JPS6028298B2 - Method of manufacturing bituminous foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in the manufacturing method of blue-green foam, and in particular, it involves mixing a urethane raw material with fillers such as asphalt and petroleum resin, and producing foam at a high liquid temperature of 90 to 250°C. The purpose is to obtain a polyurethane foam by foaming.

Polyurethane foams have recently been widely used as heat insulating materials, sound absorbing materials, vibration isolating materials, damping materials, sound insulating materials, waterproofing materials, sealing materials, and the like.

Conventionally, the method for producing torturous foam by mixing a filler such as asphalt involves impregnating a pre-produced polyurethane foam with a solution of asphalt, a volatile solvent such as petroleum resin, and then drying it. It is something that

This method is economically disadvantageous because it requires a large amount of volatile solvent, and it takes a long time to dry the solvent, which reduces productivity and makes it difficult to handle as it becomes sticky. . Another drawback is that it is difficult to add fillers. As an improvement on this, a method has been proposed in which a filler such as asphalt is mixed and foamed, and for example, water, an alkali halide, a low boiling point alkane, etc. are used as the foaming agent.

When using water as a blowing agent, the boiling point of water under normal pressure is 1
0000, and a normal foaming reaction could not be performed at a liquid temperature of around 100q0 or higher, so a normal foam could not be produced. Also, if a large amount of a substance consisting essentially of hydrocarbons, such as asphalt, is mixed in, the viscosity of the raw material will increase, and it will not be possible to mix it sufficiently and it will not be able to flow through a normal foam. Ta.

Furthermore, even if a large amount is mixed in, the filler must be made of a low molecular weight compound in order not to increase the viscosity of the raw material, resulting in poor mechanical properties such as tensile strength. Furthermore, when a large amount of filler is mixed and foaming is performed at a relatively low temperature, a large amount of catalyst is required, which is economically disadvantageous, and the resulting foam has particularly poor moist heat aging resistance and light resistance. This is because the metal catalyst causes a sensitization effect, and also acts as a dissociation catalyst, reducing the heat insulation properties and compressive ice strain. Further, even if it is attempted to use a low boiling point solvent such as monofluorotrichloromethane as a blowing agent, it is impossible to use these because the temperature of the foaming raw material is high.

Also, even if an organic solvent with a boiling point of 90oo or more is used,
It is difficult to obtain flame retardant solvents among these solvents, and solvents other than halogen compounds pose a fire hazard and are toxic. Therefore, there is a need for a foam that has low temperature sensitivity and excellent mechanical performance even though it contains a large amount of a material essentially consisting of hydrocarbons, such as asphalt or petroleum resin, which has a relatively high melting point. be.

The present invention has been made as a result of extensive research in response to such demands, and has resulted in the discovery of a method for producing a lantern-like foam that achieves the following objects. In other words, the first purpose is 90
Easily foams at high temperatures of 0.00 or higher. [ii}
The second purpose is to mix in a large amount of materials consisting essentially of hydrocarbons, such as asphalt and petroleum resin.

{iii] The third purpose is to mix in a large amount of high viscosity liquid or solid filler.

{iv} The fourth purpose is to mix a large amount of filler but only need a small amount of catalyst.

M The fifth objective is to have excellent mechanical properties even though a large amount of filler is mixed in.

The sixth purpose of M' is to have excellent heat resistance even though a large amount of filler is mixed therein.

Therefore, the method of the present invention uses a polyol, a polyisocyanate,
In the method for producing a high-quality foam by mixing and reacting raw materials of a blowing agent, filler, catalyst, and other auxiliary agents, {a) a solid or semi-solid solid material at room temperature as a filler; [b} is blended in an amount of 150 to 200 parts by weight to 10 parts by weight of polyol, and the decomposition temperature is 75 to 30% as a blowing agent.
This is a method for producing a polyurethane foam, which uses an inorganic water-containing compound of 00000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000 more.

In the present invention, as a result of various studies in order to produce a strong foam mainly made of foam, it is necessary to use a bituminous material that is solid or semi-solid at room temperature.

Furthermore, since a large amount of oak blue substance is used, there is a problem that the reaction is delayed. For this reason, it is necessary to foam using high-temperature raw materials, but water and monofluorotrichloromethane, which are commonly used, do not react with the isocyanate in the water and vaporize and escape from the system when foaming at high temperatures. could not pass through normal foam because it vaporized and escaped before mixing. Further, especially when water is used as a foaming agent, when mixed with a raw material of 90 qo or more, large pinholes are formed due to vaporized gas, and a normal foam cannot be obtained.

