JPH05209036A - Production of polyurethane foam - Google Patents

Abstract

PURPOSE:To provide a lightweight flexible polyurethane sound-proofing material excellent in sound absorption and vibration-damping properties. CONSTITUTION:A process for producing a flexible polyurethane foam having sound-absorbing and vibration-damping properties by reacting a polyhydroxy compound with an organic isocyanate in the presence of a catalyst, a blowing agent and a foam stabilizer, wherein the polyhydroxy compound comprises a mixture of a polyoxyalkylene polyol of a functionality of 2 or above and a hydroxyl value of 15-45mgKOH/g and/or a polymer-dispersion polyol (A) prepared by dispersing fine polymer particles in this polyol with a polyoxyalkylene mono- or polyol of a functionality (f) in the range of 1<=f<2 and a hydroxyl value of 30mgKOH/g or above and/or a polymer-dispersion mono- or polyol (B) prepared by dispersing fine polymer particles in this mono-or polyol in an A to B weight ratio of desirably 95/5 to 70/30.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a soundproofing material or a vibration damping material, and more particularly to a dash which is mounted on a dash portion separating an engine room of a vehicle from a vehicle interior to block noise from the engine room. The present invention relates to a method for manufacturing an insulator.

[0002]

2. Description of the Related Art Conventionally, a soundproof material for sound absorption and sound insulation has been mounted on the dash portion of an automobile, and measures have been taken to prevent vibration and noise from entering the engine room into the vehicle interior. It was As the structure of the soundproof material, a sound absorbing material made of a porous material such as felt or polyurethane foam and a sound insulating material such as rubber or vinyl chloride sheet are integrated. However, these soundproofing materials have a heavy weight, and for improvement, if the weight of rubber, vinyl chloride sheet, etc. is reduced, the sound insulation performance is deteriorated, and if the weight of polyurethane foam, etc. is reduced, the sound absorption / sound insulation performance is deteriorated. have. Polyurethane foams and the like having a density of 70 to 100 kg / m ³ were generally used.

[0003]

SUMMARY OF THE INVENTION The present invention relates to a lightweight polyurethane soundproof material which solves the above-mentioned problems of the prior art and is lightweight and excellent in sound absorption and vibration damping performance. , A dash insulator that uses a specific polyurethane foam that is attached to the dash that separates the engine room of a car from the vehicle compartment and that blocks noise from the engine room and that is excellent in sound absorption and vibration damping performance. Yes, it solves the problems of conventional products.

[0004]

In order to solve the above-mentioned problems, the present inventors have studied the formulation of polyurethane foam for dash insulators, and as a result, the resulting polyurethane foam is lightweight and has sound absorption and damping properties. It was discovered that it has excellent vibration performance.

That is, the gist of the present invention is as follows. (1) When a flexible polyurethane foam is produced by reacting a polyhydroxy compound and an organic isocyanate in the presence of a catalyst, a foaming agent and a foam stabilizer, , (A) Number of functional groups 2 or more, hydroxyl value 15 to 45 mgK
OH / g polyoxyalkylene polyol and / or polymer-dispersed polyol in which polymer particles are dispersed in the polyol, and (B) polyoxyalkylene having a functional group f of 1 ≦ f <2 and a hydroxyl value of 30 mgKOH / g or more. A method for producing a flexible polyurethane foam having soundproofing and vibration absorbing properties, characterized by using a mixture of a mono- or polyol and / or a polymer-dispersed mono- or polyol in which polymer particles are dispersed in the mono- or polyol.

In a particularly preferred embodiment of the present invention,
(2) The weight ratio of A and B is A / B = 95/5.
The method for producing a flexible polyurethane foam according to the above (1), wherein the foam density is 15 to 70/30, and (3) the density of the foam is 15.
To 65 kg / m ³ , the method for producing a flexible polyurethane foam according to (1) or (2) above, and (3) the flexible polyurethane foam for a dash insulator comprising the method according to any one of (1) to (3) above. There is a manufacturing method of.

