KR20080062455A - A semi-rigid sprayable polyurethane foam composition - Google Patents

Abstract

A composition for a semi-rigid spraying polyurethane foam, and a semi-rigid polyurethane foam obtained by foaming the composition are provided to improve foaming property, foaming stability and storage stability. A composition for a semi-rigid spraying polyurethane foam comprises 45-55 wt% of a resin premix which comprises 35-70 parts by weight of a polyether polyol having a functionality of 2-3 and a molecular weight of 1,000-5,000, 10-40 parts by weight of a polyether polyol having a functionality of 2-3 and a molecular weight of 5,000-7,000, 2-10.5 parts by weight of a crosslinking agent, 3-9 parts by weight of a reactive amine-based urethane catalyst, 0.5-2 parts by weight of a metal-based urethane catalyst, 0.1-3 parts by weight of a silicone surfactant, and 0.3-5 parts by weight of water; and 45-55 wt% of a polyisocyanate containing 14-18 wt% of an isocyanate group.

Description

Semi-foamed polyurethane foam composition {A SEMI-RIGID SPRAYABLE POLYURETHANE FOAM COMPOSITION}

The present invention relates to a semi-pushing polyurethane foam composition, and more particularly, excellent foamability, foam stability and storage stability, semi-rigid properties of the bathtub, interlayer noise, vibration removal The present invention relates to a composition for semi-rigid polyurethane foam having a good productivity and economy because it is suitable for applying a vibration damping agent and a floor buffer for the present invention.

Polyurethane foam is used in various fields such as insulation of buildings, intermediate interior materials of home appliances such as refrigerators, automobile seats, etc., and conventional polyurethane foam is mainly used for rigid urethane.

In addition, the method using the synthetic resin foam can be largely divided into two. First, the use of polystyrene foam (aka: Styrofoam) or polyurethane board processed and commercialized to a certain size has a disadvantage in that workability is poor and workability is relatively poor due to surface conditions. However, there is an advantage in the work environment because it uses a commercialized product. Second, polyurethane foaming is carried out on the spot using spray foaming machines. It is mainly used for low temperature warehouses and freezers for agricultural products. Spray foaming has a high workability, and since it uses liquid resin premix and isocyanate, it has the advantage of being able to work in a certain form regardless of surface condition bending. With the demand for semi-hard polyurethanes, there is a constant demand for semi-foamed polyurethane foams that can be sprayed with the use of FRP-based bathtubs, interlayer noise absorbers, vibration dampers, floor buffers, etc. .

In order to solve the problems of the prior art as described above, the present invention is excellent in foaming, foaming stability and storage stability, and has a semi-rigid nature of the tub, interlayer noise, vibration damper for vibration, floor It is an object of the present invention to provide a semi-foamed polyurethane foam composition and a semi-foamed polyurethane foam composition which are suitable for application of a buffer and can be sprayed. .

In order to achieve the above object, the present invention is a composition for blowing polyurethane foam,

a) iii) 35 to 70 parts by weight of a polyether polyol having 2-3 functional groups and a molecular weight of 1,000 to less than 5,000;

  Ii) 10 to 40 parts by weight of a polyether polyol having 2 to 3 functional groups and a molecular weight of 5,000 to 7,000;

 Iii) 2 to 10.5 parts by weight of crosslinking agent;

 Iii) 3 to 9 parts by weight of a reactive amine urethane catalyst;

 Iii) 0.5 to 2 parts by weight of a metallic urethane catalyst;

 Iii) 0.1 to 3 parts by weight of silicone surfactant; And

 Iii) 0.3 to 5 parts by weight of water

 45 to 55% by weight of resin premix comprising; And

b) 55 to 45 weight percent polyisocyanate comprising 14 to 18 weight percent isocyanate groups

It provides a composition for semi-rigid polyurethane foam characterized in that it comprises a.

In another aspect, the present invention provides a foamed foamed composition for the radial foaming polyurethane foam.

Hereinafter, the present invention will be described in detail.

