JP4849713B2 - Ribbon Did Chip Product Manufacturing Method for Vehicle - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing a ribbon-dipped chip product for a vehicle and a ribbon-dipped chip product for a vehicle. Ribbon dipped chip products for vehicles manufactured by the method of the present invention have sufficient hardness, excellent fogging resistance, and are useful as vehicle seat cushions despite their low density and light weight. . In addition, it has sufficient hardness equivalent to that of conventional products and has excellent fogging resistance, and is also useful as various types of vehicle interior materials such as vehicle floor mats, pads, armrests, core materials, and raising materials.
[0002]
[Prior art]
In a ribbon-dipped chip product used as a vehicle seat cushion, a toluene diisocyanate prepolymer has been conventionally used as a binder for bonding chips from the viewpoint of cushioning. In order to obtain a seat cushion having an appropriate hardness, the density must be increased, resulting in a heavy product. Furthermore, in order to improve the workability when spraying the prepolymer on the chip, methylene chloride is frequently used as a diluent that lowers the viscosity of the binder, but this diluent falls under the PRTR method. Considering the environment, air pollution, etc., it is not preferable.
[0003]
On the other hand, in ribbon-dipped chip products used as interior materials for vehicles other than seat cushions, it is necessary to increase the hardness, so diphenylmethane diisocyanate-based prepolymer is used as a binder used for chip bonding. Yes. And, in order to improve workability when spraying the prepolymer on the chip, plasticizers such as dioctyl adipate, dioctyl phthalate, dibutyl phthalate, etc. are often used as diluents, but they were manufactured using such plasticizers. There is a problem that the product is inferior in fogging resistance. These plasticizers also fall under the PRTR law and there is a movement to voluntarily restrict their use.
[0004]
[Problems to be solved by the invention]
The present invention solves the above-described problems, is lightweight, has sufficient hardness, has excellent fogging resistance, and is useful as a vehicle seat cushion. An object of the present invention is to provide a method for manufacturing a ribbon-dipped chip product having an equivalent hardness and excellent fogging resistance and useful as a vehicle interior material such as a floor mat. Another object of the present invention is to provide a vehicular ribbon-dipped chip product having the above-described excellent characteristics.
[0005]
[Means for Solving the Problems]
The method for manufacturing a ribbon-dipped chip product for a vehicle according to claim 1 is a mixture of polyisocyanate and toluene diisocyanate represented by the formula (1) or polyisocyanate represented by the formula (1), and has a molecular weight of 1,000 to 1,000 parts. 10 to 50 parts by mass of a polyol having a hydroxyl value of 250 mg / g or less and a molecular weight of 395 or more and a boiling point of 340 ° C. or more at a pressure of 101.3 kPa of 5 to 40 masses. A prepolymer prepared using a raw material containing a part is used as a binder for a chip.
[0006]
As the polyisocyanate, the “polyisocyanate” represented by the formula (1) [hereinafter abbreviated as “p-MDI”. In addition, n in Formula (1) is 0-6 normally. A mixture in which the average of n is 0.2 to 0.8 is preferable. ] And toluene diisocyanate (hereinafter abbreviated as “TDI”), it is possible to produce a vehicle seat cushion that is lightweight, has an appropriate hardness, and excellent cushioning properties. . Even if only p-MDI is used, the hardness can be made sufficiently high, but the compression set required for the seat cushion is lowered. Therefore, if TDI is used in combination, a seat cushion having excellent compression set can be obtained. As this TDI, crude TDI provided as a mixture of 2,4-TDI and 2,6-TDI can be used. The amount ratio of p-MDI and TDI is not particularly limited, but is preferably p-MDI / TDI = 100/10 to 50, particularly 100/15 to 35 in terms of mass ratio, and p-MDI / TDI = A commercially available product of 100/25 can be used as it is.
[0007]
Thus a combination of the p-MDI and TDI, by the use of a plasticizer such as a diluent with a particular polyol of claim 1, density is 25~45kg / m3, preferably 30~40kg Ribbon dipped chip product useful as a vehicle seat cushion having a hardness of 50 / 200N, preferably 70-150N. This seat cushion is lower in density and lighter than conventional seat cushions, has the same hardness, and has excellent fogging resistance.
[0008]
On the other hand, when only p-MDI is used as the polyisocyanate, it can be made into a ribbon dipped chip product with higher hardness, and for vehicles such as floor mats and armrests where cushioning properties and compression set are not so problematic. Interior materials can be manufactured.
