JPH0542971B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for manufacturing a flexible urethane foam for frame lamination. (Prior art) In contrast to polyurethane foam as a cushion material, woven fabrics, knits, double laces, moquettes, tricots, kouinnits, PVC leather,
A single-sided laminated frame laminate sheet with a welded surface material as an exterior material made of genuine leather, etc. In addition, the back material is made of tricots, gold cloth, non-woven fabric, stockinette, spunbond, plain woven fabric, etc. as a reinforcing material, etc. Frame laminate sheets, which are laminated on both sides by welding, are widely used for interior materials for vehicles such as automobiles, footwear linings, furniture, clothing, etc. Conventionally, this type of polyurethane foam uses a mixture of ester-modified polyol, ether-modified polyol, or a mixture thereof and an unmodified ordinary polyol with a molecular weight of 3000 as a polyol component, and water is added.
Using 3.5-4.5 parts by weight, with a TDI index of 110-115,
It was manufactured using other foam stabilizers, tin catalysts, amine catalysts, etc. For example, 60m using this polyurethane foam.
When making long robes, it was an excellent countermeasure against ``drinking'' on the surface of the robe and dents on the bottom.
However, depending on the frame lamination machine conditions and the type of surface material, the peel strength between the surface material and the urethane foam was sometimes less than 0.3 kg/2.5 cm. Separately, in the case of formulations in which a large number of parts of water are added and the isocyanate index is high, internal heat generation becomes large and scorch occurs in the summer months from July to September. Important conditions for frame laminating machines include gas pressure, air pressure, line speed, compression of the foam and surface material, distance between the gas burner and the foam, etc., but even if these machine conditions are optimized, the adhesion of the surface material When the material was special and complex, the peel strength sometimes exceeded the standard (0.3 kg/2.5 cm). (Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing a flexible urethane foam for frame lamination that has excellent peel strength regardless of the conditions of the frame lamination machine or the type of surface material. Another object of the present invention is to provide a method for producing a flexible urethane foam for frame lamination that does not cause the scorch phenomenon even in summer. (Means for Solving the Problems) When producing a flexible urethane foam for frame lamination, the present invention uses both an ester-modified polyol and a urethane-modified polyol as polyols, an isocyanate, water and, if necessary, a foam stabilizer and a metal. Using non-volatile components such as catalysts, amine catalysts, pigments, flame retardants, plasticizers, etc. and volatile components such as foaming aids, it is confirmed that the isocyanate ratio in the non-volatile components forming the foam is 33.3% or less. The present invention relates to a method for producing a soft urethane foam for frame laminates which is characterized by excellent peel strength. In the present invention, examples of the ester-modified polyol include Actocol L-27C (OH
56), Actocol L-28M (OH value 56), etc.
Examples of urethane-modified polyols include Asahi Glass Co., Ltd.
Exenol 3201 (OH value 62), etc., and Dainippon Ink Co., Ltd.'s Hyprox, a mixture of ester-modified polyol and urethane-modified polyol.
Examples include ODX-1511 (modified polyol 40%, OH value 58). Tolylene diisocyanate (TDI) is mainly used as an isocyanate compound, but diphenylmethane diisocyanate (MDI),
Tolidine diisocyanate (TODI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), lysine diisocyanate (LDI)
Diisocyanates such as triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (PAPI), carbodiimide-modified MDI
Examples include polyisocyanates such as. In the present invention, 1.7 to 3.9 parts by weight of water is used for both the above-mentioned ester-modified polyol and urethane-modified polyol and 100 parts by weight of the polyol in the flame retardant formulation, and the peeling is achieved by reacting with an NCO index of 102 to 110. A flexible urethane foam for frame laminate with excellent strength can be manufactured. If the amount of water is less than 1.7 parts, the density of the foam becomes too large and foaming becomes difficult. Also
If it exceeds 3.9 parts, the number of urea bonds increases and the peel strength decreases. In addition, for flame retardant foam, it is preferable to add 5 to 30 parts by weight of flame retardant, and accordingly, the amount of water used should be 2.0 to 5.5 parts by weight, and the NCO index should also be increased.
It is preferable to react at a temperature of 102 to 110. When the NCO index is less than 102, side blows and internal blows occur, and when it exceeds 110, allophanate bonds and biuret bonds increase, resulting in a decrease in peel strength. A preferred NCO index is 103-106. There are halogen flame retardants used in flame retardant formulations, but heat resistance tests (100℃, 200 hours),