In the present invention, the polyoxyalkylene polyol (A) is a polyether polyol obtained by adding an alkylene oxide to a compound having a hydrogen atom to which at least two alkylene oxides can be added (hereinafter referred to as an initiator). Is. A small amount of other monoepoxides such as halogen-containing alkylene oxides, styrene oxides, glycidyl ethers, etc. may be added with the alkylene oxide, but preferably substantially only the alkylene oxide is used. As the alkylene oxide, an alkylene oxide having 2 to 4 carbon atoms is suitable, and particularly propylene oxide alone or a combination of propylene oxide and ethylene oxide is preferable. When propylene oxide and ethylene oxide are used in combination, a mixture of both may be added, they may be added separately in sequence, or they may be combined. When ethylene oxide is added last, it is a cap of ethylene oxide. It is also possible to adjust the proportion of primary hydroxyl groups by further adding a small amount of propylene oxide after capping ethylene oxide. As the initiator, polyhydric alcohol, polyhydric phenol, mono- or polyamine, and others can be used, but polyhydric alcohol and polyhydric phenol are suitable, and polyhydric alcohol is particularly preferable. Also, two or more initiators can be used in combination. Specific examples of the initiator are shown below, but the initiator is not limited to these. A particularly preferred initiator is a trihydric polyhydric alcohol, or a mixture thereof with a dihydric or tetrahydric or higher polyhydric initiator. Divalent initiator: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, bisphenol A. Trivalent initiator: glycerin, trimethylolpropane, hexanetriol. Tetravalent or higher-valent initiator: pentaerythritol, diglycerin, ditrimethylolpropane, dextrose, sorbitol, sucrose, novolac.

Polymer-dispersed polyols are
Method of polymerizing ethylenically unsaturated monomer with
A method of mixing the produced polyol fine particles with the polyol,
Macromers with ethylenically unsaturated groups and ethylenically unsaturated groups
Made by polymerizing saturated monomer in polyol
Is built. As the ethylenically unsaturated monomer, the following
Examples include monomers. That is, styrene, α-methyl
Styrene-based products such as styrene or chlorostyrene
Mer, acrylic acid, methacrylic acid, methyl acrylate,
Methyl methacrylate, ethyl acrylate, methacrylic acid
Ethyl, butyl acrylate, butyl methacrylate, acetic acid
2-Ethylhexyl Phosphate, 2-Ethyl Methacrylate
Luhexyl, benzyl acrylate, benzyl methacrylate
Acrylic acid such as acrylamide, acrylamide, methacrylamide
Or acrylic monomers such as its esters and amides
-, Acrylonitrile, 2,4-dicyanobutene-1 etc.
Cyano group-containing monomer, vinyl acetate, vinyl propionate
Vinyl ester monomers such as nyl, butadiene, isop
Lene, chloroprene and other diene monomers, glycy
Glycols such as zirconyl acrylate and glycidylmethacrylate
Lysidyl group-containing monomer and other olefins
Amine, unsaturated esters, halogenated olefins and vinyl
Such as ruther. Free radical heavy
Polymer-dispersed poly (mer) graft-polymerized in the presence of synthetic catalyst
It is also possible to use oars as part or all of (A)
Wear. The amount of polymer fine particles depends on the polyoxyalkylene type
50% by weight or less, especially 45% by weight or less based on liol
Is preferred.

(B) is an initiator having a hydrogen atom capable of adding one alkylene oxide, or 1
A polyether mono- or polyol obtained by adding an alkylene oxide to a mixture of an initiator having a hydrogen atom capable of adding one alkylene oxide and an initiator having a hydrogen atom capable of adding two alkylene oxides. The alkylene oxide and the polymer-dispersed mono- or polyol are the same as the polyoxyalkylene polyol of (A). Specific examples of the initiator are shown below, but the initiator is not limited to these. Monovalent initiator: methanol, ethanol, isopropanol, tert-butyl alcohol, butanol, hexanol, formaldehyde Divalent initiator: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, bisphenol A.