In the present invention, in order to produce a blue foam with a large amount of clear blue mixed in at high temperatures, an inorganic hydrocarbon compound that decomposes at 75 to 300 oo is used as a blowing agent, and the mixing temperature of the raw materials is adjusted at the time of foaming. The present invention was completed based on the discovery that this could be achieved by limiting the number to a range of 90 to 250.

The polyol used in the present invention has a number average molecular weight of 50
General polyurethane polyols having a molecular weight of 0 to 10,000, preferably 500 to 5,000 may be used, and preferred are polygene polyols, castor oil polyols, and timer acid polyols.

General polyurethane polyols include polyester polyols produced by condensing alkylene oxide adducts such as ethylene oxide and propylene oxide of short chain polyols such as glycerin, sorbitol, and sugar with polyether polyols and adipic acid and short chain polyols. It is.

The polygene polyol may be one commonly used, but preferably has a number average molecular weight of 500 to 10,000.
It is a polygenic polyol obtained by terminally hydroxyl-terminating a radical or anionic copolymer of a diene compound such as butadiene, isoprene, or chloroprene or a copolymerizable pinyl compound such as styrene or acrylonitrile. Other polygene polyols include those obtained by the ozonolysis and reduction method of solid rubber containing a gene component. Castor oil polyols include commonly used castor oil or castor oil derivative polyols having a number average molecular weight of 500 to 5,000, such as castor oil polyesters, and polyesters obtained from mixed polycarboxylic acids of castor oil and other acids such as adipic acid. , a mixture of castor oil and short chain polyols such as ethylene glycol, 1,4-butanediol, and glycerin, and poly-IJ.
Examples include reaction products of castor oil with carboxylic acids, reaction products of castor oil with alkylene oxides such as propylene oxide, ethylene oxide, butylene oxide, alkylene oxide addition polymers of castor oil polyester, or mixtures thereof. It will be done.

In addition, the number average molecular weight of the dimer acid polyol is 60.
0 to 10,000, preferably 600 to 5,000 dimer acid polyesters which are reaction products of dimer acids with short chain diols, triols or polyols, or dimer acids and polyalkylene glycols, polyalkylene triols or long chain polyols such as dimer acid polyesters which are reaction products with castor oil, and alkylene oxide addition polymers of the above-mentioned dimer acid polyesters.

Also included are reaction products of dimer acids, other dicarboxylic acids such as adipic acid, and the various short chain diols, triols, or polyols mentioned above. Furthermore, reaction products of dimer acid and alkylene oxide can also be used as other conductors. First, the above polyols for polyurethane, polygene polyols, castor oil polyols, and dimer acid polyols may be used alone or in combination.

Examples of the phosphorescent substance that is solid or semi-solid at room temperature include straight asphalt and freon asphalt with a penetration degree of 10 to 200.

Also, process oils that are mixed into general solid rubber for the purpose of improving cold resistance, adhesion, and fluidity, tars such as coal tar and petroleum oil tar, and C4 or higher fractions that are by-produced during naphtha cracking. Preferably C5-C, . Petroleum resins copolymerized with the monomers in crab matter, various synthetic resins, and residual synthetic oils can also be used. Furthermore, liquid polybutene, natural rosin, ester gum, wax, polyisoprene, coumaron-indene resin, xylene resin,
Plasticizers such as tertiary butylphenol resin and terbene resin, chlorinated paraffin, and the like may be blended.

The reason for limiting the amount of the light blue material added to 150 to 200 parts by weight is that sufficient performance such as vibration damping and waterproofing cannot be obtained with 15 parts by weight, and 200 parts by weight cannot be obtained. This is because if the amount exceeds the weight part, the mechanical properties will deteriorate.

In addition, in the present invention, powdered or fibrous fillers that are blended with general plastics may be blended, such as calcium carbonate, barium sulfate, alumina, talc, diatom, clay, kaolin, mica, asbestos, glass powder, and glass. Fibers, gypsum (calcined gypsum), silica gel, carbon, thick powder, cellulose, nylon fibers, etc. are added singly or in rough combination.

These surface-treated products are also included. Further, the amount added is 400 parts by weight or less based on 10 parts by weight of polyol,
The reason for this is that if it exceeds 400 parts by weight, it will not be uniformly mixed with other raw materials and stable operation will not be possible.

