KR101985111B1 - Polyurethane composition, acoustic absorbent comprising the same and manufacturing method polyurethane foam - Google Patents

Abstract

The present invention relates to a polyurethane composition, a sound absorbing material comprising the same, and a method for manufacturing a polyurethane foam. More specifically, provided are: the polyurethane composition capable of manufacturing the polyurethane foam having a uniform sound absorption rate and mechanical strength against air-borne noise compared to existing polyurethane foam sound absorbing materials by mixing application of an amine-based catalyst and a tin-based catalyst as a gelling catalyst; and the method for manufacturing the polyurethane foam.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyurethane composition, a sound absorbing material containing the same, and a method for producing the polyurethane foam. [0002]

The present invention relates to a polyurethane composition, a sound absorbing material containing the polyurethane composition and a method for producing the polyurethane foam, and more particularly, to a method for producing a polyurethane foam by mixing an amine catalyst and a tin catalyst with a gelling catalyst, To a polyurethane composition capable of producing a polyurethane foam having a high sound absorption coefficient and a uniform mechanical strength with respect to a polyurethane foam, a sound absorbing material containing the polyurethane composition, and a process for producing the polyurethane foam.

The vehicle is also important in fuel economy and driving performance, but other factors such as environment friendliness and quietness are also important items. Typical noise introduced into the interior of the vehicle includes noise transmitted through the vehicle body or air generated by the engine. In order to suppress such engine noise, an engine cover or a hood insulator is used in a conventional vehicle. However, Through these only, there is a limitation and insufficient to remove the noise to the desired level. In order to have a good quietness, various types of sound absorbing materials are used in the interior of the vehicle, but polyurethane foam sound absorbing materials are used most frequently.

As for the polyurethane foam, the sound absorption mechanism is explained by the incidence at the foam surface. The attenuation due to reflection, the viscous resistance of the air inside the cell, the sound attenuation due to vibration, and the thermal energy conversion of the vibration energy delivered to the foam. Based on this sound absorption mechanism, the sound absorption performance depends on the surface condition of the foam, the density and the thickness, the size and the shape of the cell in terms of morphology, the microstructure of the polyurethane foam and the physical properties associated with it get affected. The cell structure, which is one of the morphological factors, is composed of the components constituting the polyurethane raw material, the type and content of the foaming agent, the chain extender, the surfactant and the relative speed of the polyurethane synthesis reaction and the foaming reaction depending on the catalyst and the reaction temperature On the other hand, directly affect the microstructure formation process of the polyurethane foam.

The sound absorbing material for a vehicle such as the polyurethane foam has a pore inside thereof so that sound can enter, and the sound thus entered is absorbed while bumping in the material. In other words, when a noise strikes a material, some of it is reflected and some of it is absorbed, and the sound absorbed here vibrates the structure of the material, and the vibration energy generated thereby is converted into heat energy, and the heat energy is dissipated. .

In the case of conventional polyurethane foam sound absorbing materials, the cell structure of the polyurethane foam is not uniformly formed, so that the physical properties and sound absorption properties are not satisfactory.

Accordingly, there is an increasing demand for a polyurethane foam sound absorbing material which can maximize the advantages of the conventional polyurethane foam and has excellent sound absorption effect and physical properties.

Disclosure of Invention Technical Problem [9] Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a polyurethane composition comprising a polyol compound and an isocyanate compound as a gelling catalyst by mixing an amine catalyst and a tin catalyst, And to provide a polyurethane composition capable of producing a uniform polyurethane foam, a sound absorbing material containing the polyurethane composition, and a process for producing the polyurethane foam.

The polyurethane composition according to one aspect of the present invention is a polyether compound having an average functional group number of 2.8 to 3.2 and having a weight average molecular weight of 5000 to 7000, 100 parts by weight of an isocyanate compound having an NCO content of 28 to 42, 0.05 to 0.15 parts by weight of a blowing catalyst, 0.5 to 1.5 parts by weight of a gelling catalyst, 3 to 5 parts by weight of a blowing agent, 0.3 to 0.9 parts by weight of a chain extender and 1 to 1.7 parts by weight of a surfactant And the gelling catalyst may comprise 20 to 80% by weight of an amine-based catalyst and 20 to 80% by weight of a tin-based catalyst.