The composition for semi-rigid polyurethane foam of the present invention comprises a) iii) 35 to 70 parts by weight of a polyether polyol having 2-3 functional groups and a molecular weight of less than 1,000 to 5,000; Ii) 10 to 40 parts by weight of a polyether polyol having 2 to 3 functional groups and a molecular weight of 5,000 to 7,000; Iii) 2 to 10.5 parts by weight of crosslinking agent; Iii) 3 to 9 parts by weight of a reactive amine urethane catalyst; Iii) 0.5 to 2 parts by weight of a metallic urethane catalyst; Iii) 0.1 to 3 parts by weight of silicone surfactant; And iii) 45 to 55% by weight of resin premix, comprising 0.3 to 5 parts by weight of water; And b) 55 to 45 weight percent polyisocyanate comprising 14 to 18 weight percent isocyanate groups.

In addition, the composition for semi-rigid polyurethane foam of the present invention may further comprise 5 to 25 parts by weight of a flame retardant which is tris (chloroisopropyl) phosphate or tris (2-chloroethyl) phosphate based on 100 parts by weight of the total resin premix. Can be. Including a flame retardant has the advantage of improving the flame retardancy, foaming stability and storage stability of the semi-reflective polyurethane foam.

The polyether polyols of a) iii) and a) ii) used in the present invention are commercially available in the art and can be used as a polyol, and propylene oxide or ethylene oxide can be added by using diol or glycerin as starting materials. It can also manufacture.

The composition for semi-rigid polyurethane foam of the present invention comprises a) iii) 35 to 70 parts by weight of a polyether polyol having 2-3 functional groups and a molecular weight of less than 1,000 to 5,000; Ii) It preferably contains 20 to 40 parts by weight of a polyether polyol having 2 to 3 functional groups and a molecular weight of 5,000 to 7,000. If it is in the above range there is an advantage to improve the foamability, foam stability and storage stability of the polyurethane foam composition.

In addition, the cross-linking agent of iii) used in the present invention may be a glycol-based or amine-based, specifically, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6- Hexanediol, pentaerythritol, diethanolamine, triethanolamine, ethylenediamine, triethylenetetraamine, methyleneorthochloraniline, 4,4-diphenylmethanediamine, 2,6-dichloro-4,4-diphenylmethanediamine , 2,4-toluenediamine, or 2,6-toluenediamine can be used.

The crosslinking agent is preferably contained in an amount of 2 to 10.5 parts by weight based on the resin premix, and more preferably 4.9 to 9 parts by weight. If it is in the above range there is an advantage that can improve the foaming rate, foaming stability and storage stability of the polyurethane foam composition.

In addition, the reactive amine-based urethane catalyst of i) used in the present invention serves to prevent the amine component from being detected in the final foam by participating in the direct reaction. That is, in the case of a foam composition using a conventional amine catalyst, the amine component in the foam remains, so that an organic chemical was detected, but the composition for the foam of the present invention does not remain harmful substances in the foam by using a reactive amine urethane catalyst It is environmentally friendly.

Reaction type amine-based urethane catalysts such as N-methyl-N'-hydroxyethylpiperazine (N-methyl-N'-hydroxyethylpiperazine), N, N-dimethylaminoethoxyethanol (N, N-dimethylaminoethoxyethanol), Or N, N, N'-trimethylaminoethylethanolamine (N, N, N'-termiethylaminoethylethanolaminet) or the like.

The reactive amine urethane catalyst is preferably included in 4 to 9 parts by weight based on the resin premix. When in the above range can improve the foaming rate, foaming stability and storage stability of the polyurethane foam composition, there is an environmentally friendly advantage.

In addition, the foam composition of the present invention includes: i) 0.5 to 2 parts by weight of a metal-based urethane catalyst, the metal-based urethane catalyst may be used in the fibiate, tin octet, potassium octate, calcium octet, etc. When used inside, there is an advantage to improve the thermal stability, foaming rate, foaming stability and storage stability of the polyurethane foam composition

The silicone surfactant of iii) used in the present invention may use a silicone oil, which serves to maintain the molded state of the urethane foam well, mainly methyl siloxane-polyether surfactant, etc., specific examples Dow Corning's DC-5619, DC-193, etc. can be used.