In addition, the blowing agent used in the present invention has a decomposition temperature of 75
~300q0, such as hydroxide compounds such as boric acid, aluminum hydroxide, magnesium hydroxide, iron hydroxide, or calcium sulfate dihydrate, terrace sand, calcium sulfite dihydrate, etc. water salt, calcium chloride hexahydrate, cobalt chloride hexahydrate, steel (0) chloride dihydrate, barium chloride dihydrate, copper (0) sulfate pentahydrate, sodium sulfate decahydrate, magnesium sulfate decahydrate It is a hydrated salt type.

In addition, there is a correlation between blowing agents and polyols, and it is necessary to select and use them appropriately.When using general polyols or gene-based polyols as the polyol, hydroxides or hydrated salts should be used as the blowing agent. use.

Furthermore, in the case of castor oil-based polyols and dimer acid-based polyols, hydroxides are used as blowing agents. In the foaming agent of the present invention, all of the active hydrogen in the foaming agent reacts with the isocyanate, and there is no need to use it for the foaming reaction, and the active hydrogen (water) may remain as a stable salt with a low water content, or it may remain unreacted. It may be allowed to remain as a property.

The polyisocyanate used in the present invention is
Those commonly used in the production of bedding or rigid polyurethane foams may be used, such as tetramethylene diisocyanate, hexamethylene diisocyanate, /namethylene diisocyanate, cyclohexane-1,3-diisocyanate, and cyclohexane-diisocyanate. 1,4-diisocyanate, 1
・3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4' diisocyanate (MDI) ), crude MD
1 (crude MDI), liquefied MD1 (liquid M
DI), or a prepolymer containing a terminal isocyanate group prepared from a compound containing polyisocyanate and active hydrogen, either singly or as a mixture.

Note that the blowing agent used in the present invention does not need to use all of the active hydrogen in the blowing agent for the foaming reaction with isocyanate, and the ratio of isocyanate to total active hydrogen (NCO/H)
is preferably in the range of 0.2 to 2.0.

However, this does not apply to a reaction material system without a hydroxyl value called the prepolymer method. The catalyst used in the present invention may be one commonly used in the production of polyurethane foams or rigid polyurethane foams, such as triethylamine, N-methylmorpholine, N-ethylmorpholine, N-ethylmorpholine,
N・N'. N'-tetramethylpropyldiamine, N.
N・N′・N′-tetramethylhexamethyldiamine,
Tertiary amines such as triethylene diamine, tin compounds such as tributyltin acetate, dibutyltin acetate, dibutyllaurylate, ditin chloride, stannath octoate, stannath oleate, lead compounds such as lead penzoate, lead oleate, Cobalt compounds such as cobalt naphthenate and cobalt benzoate, and carboxylic acids such as n-butyric acid and valeric acid.

Further, in the present invention, other additives such as a crosslinking agent, a silicon compound, an ultraviolet absorber, and an antioxidant may be added.

Next, examples of the present invention will be described.

(All parts below refer to parts by weight.) Examples 1-
3 Hydroxyl group content 0.83me polybutadiene polyol (polyBDR-4 spot T manufactured by Alco Chemical Co., Ltd.)
89.7 parts, 1 part silicone, 20.6 parts of boric acid/polybutadiene polyol (weight ratio 1/1) mixture, and straight asphalt (penetration 80-100) 300-80
Mix and heat to 1000C, and when the temperature becomes constant, add DABCO-34V (a dipropylene glycol solution of triethylene diamine manufactured by Mitsui Air Protac, weight ratio 1/2) and dibutyltin dilaurylate (DBTD).
L) were added as shown in Table 1, and after lighting for 30 seconds at 600 pm, 62.0 parts of CRIO0 (NC031% manufactured by Mitsui Toatsu Chemical) was added and 1-stage. A blue-green foam was obtained after some damage.

The results of measuring the density and mechanical properties of the turquoise foam thus obtained are shown in Table 1. 1st expression king [1'
The tensile strength (T8) was measured in accordance with JISK-6301 using a dumbbell-shaped test piece with a thickness of 1 mm at a tensile rate of 20 ratios/min.

[21 Stress at 50% compression is 5 according to ASTM2406
50% from the chart obtained by compressing the test piece on the 0 x 50 x 40 (t) side to 60% at a compression speed of 50 side/min.
The stress during compression was determined.

In addition, when the foam according to Example 3 was used as a vibration isolating material, it had good characteristics, and when its sound absorption coefficient was measured, it was found that it had strong absorption in bass frequencies.

Examples 4-7 polyBDR-4 vs. T, 80.5 parts, 1 part silicon,
Calcium sulfate dihydrate/polyBDR-4 group T (weight ratio 1/1) kneaded product 39. Straight asphalt (penetration 80-100) and blown asphalt (
Penetration of 20 to 30) was added as shown in Table 2,
After heating to 120 to 130 qo and maintaining at this temperature, DABCO and DBTDL were further blended as shown in Table 2, mixed with 3M sand at 600 pm, and then MDI-CRI.
OO to 63. After adding Yuito and adding 10% of sand, a roaring quality foam was obtained.