In the production of the specific polyurethane foam of the present invention, the other main raw material is a polyisocyanate compound. As the polyisocyanate compound, various compounds having two or more isocyanate groups can be used, but aromatic polyisocyanates are particularly suitable. As the aromatic polyisocyanate, a mononuclear or polynuclear compound having an isocyanate group bonded to an aromatic nucleus or a modified product thereof is suitable. Specific examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, and prepolymer type, carbodiimide type, urea type and other modified products thereof. Two or more of these polyisocyanate compounds can be used in combination. The amount of the polyisocyanate compound used is expressed as 100 times the number of isocyanate groups with respect to the number of active hydrogens of all the active hydrogen-containing compounds (usually called isocyanate index) and is about 50 to 12
0, especially about 60 to 110, is suitable. The active hydrogen-containing compound is mainly a mono- or polyol such as the above polyoxyalkylene-based mono- or polyol, but it also contains a small amount of water as a foaming agent, and in some cases, a chain extender or a cross-linking agent is used. In some cases, they are also included.

Another one of the essential components of the foamable mixture is a catalyst. As a catalyst for producing a polyurethane foam, a tertiary amine-based catalyst and an organic metal compound, particularly an organic tin-based compound are usually used. Various tertiary amine-based catalysts can be used as the tertiary amine-based catalyst.
Triethylenediamine, N-ethylmorpholine, N, N
-Dimethylaminoethylmorpholine, triethylamine, N, N, N ', N'-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, N, N', N'-trimethylaminoethylethanolamine, etc. is there. These can be used in combination of two or more. The organometallic compound catalyst is most preferably an organotin compound catalyst, and examples thereof include stannas octoate, stannas laurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate and dioctyltin diacetate. In particular, stanna octoate, dibutyltin dilaurate and the like are preferable.

Another component added to the foamable mixture is a foaming agent. As the foaming agent, only water is particularly preferable, but a halogenated hydrocarbon-based foaming agent, a low boiling point gas such as air, or another foaming agent may be used together in a small amount. Examples of the halogenated hydrocarbon-based foaming agent include trichlorofluoromethane,
Examples include dichlorodifluoromethane, methylene chloride, monochlorodifluoromethane, 1,1-dichloro-2,2,2-trifluoroethane, and 1,1-dichloro-1-fluoroethane. The amount of the foaming agent used may vary depending on the density of the desired foam, but in the case of water, the polyol 1 is usually used.
It is about 1 to 10 parts by weight, especially about 2 to 8 parts by weight, relative to 00 parts by weight. Still another normally required component is a siloxane-based foam stabilizer, such as polydialkylsiloxane and polydialkylsiloxane-polyoxyalkylene block copolymer. Other optional components include, for example, colorants, antioxidants, UV absorbers, light stabilizers, flame retardants, and other additives that can be used in the production of urethane foam.

The component (A) of the polyoxyalkylene polyol used in the present invention has a hydroxyl value of 15 to 45 m.
gKOH / g polyether polyol and / or polymer-dispersed polyol in which polymer particles are dispersed in the polyol, but when the hydroxyl value is less than 15 mgKOH / g, the viscosity of the polyol is too high, the flowability of the foam is poor, and the density is low. I won't. Also, the hydroxyl value is 45 mg KO
If it exceeds H / g, there is a drawback that hardness, which is important for sound absorption and vibration damping performance, increases.

The component (B) has a hydroxyl value of 30 mgKOH.
/ G or more of a polyoxyalkylene-based mono- or polyol and / or a polymer-dispersed mono- or polyol in which polymer particles are dispersed in the mono- or polyol, but when the hydroxyl value is less than 30 mgKOH / g, the compression set and mechanical properties of the foam The physical properties are lowered, the viscosity of the system is not lowered, the flowability of the foam is poor, and the density is not lowered.

The use ratio of (A) and (B) is preferably 95/5 to 70/30 as a weight ratio. If the ratio is outside this range, the foam density will not decrease, or the compression set of the foam, mechanical properties, and sound absorption. It is also not preferable because it causes deterioration of vibration damping performance.