 The silicone surfactant is preferably included in an amount of 0.1 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight based on the resin premix. If it is in the above range there is an advantage that can improve the foaming rate, foaming stability and storage stability of the polyurethane foam composition.

The resin premix containing the above components further includes water in addition to the above components, and the content thereof is preferably included in an amount of 0.3 to 5 parts by weight with respect to the resin premix, and more preferably 0.5 to 2 parts by weight. If it is in the above range there is an advantage that can improve the foaming rate, foaming stability and storage stability of the polyurethane foam composition.

Resin premix of a) consisting of the above components is preferably included in the total content of the composition for the polyurethane foam for spraying of the present invention in 45 to 55% by weight, tris (chloroisopropyl) phosphate or tris ( The flame retardant, 2-chloroethyl) phosphate, may be further included in an amount of 10 to 25 parts by weight based on 100 parts by weight of the total resin premix.

In addition, the polyisocyanate of b) used in the present invention may include isocyanate groups in an amount of 14 to 18% by weight, and the polyisocyanate is included in an amount of 55 to 45% by weight in the total content of the composition for blowing polyurethane foam of the present invention. It is desirable to be. If it is in the above range there is an advantage that can improve the foaming rate, foaming stability and storage stability of the polyurethane foam composition.

The foam composition of the present invention can be foamed using a known spray foaming machine, and the foaming ratio is 1.5 by using complete carbon dioxide, which is a chemical foaming agent, as a foaming agent in the resin premix of a) and the polyisocyanate of b). It can maintain about ~ 5 times, has excellent foaming stability and storage stability, and the composition for semi-rigid polyurethane foam according to the present invention is made of conventional FRP because it has the properties of semi-rigid When using the composition for the semi-swelling polyurethane foam of the present invention as an intermediate filling of the bath, the soft feel and high quality of the product can be achieved, and also, the interlayer noise absorber, vibration damping agent for removing vibration, and floor buffer are applied. It is suitable for the work, and it is possible to work to be sprayed, which has the advantage of good productivity and economic efficiency.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example 1

350 parts by weight of a polyether polyol (OHv 35 mgKOH / g2) having a molecular weight of 4000 prepared by addition polymerization of propylene oxide with glycerin as an initiator, and a polyether polyol having a molecular weight of 6000 produced by addition polymerization of propylene oxide with glycerin as an initiator. (OHv 28 mgKOH / g2) 100 parts by weight, 20 parts by weight of crosslinking agent diethanolamine, 2.5 parts by weight of silicone surfactant, 35 parts by weight of flame retardant, 20 parts by weight of HPW (Japan Tosho Co., Ltd.) with a reactive amine urethane catalyst, metal The urethane catalyst was mixed with a resin premix containing 5 parts by weight of potassium octane and 2.5 parts by weight of distilled water and 535 parts by weight of polymethyldiphenyl diisocyanate containing 14% by weight of NCO to prepare a polyurethane foam composition for semi-rigid blowing. .

Comparative Examples 1 to 4

To prepare a composition for the foam using the components and compositions shown in Table 1.

The unit in Table 1 is parts by weight.

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Resin premix (part by weight) Polyol ^{1 )} 350 250 150 350 350 Polyol ^{2 )} 100 200 100 100 100 Polyol ^{3 )} 0 0 200 0 0 Crosslinker ^{4 )} 20 20 20 50 20 Surfactant ^{5 )} 2.5 2.5 2.5 2.5 2.5 Flame Retardant ^{6 )} 35 35 35 35 35 HPW ^{7 )} 20 20 K-15 ⁸⁾ 5 5 5 5 5 Amine Catalyst ^{12 )} 20 20 20 Water ^{9 )} 2.5 2.5 2.5 2.5 2.5 Isocyanate (parts by weight) KS-1 ¹⁰⁾ 535 535 535 565 KS-2 ¹¹⁾ 535 1) Polyether polyol having a molecular weight of 4000 obtained by addition polymerization of propylene oxide with glycerin as an initiator, OHv 35mgKOH / g 2) Polyether polyol having a molecular weight of 6000 obtained by addition polymerization of propylene oxide with glycerin as an initiator , OHv 28mgKOH / g 3) Polyether polyol having a molecular weight of 500 obtained by addition polymerization of propylene oxide and propylene oxide, OHv 240mgKOH / g 4) Functional divalent crosslinking agent, OHv 1057mgKOH / g 5) Silicone oil, DC-193 , Air Products Co., Ltd. 6) Tris (chloroisopropyl) phosphate 7) Reaction type amine catalyst, Japan TOSHO Co., Ltd. 8) Metal catalyst-Potassium Octate, Sehotech 9) Distilled or ion-exchanged water 10) NCO 14% Polymerized Methyl Diphenyl Diisocyanate Containing Weight 11) NCO Polymerized Methyl Diphenyl Diisocyanate Containing 27% Weight 12) Amine Catalyst TEDA-L33 Japan TOSHO