The amine catalyst may be at least one selected from the group consisting of triethylamine, tributylamine, triethylenediamine, triethanolamine, dimethylcyclohexylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N- (dimethylaminoethoxy) ethanol, and diazabicyclo [2.2.2] octane.

The tin catalyst is selected from the group consisting of tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate, tin (II) laurate, dibutyltin oxide, dibutyltin diacylide, dibutyltin diacetate, At least one selected from the group consisting of dibutyl tin dilaurate, dibutyl tin maleate and dioctyltin diacetate.

Wherein the blowing catalyst is at least one selected from the group consisting of pentamethylenediethylenetriamine, dimethylcyclohexylamine, tris (3-dimethylamino) propylhexahydrotriamine, bis (2-dimethylaminoethyl) It can be one.

The polyurethane foam sound absorbing material according to another aspect of the present invention may comprise the polyurethane composition.

Another aspect of the present invention is a method for producing a polyurethane foam, which comprises a polyether compound having an average number of functional groups of 2.8 to 3.2 and having a weight average molecular weight of 5,000 to 7,000, 0.1 to 5 parts by weight of a gelling catalyst, 0.5 to 1.5 parts by weight of a gelling catalyst, 3 to 5 parts by weight of a foaming agent, 0.3 to 0.9 parts by weight of a chain extender and 1 to 1.7 parts by weight of a surfactant, 55 to 65 parts by weight of an isocyanate compound having an NCO content of 28 to 42% with respect to 100 parts by weight of the compound are added to the polyol raw material and mixed with a foaming stirrer to prepare a foaming stock solution, and the foaming stock solution is injected into a mold and aged Wherein the gelling catalyst comprises 20 to 80 wt% of an amine catalyst and 20 to 80 wt% of a tin catalyst.

The polyurethane composition according to the present invention can be applied to a polyurethane composition containing a polyol compound and an isocyanate compound by mixing an amine catalyst and a tin catalyst with a gelling catalyst to improve the uniformity of pore distribution and size in the polyurethane foam, And a polyurethane foam and a sound absorbing material having uniform mechanical strength can be produced.

1 is a graph showing a sound absorption rate with respect to a frequency of an embodiment of the present invention and a comparative example.
Fig. 2 is a view showing positions for collecting samples of polyurethane foam sound absorbing materials.
FIG. 3 is a graph showing sound absorption ratios with respect to frequencies for the respective parts of the embodiment of the present invention and comparative example, wherein (a) is a sound absorption ratio for the first comparative example, and (b) is a second sound absorption ratio graph for the second embodiment.
Fig. 4 is a graph showing the stress deformation curve for each part of the embodiment of the present invention and comparative example, wherein (a) is a stress strain graph for each part, (b) It is a variation graph.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, the terms first, second, A, B, (a), (b), and the like can be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements.

According to one embodiment of the present invention, 100 parts by weight of a polyether compound having an average functional group number of 2.8 to 3.2 and a weight average molecular weight of 5000 to 7000, 55 to 65 parts by weight of an isocyanate compound having an NCO content of 28 to 42% 0.05 to 0.15 parts by weight of a catalyst (Blowing Catalyst), 0.5 to 1.5 parts by weight of a gelling catalyst, 3 to 5 parts by weight of a foaming agent, 0.3 to 0.9 parts by weight of a chain extender and 1 to 1.7 parts by weight of a surfactant, The gelling catalyst provides a polyurethane composition comprising 20 to 80 wt% of an amine-based catalyst and 20 to 80 wt% of a tin catalyst.