[0009]
By thus using only p-MDI, the use of a plasticizer such as a diluent with a particular polyol of claim 1, density is 70~140kg / m3, preferably 80 to 110 kg / m3 Ribbon dipped chip products useful as vehicle interior materials having a hardness of 500 to 1700 N, preferably 650 to 1200 N, and a fogging resistance of 10% or less, preferably 5% or less. This vehicle interior material has the same hardness as a conventional interior material, and is extremely excellent in fogging resistance.
[0010]
Furthermore, it is particularly preferable to use p-MDI having a lower viscosity. If p-MDI having a viscosity at 25 ° C. measured by JIS K1603 of 100 mPa · s or less, particularly 80 mPa · s or less, and even 50 mPa · s or less is used, the diluent can be reduced and the prepolymer is applied to the chip. A ribbon-dipped chip product with better fogging resistance can be easily manufactured without deteriorating the workability when spraying.
[0011]
As the polyol, a polyether polyol can be used. As this polyol, it is preferable to use a bifunctional or trifunctional one obtained by addition-polymerizing an alkylene oxide in a random or block form in the presence of a basic catalyst to a starting material having two or more active hydrogens. Examples of such polyols include compounds having active hydrogen such as propylene glycol, dipropylene glycol, glycerin and trimethylolpropane, ethylene oxide, propylene oxide, trimethylene oxide, butylene oxide, styrene oxide, α-methyltrimethylene oxide. , 3,3′-dimethyltrimethylene oxide and the like obtained by addition polymerization.
[0012]
The molecular weight of the polyol is 1000 to 4000, preferably 1000 to 3000, and particularly preferably 1000 to 2500. As the molecular weight increases, the viscosity of the polyol increases and the prepolymer is easily solidified. For this reason, after spraying the prepolymer on the chips, the chips start to form in a relatively short time, and the fluidity of the chips flowing smoothly decreases, making it difficult to put them into the mold. As a result, there may be a case where voids are formed inside the product, or the surface is thinned, so that a product having a predetermined shape cannot be obtained.
[0013]
Further, the hydroxyl value of the polyol is less than 250 mg / g, preferably at 200 mg / g or less, in particular, as claimed in claim 2, is preferably 40 to 120 mg / g. Since this hydroxyl value increases and the reactivity also increases, the prepolymer is easily solidified, and after spraying the prepolymer onto the chip, the chip starts to solidify in a shorter time, causing the same problem as above. There is.
[0014]
When the molecular weight of the polyol is 2500 or less and the hydroxyl value is 120 mg / g or less, a polyol having a sufficiently low viscosity can be selected. In particular, as measured according to claim 3, it is measured by the above method. A polyol having a viscosity at 25 ° C. of 400 mPa · s or less can be used. And, if a prepolymer prepared using a low-viscosity polyol is used in this way, after spraying the prepolymer onto the chip, it will be put into the mold even after 1 hour or more, especially 2 hours. Therefore, a ribbon-dipped chip product having a predetermined shape can be obtained without causing voids, lack of thickness or the like in the product.
[0015]
As a diluent blended to give sufficient spray coating performance to the prepolymer, it has a relatively high molecular weight and a high boiling point, has a high volatility plasticizer and a high boiling point, and lowers the fogging resistance. At least one of propylene carbonate without any is used. As the plasticizer, those having a molecular weight of 395 or more and a boiling point of 340 ° C. or more at a pressure of 101.3 kPa can be used. Particularly, the molecular weight is 400 or more, the boiling point of 350 ° C. or more, and further 370 ° C. The above is preferable. When the plasticizer has a molecular weight of less than 395 or a boiling point of less than 340 ° C., the fogging resistance is lowered and cannot be put to practical use as a ribbon-dipped chip product for vehicles. The plasticizer having a boiling point of 340 ° C. or higher at a pressure of 101.3 kPa includes a plasticizer having a very high boiling point at a pressure of 101.3 kPa and usually measured at a lower pressure.