Storage stability, organic volatility, density and foam state were measured using the foam compositions prepared in Example 1 and Comparative Examples 1 to 4, and the results are shown in Table 2 below.

The storage stability was visually observed after the resin premix was added to the measuring cylinder.

The organic volatility was measured by a small chamber method (managed by Korea Air Cleaning Association) of the environmental quality building material quality test method for measuring the emission intensity of organic volatile compounds in building materials.

Density measurement in the experiment was carried out by weight to volume by cutting the foam to a certain standard in accordance with KS M ISO 845 (measurement of foamed plastic and rubber-apparent density), the applied density is 200 ~ 700 kg / m ³ , More preferably, it is 360-500 kg / m <^3> . If the density is too low, the deformation width is large due to the influence of relative weight, and if too high, there is a negative effect in terms of productivity and cost.

The foam state was determined whether the urethane foam is maintained in a constant form without shrinkage or deformation of the appearance.

division Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Storage stability Good Good Good Good Bad Organic volatility Not detected detection detection detection Not detected Density kg / m ³ Good 410 Relatively low 290 Relatively high 550 Relatively low 350 Relatively high 580 Foam state Good Relative flexibility Relative crackle Relative flexibility Relative crackle

As shown in Table 2, the composition for the semi-hard polyurethane foam of Example 1 prepared according to the present invention is compared to Comparative Examples 1 to 4 storage stability, organic volatility The total organic volatility of less than -0.01 mg / m ² h, formaldehyde -0.03 mg / m ² h), density and foam state were all excellent.

In addition, as a result of measuring the foaming rate of the foam composition of Example 1 by the method of KS M ISO-845, it showed foaming properties of about 1100%.

The semi-rigid polyurethane foam composition according to the present invention has excellent foamability, foaming stability and storage stability, and has semi-rigid properties, so it is a tub, an interlayer noise absorber, a vibration damper for vibration removal, and a floor. It is suitable for the application of buffers and can be sprayed to improve productivity and economy.

The present invention described above is not limited to the above-described embodiments, and various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention. It is obvious to those who have it.

Claims (4)

In the composition for blowing polyurethane foam, a) iii) 35 to 70 parts by weight of a polyether polyol having 2-3 functional groups and a molecular weight of 1,000 to less than 5,000;   Ii) 10 to 40 parts by weight of a polyether polyol having 2 to 3 functional groups and a molecular weight of 5,000 to 7,000;  Iii) 2 to 10.5 parts by weight of crosslinking agent;  Iii) 3 to 9 parts by weight of a reactive amine urethane catalyst;  Iii) 0.5 to 2 parts by weight of a metallic urethane catalyst;  Iii) 0.1 to 3 parts by weight of silicone surfactant; And  Iii) 0.3 to 5 parts by weight of water  45 to 55% by weight of resin premix comprising; And b) 55 to 45 weight percent polyisocyanate comprising 14 to 18 weight percent isocyanate groups A composition for semi-rigid polyurethane foam, comprising a. The method of claim 1, The composition for semi-rigid polyurethane foam, characterized in that it further comprises a flame retardant which is the tris (chloroisopropyl) phosphate or tris (2-chloroethyl) phosphate. The method of claim 1, A composition for semi-rigid polyurethane foam, characterized in that the density is 200 to 700 kg / m ³ . A semi-rigid polyurethane foam having a foamed composition for semi-rigid polyurethane foam according to claim 1.