The polyol compound may be triol and the polyol having a mass average molecular weight of 5000 to 7000 may include all polyether-based products having an average number of functional groups of 2.8 to 3.2. The polyether-based polyol is obtained by adding a polyol such as ethylene oxide, propylene glycol, propylene glycol monomethyl ether, etc. to a polyhydric alcohol such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylol propane, sorbitol, A polyether polyol to which an alkylene oxide such as an oxide is added, and the like can be used, but the present invention is not limited thereto. For example, the polyether polyols may be GP-3000, GP-4000, GP-5000, KE-810, KPX products / PY3553, PY3328, SKC products and the like.

If the mass average molecular weight of the polyol is less than 5,000, the polyurethane foam may not be formed due to the short chain length of the polyol. If the weight average molecular weight exceeds 7000, the polyurethane foam may have a low strength due to the long chain length Can be. If the average number of functional groups of the polyol is less than 2.8, there may be a problem that the polyurethane foam is unevenly formed because the number of branches of the polyol is small. If the average number of functional groups is more than 3.2, sound permeability is poor due to insufficient permeability to the formed polyurethane foam Can be.

The isocyanate compound may be a monoisocyanate, a diisocyanate or the like, and diisocyanate is preferably used, but not limited thereto. The diisocyanate may be at least one selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, torilene diisocyanate, and derivatives thereof.

The isocyanate compound preferably has an NCO content of 28 to 42%, and applicable isocyanates include various common MDI (Methylene diphenyl iisocyanate) products such as Cosmonate CG3701S (manufactured by Kumho Mitsui Chemical) and KW 5029 / 1C-B (manufactured by BASF) can do. If the NCO content of the isocyanate compound is less than 28, there may be a problem that the strength of the polyurethane foam is lowered due to a small network structure. If the NCO content is more than 42, the pores of the polyurethane foam may be clogged to prevent sound from penetrating into the foam. There may be a falling problem.

On the other hand, NCO% means (mass of the NCO group in the molecule / total molecular weight).

The isocyanate compound may be used in an amount of 55 to 65 parts by weight based on 100 parts by weight of the polyol compound. If the amount of the isocyanate compound is less than 55 parts by weight based on 100 parts by weight of the polyol compound, there may be a problem that the internal structure of the polyurethane foam is uneven and the strength is lowered due to the unreacted polyol. When the amount of the isocyanate compound exceeds 65 parts by weight, There is a problem that the sound absorption performance is deteriorated because sound can not be transmitted through the speaker.

The polyurethane composition may include a catalyst for promoting the reaction of the components, a blowing catalyst for promoting the foaming reaction with the catalyst, and a gelling catalyst for promoting the polyurethane chain forming reaction .

The blowing catalyst is a catalyst for promoting the saturation reaction between the isocyanate and the foaming agent during the foaming reaction. The blowing catalyst may be at least one selected from the group consisting of pentamethylenediethylenetriamine, dimethylcyclohexylamine, tris (3-dimethylamino) propylhexahydrotriamine, bis (2-dimethyl Bis (2-dimethylaminoethyl) ether}, and derivatives thereof. However, the present invention is not limited thereto.

The blowing catalyst may be used in an amount of 0.05 to 0.15 part by weight based on 100 parts by weight of the polyol compound. If the amount of the blowing catalyst is less than 0.05 parts by weight based on 100 parts by weight of the polyol compound, the reaction may be delayed, resulting in poor curing and lower productivity. If the blowing catalyst is used in excess of 0.15 parts by weight, May cause problems.

The gelling catalyst is a catalyst for promoting an isocyanate reaction with a polyol in the polyurethane chain forming reaction, and is preferably used by mixing an amine catalyst and a tin catalyst.

The constant gelling catalyst may be used in an amount of 0.5 to 1.5 parts by weight based on 100 parts by weight of the polyol compound. If the amount of the gelling catalyst is less than 0.5 parts by weight based on 100 parts by weight of the polyol compound, the reaction may be delayed, resulting in poor curing and lower productivity. If the amount is more than 1.5 parts by weight, Problems can arise.