The results of measuring the density and mechanical properties of the translucent foam thus obtained are shown in Table 2.

The waterproof properties of the foams according to Table 2 and Example 4 were measured by the method shown in FIG.

That is, a U-shaped foam 2 is placed between two sheets of transparent Acrylic resin 1.
Water 5 was injected at a height of 100 skin from the upper part of the vertically attached pipe with scissor bolts 4 at a compression ratio of 50% through the spacer 3, and a test was conducted to see if water would leak.

As a comparative example, the crab blue foam 6 impregnated with asphalt having a density of 0.13 mm/lump was also tested in the same manner as above.

As a result, the foam of the comparative example leaked water for 2 hours after being injected with water, but the foam of the present invention did not leak any water even after 1 day, indicating that its waterproof properties were significantly improved.

Examples 8 to 11 80.5 parts of polyBDR-4 beat T, 1 part of silicon, calcium sulfate dihydrate/polyBD4 spot T (weight ratio 1/
1)39. 1 anchor straight asphalt (penetration 8
0-100), blown asphalt (penetration 20-3
0) and filler were added as shown in Table 3, and 20 parts of DABCO-3 Maru V, DBTDLI. 0 copies, M
63.DI-CRIOO. A translucent foam was obtained in the same manner as in Example 4.

Note that calcium carbonate or barium sulfate was used as a filler, and this was mixed with asphalt.

The results of measuring the density and mechanical properties of the translucent foam thus obtained are shown in Table 3. Table 3 Example 1
2-15 polyBDR-4 spot T 55.4 parts, silicone 1 part, calcium sulfate dihydrate/polyBDR-4 melon T (weight ratio 1/1) 89.2 hot straight asphalt (penetration 80-100) and Blown asphalt (penetration 20
~30), BABCO-3 Maru V and DBTDL were added as shown in Table 4, and MDI-CRIOO was added to 12
8.2 parts were mixed and the same machine as in Example 4 was used to obtain a light blue foam.

The results of measuring the density and mechanical properties of the translucent foam thus obtained are shown in Table 4.

The thermal conductivity of the polyurethane foam according to Table 4 and Example 12 is 0.04 i cal/hr°C, and the thermal conductivity of the general foam graph is 0.05 cal' hrqC(d
= 0.17) showed better heat insulation properties.

In addition, the results of measuring the normal incidence sound absorption coefficient (thickness: 2 mm) for the foam of Example 13 and the comparative bituminous foam (density: 0.02 mm/clump) are shown in Figure 2. can be,
The clear blue foam according to the invention exhibited excellent sound absorption coefficients.

The vibration damping properties of the foam of Example 14 and the comparative foam (density 0.02 m/clump) were measured using an apparatus as shown in FIG.

As shown in FIG. 4, the results showed that the blue-green foam according to the present invention exhibited excellent vibration damping properties. Example 16-20poly
80.5 parts of BDR45-HT, 1 part of silicon, calcium sulfate, dihydrate/polyBDR-4 Team T (weight ratio 1/
1) 39.0 parts, straight asphalt (penetration 80
-100) 800 copies, DABCO-3 Maru V, DBTDL
and HDI-CRIOO were blended in amounts of 57.3 to 86.0 parts, and a blue-green foam was obtained in the same manner as in Example 4.

The results of measuring the density and mechanical properties of the foam thus obtained are shown in Table 5.

Table 5 Examples 21 to 23 80.5 parts of polyBDR4 T, 1 part of silicon, calcium sulfate dihydrate/polyBDR4 HuT (weight ratio 1/
1)39. Boguni, straight asphalt (penetration 80
~100) and/・Yizol distillation residue (/・Yizol,
Japan Petrochemical Synthetic Oil) were added as shown in Table 6, and DABCO-3 Maru V and DBTDL were added in specified amounts and M
63.DI-CRIOO. The base was blended and the same procedure as in Example 4 was carried out to obtain a lantern foam.

The results of measuring the density and mechanical properties of the foam thus obtained are shown in Table 6.

Table 6 Example 24 80.5 parts of polyBDR-4T, 1 part of silicon, calcium sulfate dihydrate/polyBDR-4T (weight ratio 1/1) 39. Straight asphalt (penetration 80-100) / AH-10 process oil (manufactured by Idemitsu Kosan) (weight ratio 9/1) 300 parts, DABCO-34V,
Specified amount of DBTDL and 63.0 MDI-CRIOO
A translucent foam was obtained in the same manner as in Example 4 by blending the respective parts.