[0016]
As the high molecular weight, high boiling point plasticizer, diisononyl adipate [molecular weight: 398, boiling point: 227 ° C. (however, the pressure is 0.67 kPa)], diisodecyl adipate [molecular weight; 427, boiling point: 239-248 ° C. (however, the pressure is 0.53 kPa)], diisononyl phthalate (molecular weight: 419, boiling point: 410 ° C.) and diisodecyl phthalate (molecular weight: 447, boiling point: 420 ° C.) It is preferable to use at least one kind. These plasticizers are also inexpensive and advantageous in terms of prepolymer costs. In addition, as a preferable plasticizer, bis (butyldiglycol) adipate [molecular weight: 435, boiling point: 230 to 240 ° C. (however, the pressure is 0.27 kPa)], bis (2-ethylhexyl) azelate ( Molecular weight; 413, boiling point: 376 ° C.), bis (2-ethylhexyl) sebacate (molecular weight: 427, boiling point: 377 ° C.) and the like can be used.
[0017]
The blending amount of the polyisocyanate, the polyol and the plasticizer or propylene carbonate is 10 to 50 parts by mass of the polyol, particularly preferably 15 to 40 parts by mass, when the polyisocyanate is 100 parts by mass. When the polyol is less than 10 parts by mass, the hardness of the ribbon-dipped chip product becomes insufficient, and when it exceeds 50 parts by mass, the prepolymer starts to gel. Further, the plasticizer or propylene carbonate is 5 to 40 parts by mass, and if they are less than 5 parts by mass, the viscosity of the prepolymer is increased, the workability when spraying on the chip is lowered, and exceeds 40 parts by mass. As a result, the chip cannot be firmly bonded. In addition, if a thing with a lower viscosity is used as polyisocyanate, a plasticizer etc. can be reduced, However It is preferable to adjust the compounding quantity of a plasticizer etc. suitably considering the viscosity of this polyisocyanate.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to examples.
[1] Preparation of prepolymer Prepolymers were prepared as follows using the polyisocyanates, polyols and diluents shown in Table 1 in the quantitative ratios shown in Table 1.
A mixture of p-MDI and TDI, p-MDI or TDI is charged into a reaction kettle capable of adjusting the temperature, and while maintaining the liquid temperature at 30 ± 5 ° C., the polyol and the diluent are added in small amounts while stirring. Added over 30 minutes to prepare a prepolymer.
[0019]
The following were used as the polyisocyanate, polyol and diluent in Table 1.
(1) p-MDI / TDI; manufactured by Takeda Pharmaceutical Co., Ltd., trade name “4040MC”, isocyanate group content 32.2%
(2) p-MDI; manufactured by BASF, trade name “Luprinate M-12S”, isocyanate group content 30.7%, viscosity at 25 ° C. 111 mPa · s
(3) Low-viscosity p-MDI; manufactured by BASF, trade name “Luprinate MB-5S”, isocyanate group content 31.7%, viscosity at 25 ° C. 50 mPa · s
(4) TDI (toluene diisocyanate); manufactured by Takeda Pharmaceutical Co., Ltd., trade name “Takenate 80”, isocyanate group content 48%
[0020]
(5) # 1000 (polyether polyol); manufactured by Takeda Pharmaceutical Co., Ltd., trade name “ACTCOL 32-160”, hydroxyl value 160 mg / g , number of functional groups 3 (6) # 2000 (polyether polyol); Takeda Product name “Actol P-21”, hydroxyl value 56 mg / g , number of functional groups 2 (7) # 3000 (polyether polyol); product name “Actol 31-56” manufactured by Takeda Pharmaceutical Co., Ltd. , Hydroxyl value 56 mg / g , functional group number 3
[0021]
(8) DINA (Diisononyl Adipate); manufactured by Daihachi Chemical Co., Ltd., trade name “DINA”, molecular weight 398, boiling point 227 ° C. (however, the pressure is 0.27 kPa), not applicable to the PRTR method (9) DIDA (diisodecyl adipate); manufactured by Daihachi Chemical Co., Ltd., trade name “DIDA”, molecular weight 427, boiling point 239-248 ° C. (however, the pressure is 0.53 kPa), not applicable to the PRTR method (10) PC (Propylene carbonate); Nisso Oil Chemical Co., Ltd., molecular weight 102, boiling point 241.7 ° C., stable and non-toxic (11) MC (methylene chloride); Shin-Etsu Chemical Co., Ltd., molecular weight 85, boiling point 40 ° C.