[0016]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. Hereinafter, parts are parts by weight. Table 1 and Table 2
(Table 1 is an example, Table 2 is a comparative example), 1000
A flexible polyurethane foam was produced with a mold of cm □ × 2 cmt. The physical properties (total density, surface hardness, compression set, elongation and tensile strength) and sound insulation performance of the obtained foam were measured. The measurement results of physical properties are shown in Tables 3 and 4, and the sound insulation performance is shown in FIG.

The symbols shown in Tables 1 and 2 mean the following. Polyether polyol (A-1) Polyether polyol having 3 functional groups and hydroxyl value of 36 mgKOH / g and added with terminal EO Polyether polyol (A-2) 3.5 functional groups and terminal E of 30 mg KOH / g hydroxyl value
O-added polyether polyol Polyether polyol (A-3) Functional group number 3, hydroxyl group value 28 mgKOH / g terminal EO addition polymer dispersed polyol Polyether polyol (B-1) Functional group number 1.3, hydroxyl value 60 mgKOH / g End E of
O-added polyether polyol Polyether monool (B-2) PO having a functional group number of 1.0 and a hydroxyl value of 120 mgKOH / g
/ EO random addition polyether monool polyether polyol (C-1) Functional group number 3, hydroxyl value 56 mgKOH / g terminal EO addition polyether polyol Polyether polyol (C-2) Functional group number 3, hydroxyl value 14 mgKOH / g Polyether polyol with terminal EO addition Polyether polyol (C-3) Terminal E with 3.5 functional groups and hydroxyl value 50 mgKOH / g
O-added polyether polyol Polyether polyol (D-1) Terminal E with 1.3 functional groups and hydroxyl value of 25 mgKOH / g
O-added polyether polyol Polyether polyol (D-2) PO / having a functional group number of 1.3 and a hydroxyl value of 20 mgKOH / g
EO random addition polyether polyol

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

[0022]

According to the present invention, the problems of the prior art can be solved, and a soft polyurethane soundproof material which is lightweight and has excellent sound absorbing and damping performance can be obtained, and particularly, it separates the engine room and the vehicle interior of an automobile from each other. (EN) Provided is a dash insulator that uses a specific polyurethane foam that is attached to a dash part and shields noise from an engine room and that is excellent in sound absorption and vibration damping performance.

[Brief description of drawings]

FIG. 1 is a graph showing the sound insulation performance of polyurethane foams of Examples and Comparative Examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI technical display location C08L 75:04 (72) Inventor Hiroshi Wada 7-21-626 Kitaderao, Tsurumi-ku, Yokohama-shi, Kanagawa ( 72) Inventor Shoji Hayashida 484-23 Imai-cho, Hodogaya-ku, Yokohama-shi, Kanagawa (72) Inventor Osamu Totaka 568 Futako, Takatsu-ku, Kawasaki-shi, Kanagawa

Claims (4)

[Claims] 1. When producing a flexible polyurethane foam by reacting a polyhydroxy compound and an organic isocyanate in the presence of a catalyst, a foaming agent and a foam stabilizer, the polyhydroxy compound (A) has 2 or more functional groups, A polyoxyalkylene polyol having a hydroxyl value of 15 to 45 mgKOH / g and / or a polymer-dispersed polyol in which polymer particles are dispersed in the polyol, and (B) the number of functional groups f is 1 ≦ f <2, and the hydroxyl value is 30 mgKOH / g.
A method for producing a flexible polyurethane foam having soundproofing and vibration absorbing properties, characterized by using a polyoxyalkylene-based mono- or polyol of g or more and / or a mixture of polymer-dispersed mono- or polyol in which polymer particles are dispersed in the mono- or polyol. .. 2. The weight ratio of A and B is A / B =
The method for producing a flexible polyurethane foam according to claim 1, which is 95/5 to 70/30. 3. The foam has a density of 15 to 65 kg / m ^3.
The method for producing a flexible polyurethane foam according to claim 1 or 2, wherein 4. A method for producing a flexible polyurethane foam for a dash insulator, which comprises the method according to claim 1.