C.
When sulfuric acid is removed by washing with water, xylene 4
It was possible to obtain 190 parts of rj,j fat (solid content 57.9%). The oxygen content of this xylene resin was 125% (per solid content).

For 100 parts of xylene resin It was made into a composition.

Using this, a strength test was conducted using the rock bead test method. The results are shown in Table B.

Rock bead test method The above composition was added at a solid content of 4 parts to 100 parts of rock beads (particle size 149 to 297μ), mixed thoroughly, and then placed in a cylindrical mold with an inner diameter of 20 mm. Pack a sample of N, 1. 20 mm in diameter and 2 in height using a standard testing machine.
It was molded into a cylindrical shape of 0 ma. After that, 180°C x 20
It was heat cured under curing conditions of 10 minutes. The strength of this cured product was measured.

Comparative Example 8 In Example 18, except for using phosphonic acids, all the same operations were carried out, and the hardened product was determined by the rock bead test method.
'f training was conducted and Table 37C is shown.

Table 6 (Note 4) Normal compressive strength: The compressive strength was determined using a material testing machine.

(Note 5) ifiJ groove compressive strength and moisture absorption rate: The test piece was exposed to fd at a temperature of 40'C1RH=96.5% for 5 days, and the compressive strength and moisture absorption rate were measured.

Example 19 100 parts of furfural resin with 100% non-volatile content, 1,2
-10 parts of diphosphonoethane detra(2-chloroethyl) ester, curing catalyst 2 to 1 part of para-toluenesulfonic acid
, c ro mixture! 5 parts of the snout and 100 parts of glass wool were mixed well and molded and processed in the same manner as Examples 15 to 17 to obtain shape retention.
i. 1. A 2-month test was conducted for fever.

Its unity, thermal deterioration of cured glass wool is small, 2
It retained its initial shape even after several months, and had an excellent heat insulating effect.

Example 20 Phenol 188N, melamine 252 parts, 37.2%
After adjusting the pH to 10.5 with an aqueous IJ solution, the mixture was reacted for 6 hours at a reaction temperature of 70"C. By dehydration under reduced pressure, a phenol-melamine cocondensate with a non-volatile content of 475% was obtained. 2060 parts (yield 94
%) was obtained. 5 parts of dimethylphosphonosuccinic acid dimethyl ester was added to 100 parts of this resin and mixed well to prepare a phenol-melamine cocondensation resin binder.

Rockwool'+D
m, heavy! It was molded into a donut shape and hardened to weigh 250 kg7 m2.

This hardened material was installed around a source of 6oo"c straight (6.100s+ yen 1) υ, and the surface of the insulation material was turned over with iron. Heat 4W surface force. A thermocouple was installed at a position 4 mm from the rock wool insulation shell to measure the temperature change inside the rock wool insulation shell.
It was C.

Example 21 66 parts of melamine, 180 parts of urea, 37.2% Forma 1]
After reacting 7629 parts at pH 10.5, the pH was adjusted to 4.
2, 720 parts of methanol was added to evaporate methyl ether, and the mixture was concentrated under reduced pressure to obtain 640 parts of a urea-modified melamine resin with a solid concentration of 70%.

To 100 parts of this urea-modified melamine resin, 11 parts of 6-(dimethyl)phosphono-2-methylpropionic acid-N,N-dimethylaminoethyl ester and 1 part of ammonium chloride as a curing catalyst were added and mixed thoroughly at t7. The composition thus obtained was cured at 150'C for 30 minutes.

While maintaining the temperature of this cured product at 600° C., thermobalance/differential thermal analysis was performed to examine the weight retention rate.

The results are shown in Table-4.

Comparative Example 8 Thermobalance/differential thermal analysis was carried out in the same manner as in Example 21, except for excluding 11 parts of 6-(dimethyl)phosphono-2-methyl-propionic acid-N,N-dimethylaminoethyl ester. I did it.

The results are shown in Table-4.

Table-A Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. An inorganic fiber treated with an aromatic thermosetting resin and a phosphonic acid. 2. The inorganic fiber according to claim 1, characterized in that the heteroarticulated cyclic striations/and the aromatic thermosetting resin are triazine thermosetting resin striations/and the phenolic thermosetting resin. . 6 Phosphonic acids have the general formula [[], [JD, (+10
The inorganic fiber according to claim 1, which is a compound represented by: Rd-j-COOR.
11 R5 and R6 can be the same or different, and 01 to . to Archi 1