(12) DOA [bis (2-ethylhexyl) adipate)]; manufactured by Daihachi Chemical Co., Ltd., trade name “DOA”, molecular weight 371, boiling point 335 ° C., applicable to PRTR method
[2] Manufacture of Ribbon Dipped Chip Product The ribbon dipped chip is put into a mixer, and 10 to 40 parts by mass of each prepolymer prepared in [1] is sprayed on 100 parts by mass of the chip. Then, after mixing for 3 minutes, an amount of the mixture having a product density of a predetermined value was put into the mold. Next, the mold is closed, steam is blown out from the lower mold having fine through-holes, the steam is filled in the mold for 2 minutes to react, and after the reaction is completed, the mold is removed, and then the temperature of the product is adjusted to 70 ° C. The ribbon dipped chip product was obtained by standing in a heating furnace and drying.
[0023]
[3] Evaluation of Ribbon Did Chip Product The density, hardness and fogging resistance of the ribbon dipped chip product obtained in [2] were measured by the following methods.
(1) Density: Measured according to JIS K 6401.
(2) Hardness: Measured according to JIS K 6400.
(3) Fog resistance: Measured according to the haze evaluation method of JASO M 313-83 (after 80 ° C. for 20 hours).
The results are also shown in Table 1.
[0024]
[Table 1]
[0025]
According to the result of Table 1, in Example 1, compared with the comparative example 1 using the conventional prepolymer for seat cushions, hardness is equivalent and a density is considerably low, and a product can be reduced in weight sufficiently. I understand that. Moreover, in Example 1, since the methylene chloride which concerns about environmental pollution is not used as a diluent, it can be said that it is preferable also from this viewpoint.
[0026]
Furthermore, in Examples 2-5, compared with Comparative Example 2 using a conventional prepolymer for a vehicle interior material having a high hardness such as a floor mat, the hardness is equal to or slightly higher than that of Comparative Example 2 and is conventionally used as a diluent. It can be seen that the fogging resistance is greatly improved because a plasticizer having a low molecular weight and a low boiling point is not used.
[0027]
【The invention's effect】
According to the manufacturing method of the first aspect, it is possible to obtain a ribbon-dipped chip product for a vehicle having a low density and a light weight while having a sufficient hardness. In particular, as described in claim 2, workability can be improved by using a polyol having low activity and adjusting the curing time to about 30 minutes which is optimum in terms of process control. Furthermore, it can be a useful vehicle for ribbon Secluded chip products as sheets over cushions, also has a conventional equivalent sufficient hardness and excellent fogging resistance, full Roamatto, various interior materials such as armrest It can also be used as a ribbon dipped chip product for vehicles useful as Since these products do not use a diluent that may cause environmental pollution such as methylene chloride, they are preferable ribbon-dipped chip products from this point of view.

Claims (6)

Polyisocyanate represented by the following formula (1)
[However, in Formula (1), n is an integer greater than or equal to 0, and the said polyisocyanate is a mixture of a binuclear body and a polynuclear body. ] And a toluene diisocyanate or 100 parts by weight of the above polyisocyanate, a molecular weight of 1000 to 4000, a polyol having a hydroxyl value of 250 mg / g or less, 10 to 50 parts by weight, and a molecular weight of 395 or more, pressure A prepolymer prepared by using a raw material containing 5 to 40 parts by mass of at least one of a plasticizer and propylene carbonate having a boiling point at 101.3 kPa of 340 ° C. or higher is used as a chip binder. Manufacturing method for ribbon-dipped chip products. The method for producing a ribbon-dipped chip product for a vehicle according to claim 1, wherein the polyol has a hydroxyl value of 40 to 120 mg / g . The method for producing a ribbon-dipped chip product for a vehicle according to claim 1 or 2, wherein the polyol has a viscosity at 25 ° C of 400 mPa · s or less. The method for producing a ribbon-dipped chip product for a vehicle according to any one of claims 1 to 3, wherein the plasticizer is at least one of diisononyl adipate, diisodecyl adipate, diisononyl phthalate, and diisodecyl phthalate. The step of preparing a prepolymer by mixing and stirring the raw materials, the step of mixing the prepared prepolymer with 10 to 40% by mass with respect to 100% by mass of the chip, and obtaining the mixture, And a step of filling the mold with a steam blown and filled with the mold, reacting the adjusted prepolymer, and demolding after completion of the reaction to obtain a product. The method for manufacturing a ribbon-dipped chip product for a vehicle according to any one of claims 1 to 4. 6. The method of manufacturing a ribbon-dipped chip product for a vehicle according to claim 5, wherein the mold has a fine through hole, and steam is blown out from the fine through hole .