It is difficult to use on flame laminate forms because it changes color during the light fastness test (weatherometer test). Powder-based flame retardants also worsen peel strength. For flame laminate foams, Stocha Chemical's Phosflex 112A (OH value 99), which is a mixture of triallylphosphate and dibromoneopentyl glycol, is suitable. In the present invention, it is essential that the isocyanate ratio in the non-volatile components forming the foam, expressed by the following formula, is 33.3% or less; if it exceeds 33.3%, the foam becomes hard and has poor compatibility with the fibers. The peel strength decreases and scorch occurs in the summer. Isocyanate ratio = a x 100 / b a: Isocyanate usage b: A liquid + B liquid - foaming aid A particularly preferred isocyanate ratio is in the range of 20 to 33%. In the present invention, other components as required include:
Non-volatile components such as known foam stabilizers, metal catalysts, amine catalysts, pigments and plasticizers, and volatile components such as foaming aids can be used. As the metal catalyst, for example, a tin catalyst such as stannous octate is used. As an amine catalyst, for example, Fudry's
Dabco T (N,N,N'-trimethylaminoethylethanolamine), Toyo Soda Kogyo Co., Ltd.'s Toyokyat NP, trimethylaminoethylpiperazine, Sanabbot Co., Ltd.'s Polykyat-12 (N-methyldicyclohexylamine), etc. are used. be done. These amine catalysts are resistant to discoloration of fibers and vinyl chloride sheets (heat resistance test at 100°C for 200 hours).
N-methylmorpholine, DABCO (triethylenediamine),
Pentamethyldiethylenetriamine and the like are also used. Freon gas, methylene chloride, ethylene chloride, etc. are also used for density adjustment. In the case of the urethane foam suitable for the present invention, when 1.7 to 3.9 parts of water is added, the urethane foam has two heat generation peaks in differential thermal analysis, and the first heat generation starting point is at 230 to 270°C. In this case, the peel strength is excellent and the scorch phenomenon does not occur even in summer. In the case of flame-retardant foam, when the water content exceeds 4.0 parts, there is only one peak of heat generation in differential thermal analysis, but the starting temperature of heat generation is 285℃.
When the maximum exothermic temperature is 300°C or less, the peel strength is particularly excellent and no scorch phenomenon occurs in summer. (Example) Examples and comparative examples will be described below. Examples 1 to 10 and Comparative Examples 1 to 6 Hyprox ODX-1511S (OH value 59)
Pour 4,000g into a jotsky, stir with a propeller mixer, and add 8g of tin catalyst (equivalent to 0.2 parts) and silicone foam stabilizer SF2904 (Toray Silicone) 24g (0.6
part equivalent), amine catalyst (A) Polycat-12 (4.0g,
Add 0.10 parts (equivalent to 0.10 parts) and (B) Toyocat NP (4.0 g, 0.10 parts equivalent), stir for 30 minutes, and use this as Solution A. Based on Table 1, 202 of liquid A is added to the descap of 500 c.c.
gram, add the missing amount of each chemical solution using a graduated dropper, and add the necessary amount of water into it. separately
Prepare the required amount of TDI for a 200 c.c. descap and use this as liquid B. A adjusted to 25℃ under the rotor of the homomixer
Bring the liquid-filled descap, stir for 5 seconds at the highest rotation speed, and add liquid B adjusted to 23°C. After 5 seconds of stirring, the mixture is poured into a paper-covered box measuring 240 x 240 x 240 mm, placed in a dryer at 170°C, taken out after 60 minutes, and left for 24 hours. After that, form 10mm×
Divide into 150mm x 230mm and check the scorch condition of the foam in the center. The slotted foam was processed using a small frame laminating machine at a speed of 20 m/min, a distance between the burner and the foam of 20 mm, and a gas pressure of 0.1 Kg/cm ² .
The foam was compressed by 50%, the fabric was cut into 150 mm widths, laminated with a frame, and left for 24 hours. The density of the foam was determined by JIS K6401 after being left for 24 hours after injection, and the peel strength was determined by tensile speed using Tensilon (manufactured by Toyo Baldwin).
Three sheets were measured at 50 mm/min and 2.5 cm x 15 cm in the vertical direction, and the average value of max3 and min3 was calculated. Differential thermal analysis was performed using a DSC manufactured by Rigaku Denki in an aluminum container, a sample amount of 3 to 4 mg, an air atmosphere, a heating rate of 5° C./min, and a sample open state.
The results are shown in Table 1.

【table】

[Table] Test Example 1 Table 2 shows the results of measuring the tensile strength, elongation, tear strength, compression set, and impact resilience of the urethane foams obtained in Examples 1 to 10 in accordance with JIS K6401.

【table】

Claims (1)

[Claims] 1 When producing flexible urethane foam for frame lamination, both ester-modified polyol and urethane-modified polyol are used as polyols, isocyanate, water, and if necessary, foam stabilizers, metal catalysts, amine catalysts, pigments, flame retardants, and plasticizers. A soft material for frame lamination with excellent peel strength, characterized by using non-volatile components such as , and volatile components such as foaming aids, and having an isocyanate ratio in the non-volatile components forming the foam of 33.3% or less. Method of manufacturing urethane foam.