The amine catalyst may be at least one selected from the group consisting of triethylamine, tributylamine, triethylenediamine, triethanolamine, dimethylcyclohexylamine, dimethylbenzylamine, N-methyl N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, N, N- (dimethylaminoethoxy) ethanol (N, (Dimethylaminoethoxy) ethanol and diazabicyclo [2.2.2] octane, but the present invention is not limited thereto.

The tin catalysts include tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate, tin (II) acetate, (II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dilaurate, , Dibutyltin maleate, and dioctyltin diacetate. However, the present invention is not limited thereto.

The gelling catalyst may be used including 20 to 80 wt% of an amine catalyst and 20 to 80 wt% of a tin catalyst. If the tin-based catalyst is less than 20 wt%, the productivity may be lowered due to a slow reaction rate. If the tin-based catalyst is more than 80 wt%, there may be a problem of non-uniform cell formation due to rapid gelling.

The blowing agent may be water or cyclopentane, and may be used in an amount of 3 to 5 parts by weight based on 100 parts by weight of the polyol compound. When the amount of the foaming agent is less than 3 parts by weight, the polyurethane foam may not be sufficiently foamed. When the amount of the blowing agent is more than 5 parts by weight, cracks may be generated in the polyurethane foam due to rapid expansion.

The chain extender is a substance used in a chain-extension reaction in which a hydrophilic polymer is modified, and the kind thereof is not limited, but may be selected from the group consisting of ethanolamine, diethanolamine, triethanolamine, 1,4-butanediol, and ethylenediamine And may preferably be diethanolamine. The chain extender may be used in an amount of 0.3 to 0.9 parts by weight based on 100 parts by weight of the polyol compound. If the chain extender is used in an amount of less than 0.3 parts by weight, the melting point of the polyurethane may be lowered due to the lack of a hard segment, If it exceeds 0.9 part by weight, the sensitivity of the polyurethane (TPU) may deteriorate due to an excessive hard segment.

The surfactant serves to prevent the cells generated when the cells are formed in the foam and to prevent them from being broken and to form a uniform cell. The type of the surfactant is not particularly limited as long as it is used in the related art, It is possible to use an excellent silicone surfactant in terms of acidity. The surfactant is used in an amount of 1 to 1.7 parts by weight based on 100 parts by weight of the polyol compound. When the amount is less than 1 part by weight, the foam is unevenly formed. When the amount is more than 1.7 parts by weight, Wasteful problems can arise.

According to another embodiment of the present invention, there can be provided a polyurethane foam sound absorbing material comprising the polyurethane composition. According to the polyurethane foam sound absorbing material, the sound absorption rate at a frequency of 800 to 3200 Hz is 0.7 or more, and the sound absorption rate at a frequency of 1500 to 3000 Hz is 0.8 or more.

According to another embodiment of the present invention, 0.05 to 0.15 part by weight of a blowing catalyst is added to 100 parts by weight of a polyether compound having an average functional group number of 2.8 to 3.2 and a weight average molecular weight of 5000 to 7000, 0.5 to 1.5 parts by weight of a catalyst (Gelling Catalyst), 3 to 5 parts by weight of a foaming agent, 0.3 to 0.9 parts by weight of a chain extender and 1 to 1.7 parts by weight of a surfactant, 55 to 65 parts by weight of an isocyanate compound having an NCO content of 28 to 42% is added to the polyol raw material and mixed with a foaming stirrer to prepare a stock solution for foaming, and a step of pouring the foaming stock solution into a mold and aging the polyurethane foam Can be provided.

In the step of preparing the foaming stock solution, the gelling catalyst may be mixed with 20 to 80% by weight of the amine catalyst and 20 to 80% by weight of the tin catalyst and added to the polyol raw material.

And stirring the mixture at a stirring speed of 5000 to 7000 rpm so that the polyol raw material and the isocyanate compound can be uniformly mixed in the step of preparing the foaming stock solution. If the agitation speed is less than 5000 rpm, the possibility of unreacted products in the polyol raw material and isocyanate compounds is increased, and the physical properties and adhesive force of the final polyurethane foam can be lowered. When the stirring speed exceeds 7000 rpm , Bubbles may be generated in the mixture of the polyol raw material and the isocyanate compound, and the physical properties of the polyurethane foam may be deteriorated.