The density of this foam was 0.156 m/clump. Example 25 Reagent 1st grade castor oil (hydroxyl value 16.0, acid value 1.0) 1
0 eaves, boric acid 7. Take the side part, 1 part of silicone, and 30 parts of straight asphalt (penetration 80-100) on a stainless steel pad, and apply about 100 liters.

Heat to 0 and hold at this temperature to DABCO-3 mountain V3
．． Add 0 parts and mix with 3 current sand at 600 ratio pm, then MDI
-92.2 parts of CRIOO was added and the mixture was subjected to sand treatment for 1 to obtain a ridged foam.

The density of this foam was 0.379 mm/lump and was semi-hard. Example 26 polyBDR-4 group T5 base, reagent 50 parts of first grade castor oil, boric acid 7. $ section, silicon 1.
$ section, straight asphalt (penetration 80-100)
30 Ikari-gun, DABCO-3 Maru V prescribed amount, MDI-CRI
78.1 parts of OO was added, and a light blue foam was obtained in the same manner as in Example 20.

The density of this foam was 0.236 mm/lump, and it was a soft foam. Example 27 Dimer acid polyester polyol synthesized from dimer acid and diethylene glycol (hydroxyl value 50, acid value 1)
．． 5) 10 parts of anchorage, 1 part of silicon, 10.3 parts of boric acid, 100 parts of straight asphalt (penetration 80-100), predetermined amount of DABCO-3 round V and DBTDL, and MDI
-CRIOO was added in an amount of 63.4 parts, and a blue-green foam was obtained in the same manner as in Example 25.

The density of this foam was 0.085 m/m. According to the present invention, the following effects are achieved.

Since foaming can be carried out at a high temperature such as m 90 to 25,000, a large amount of filler such as asphalt or petroleum resin can be blended, and a torturous foam with excellent mechanical properties can be obtained.

[21] Since foaming can be carried out at a high temperature of 90 to 250 qo, it is possible to obtain a blue-green foam that is economical with a small amount of catalyst and has excellent aging resistance.

[3] It is possible to obtain a light blue foam with excellent heat insulation, sound absorption, vibration damping, and sound insulation properties. [4] It is possible to obtain a blue-green foam that is easy to operate and inexpensive.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram for testing the water resistance of the noise-reducing foam according to the present invention, FIG. 3 is an explanatory diagram of the apparatus for testing the vibration resistance of the growth quality foam according to the present invention, and FIG. Figure 2 is a graph showing the relationship between time and sound pressure in the tortoise foam according to the present invention, an iron plate, and a composite structure in which the polyurethane foam of the present invention is attached to an iron plate. FIG. 3 is a relationship curve diagram between frequency and sound absorption coefficient for a soft polyurethane foam. 1... Acrylic resin plate, 2... Foam according to the present invention, 3... Baser, 4...
Bolt, 5...Water, 6...Comparative foam, 7...Foam, 8...Iron plate, 9...
・Microphone, 10...Anterior pupil intensifier, 11・
...Sound pressure meter, 12...Recorder. Figure 1 Figure 2 Figure 3 Figure 4

Claims (1)

[Claims] 1. In producing a bituminous foam by mixing and reacting various raw materials of polyol, polyisocyanate, blowing agent, filler, catalyst and other auxiliary agents, (a) a solid to a solid at room temperature; 150 to 2000 parts by weight of a semi-solid bituminous substance is blended to 100 parts by weight of polyol, (b) an inorganic hydrate with a decomposition temperature of 75° to 300°C is used as a blowing agent, and (
c) A method for producing a bituminous foam, which is carried out at a mixing temperature of various raw materials during foaming of 90° to 250°C. 2. The method for producing a bituminous foam according to claim 1, wherein the bituminous material is straight asphalt or blown asphalt. 3 The blowing agent is boric acid, aluminum hydroxide, magnesium hydroxide, iron hydroxide, calcium sulfate dihydrate, borax, calcium sulfite dihydrate, calcium chloride hexahydrate, sodium sulfate decahydrate, magnesium sulfate decahydrate A method for producing a bituminous foam according to claim 1. 4. The method for producing a bituminous foam according to claim 1, wherein the polyol is a polydiene polyol, a castor oil polyol, or a dimer acid polyol. 5. The method for producing a bituminous foam according to claim 1, which contains 400 parts by weight or less of filler per 100 parts by weight of polyol.