It is preferable to proceed at a temperature of 50 to 70 DEG C so that polymerization of the polyol raw material and the isocyanate compound proceeds smoothly in the aging step. If the temperature is lower than 50 ° C, the reaction rate becomes too slow and the reaction yield is lowered. If the temperature is higher than 70 ° C, the polyol raw material and the isocyanate compounds may be decomposed or deformed.

Meanwhile, the materials used in the method for producing the polyurethane foam may be used in the same meaning as the materials applied to the polyurethane composition.

[ Manufacturing example ]

The polyurethane compositions according to the following Examples and Comparative Examples were prepared using the compositions shown in Table 1 below and mixed at a stirring speed of 6000 rpm in a foaming stirrer to prepare a foaming stock solution. The foaming stock solution was injected into a mold to prepare 60 Lt; RTI ID = 0.0 > C, < / RTI > to produce a polyurethane foam.

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Polyol ⁽¹⁾ 100 100 100 100 100 Gelling Catalyst 1 ⁽²⁾ 0.72 0 0.50 0.36 0.22 Gelling Catalyst 2 ⁽³⁾ 0 0.72 0.22 0.36 0.50 Blowing catalysts ⁽⁴⁾ 0.08 0.08 0.08 0.08 0.08 Chain extenders ⁽⁵⁾ 0.60 0.60 0.60 0.60 0.60 Blowing agent (water) 4 4 4 4 4 Surfactants ⁽⁶⁾ 1.32 1.32 1.32 1.32 1.32 Isocyanates ⁽⁷⁾ 61.38 55.24 49.10 42.96 36.83 Unit: parts by weight
(1) Polyol: KE-810, polyether polyol, mass average molecular weight 6000, average number of functional groups 3
(2) Gelling catalyst 1: Dabco 33LV, a mixture of triethylenediamine and dipropylene glycol
(3) Gelling catalyst 2: DBTDL, Dibutyltin dilaurate
(4) Blowing catalyst: BL11, a mixture of bis (2-dimethylaminoethyl) ether and dipropylene glycol
(5) Chain extenders: Diethanolamine
(6) Surfactant: L-3002, a silicone surfactant
(7) Isocyanate: KW 5029 / 1C-B, 78wt% 4,4'-methylene bis (phenyl isocyanate), 5wt% benzene 1,1-methylene bis (4-isocyanato) homopolymer, 17wt% toluene diisocyanate

Experimental Example

Sound absorbing ratio evaluation, sound absorption uniformity evaluation, and compressive strength evaluation were performed using the polyurethane foam sound absorbing materials prepared through the above examples and comparative examples.

[ Experimental Example  One] Sound absorption rate  evaluation

The sound absorption rate of each polyurethane foam sound absorbing material prepared through the above examples and comparative examples was measured and shown in FIG. The closer the value of the sound absorption rate to 1, the better the sound absorption property of the material.

1, in Examples 1 to 3 of the present invention in which an amine catalyst and a tin catalyst were mixed with a gelling catalyst, the absorbance of the gelling catalyst was lower than that of Comparative Examples 1 and 2 using an amine catalyst or a tin catalyst alone It can be seen that it is improved.

[ Experimental Example  2] Sound absorption uniformity evaluation

As shown in FIG. 2 (a), the horizontal samples of the respective parts were collected from the polyurethane foam sound absorbing materials of Example 2 and Comparative Example 1 which showed high results in the above evaluation of the sound absorption rate, Respectively.

2, in Comparative Example 1 in which the sound absorption rate of the second embodiment of the present invention in which the amine-based catalyst and the tin-based catalyst were mixed with the gelling catalyst in each portion of the polyurethane foam sound- It can be seen that the sound absorption rate is improved more uniformly.

[ Experimental Example  3] Evaluation of compressive strength

As shown in FIG. 2 (a), in the polyurethane foam sound absorbing material of Example 2 of the present invention and the comparative example 1 showing high results in the above-described sound absorption rate evaluation, vertical samples of the horizontal and intermediate layers of each portion were collected, The curve is shown in Fig.

4 (a), the horizontal compression strength in Example 2 of the present invention in which an amine-based catalyst and a tin-based catalyst were mixed with a gelling catalyst in each portion of a polyurethane foam sound- 4 (b), it can be understood that the horizontal and vertical compressive strengths of the second embodiment of the present invention in the middle layer portion of the polyurethane foam sound absorbing material It can be seen that the strength was improved more uniformly than the horizontal and vertical compressive strengths of Comparative Example 1. [

It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that various changes and modifications may be made without departing from the spirit and scope of the present invention as defined by the appended claims. It will be possible. Therefore, the disclosed embodiments and experiments should be considered from an illustrative point of view, not from a limiting viewpoint. The scope of the present invention is defined by the appended claims rather than by the foregoing description, and all differences within the scope of equivalents thereof should be construed as being included in the present invention.

Claims (6)

100 parts by weight of a polyether compound having an average number of functional groups of 2.8 to 3.2 and a mass average molecular weight of 5000 to 7000;
55 to 65 parts by weight of an isocyanate compound having an NCO content of 28 to 42% by mass;
0.05 to 0.15 parts by weight of a blowing catalyst;
0.5 to 1.5 parts by weight of a gelling catalyst;
3 to 5 parts by weight of a foaming agent;
0.3 to 0.9 parts by weight of a chain extender; And
1 to 1.7 parts by weight of a surfactant,
Wherein the gelling catalyst comprises 20 to 80 wt% of an amine catalyst and 20 to 80 wt% of a tin catalyst,
And a sound absorption ratio at a frequency of 1500 to 3000 Hz of 0.8 or more. The method according to claim 1,
The amine catalyst may be at least one selected from the group consisting of triethylamine, tributylamine, triethylenediamine, triethanolamine, dimethylcyclohexylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N, N- (dimethylaminoethoxy) ethanol, and diazabicyclo [2.2.2] octane. The method according to claim 1,
The tin catalyst is selected from the group consisting of tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate, tin (II) laurate, dibutyltin oxide, dibutyltin diacylide, dibutyltin diacetate, Is at least one selected from the group consisting of dibutyl tin dilaurate, dibutyl tin maleate and dioctyl tin diacetate. The method according to claim 1,
Wherein the blowing catalyst is at least one selected from the group consisting of pentamethylenediethylenetriamine, dimethylcyclohexylamine, tris (3-dimethylamino) propylhexahydrotriamine, bis (2-dimethylaminoethyl) Lt; / RTI > A polyurethane foam sound absorbing material comprising the polyurethane composition of any one of claims 1 to 4. 0.05 to 0.15 parts by weight of a blowing catalyst and 0.5 to 1.5 parts by weight of a gelling catalyst are added to 100 parts by weight of a polyether compound having an average functional group number of 2.8 to 3.2 and a weight average molecular weight of 5000 to 7000, 3 to 5 parts by weight of a blowing agent, 0.3 to 0.9 parts by weight of a chain extender, and 1 to 1.7 parts by weight of a surfactant;
55 to 65 parts by weight of an isocyanate compound having an NCO content of 28 to 42% by weight based on 100 parts by weight of the polyol compound are added to the polyol raw material and mixed with a foaming stirrer so that the stirring speed becomes 5000 to 7000 rpm, ; And
Injecting the foamed stock solution into a mold and aging at a temperature of 50 to 70 DEG C,
Wherein the gelling catalyst comprises 20 to 80 wt% of an amine catalyst and 20 to 80 wt% of a tin catalyst,
Wherein a polyurethane foam having a sound absorption rate at a frequency of 1500 to 3000 Hz of 0.8 or more is produced.

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