JPH0326694B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention is directed to polyvinyl chloride skin material (hereinafter referred to as PVC).
This invention relates to a method for producing semi-rigid polyurethane foam that is integrally foamed with a skin material (hereinafter referred to as a skin material) or a polyvinyl chloride, polyacrylonitrile butadiene styrene mixed skin material (hereinafter referred to as a PVC/ABS skin material). [Prior technology] Integral foam molded products of PVC skin material or PVC/ABS skin material and semi-rigid polyurethane foam are often used for automobile interior materials such as crash pads, armrests, head rests, console boxes, knee pads, etc. It is well known that a semi-rigid foam is used in which a polyol component mainly composed of a crosslinking agent, a blowing agent, a catalyst, etc. is reacted with an organic polyisocyanate. On the other hand, integrally molded urethane foam with a skin material that uses polyester polyol as a polyol component has poor workability because the polyester polyol has a high viscosity. Poor liquid flow during foam molding results in molding defects. Poor compatibility with isocyanates. Furthermore, polyester polyols have the disadvantage that they are more expensive than polyether polyols, so they have not been put into practical use. [Problems to be solved by the invention] In recent years, there has been a strong demand for lighter automobiles, improved productivity, and softer interior materials, leading to demands for lower density and shorter curing times for semi-rigid polyurethane foams. Highly desired. Will use again
Even PVC skin materials and PVC/ABS skin materials are required to be made softer. The trend towards lowering the density of foam, increasing the reactivity of foam raw materials, and softening skin materials is as follows.
The problem of reduced adhesion between the PVC skin material or PVC/ABS skin material and the urethane foam, resulting in peeling of the interface between the skin material and the urethane foam, has become a major problem. [Means for Solving the Problems] The present inventors have made extensive studies to solve these problems, and as a result, have arrived at the present invention. That is, the present invention applies to PVC skin material or PVC/ABS
Component A, whose main components are polyol, crosslinking agent, water and/or other blowing agents, catalysts, etc., and component B, whose main component is organic polyisocyanate, are reacted in a mold with a skin material installed inside. ,PVC
When manufacturing semi-rigid polyurethane foam that is integrally foamed with skin material or PVC/ABS skin material, polyether polyol is used as the polyol.
For 100 parts by weight, add a polyester polyol having a molecular weight of 200 to 2000 per difunctional monomer.
This is a method for producing a semi-rigid polyurethane foam integrally foam-molded with a PVC skin material or a PVC/ABS skin material, characterized in that 0.2 to 20 parts, preferably 0.5 to 10 parts are used. As the polyester polyol used in the present invention, dicarboxylic acid (or dicarboxylic acid anhydride)
Examples include condensed polyester polyols obtained by reacting lactone with dihydric alcohol, polyester polyols obtained by ring-opening polymerization of lactone, and mixtures thereof. The dicarboxylic acids include succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, dimer acid, and mixtures thereof. Examples of dihydric alcohols include diols such as ethylene glycol, propylene glycol, 1.5-pentanediol, 1.6-hexanediol, diethylene glycol, neopentyl glycol, bis(hydroxymethyl)cyclohexane, bis(hydroxyethyl)benzene, and mixtures thereof. It will be done. The method for synthesizing polyester polyol using these raw materials may be the usual manufacturing method for polyester polyols used as urethane raw materials, such as a method of dehydration condensation at 150 to 200°C. The polyester polyol in the present invention is a polyester polyester obtained by the above-mentioned conventional method, which is liquid at 25°C, bifunctional, and has a molecular weight per functional of 300 to 2000, preferably 500 to 2000. can be given. If it is solid at 25℃, the polyester polyol will solidify and precipitate in component A, making it difficult to react uniformly with the isocyanate compound.
The effects of the present invention cannot be expected. Also, the number of functional groups is 3
In the above case, problems such as shrinkage of the obtained semi-rigid urethane foam and poor liquid flow during foaming occur, which is not preferable. Further, if the molecular weight per functional unit is less than 300, the effect of the present invention cannot be obtained, and if the molecular weight per functional unit exceeds 2,000, the viscosity of the polyester polyol is too high to be used. The polyether polyol in component A may be a polyether polyol that is a raw material for ordinary urethane foam, such as polyhydric alcohols such as ethylene glycol, propylene glycol, triethanolamine, glycerin, trimethylolpropane, pentaerythritol, and sorbitol. alkylene oxide adducts. Among these, preferred are propylene oxide or ethylene oxide block or random adducts (ethylene oxide content usually 8 to 20%) with a molecular weight of 3,000 to 10,000 and a functional group number of 2 to 4. Further, a graft polyol may be used as a part of the polyether polyol, and as the graft polyol, a material having a hydroxyl value of 20 to 40, which is obtained by polymerizing monomers such as styrene and acrylonitrile in a polyether polyol, can be used. . In the present invention, the amount of polyester polyol used is 0.2 to 20 parts, preferably 0.5 to 10 parts, per 100 parts by weight of polyether polyol. If the amount is less than 0.2 parts, the effect of the present invention cannot be obtained, and if it is used in excess of 20 parts, there will be adverse effects such as poor liquid flow during foaming of the semi-rigid foam, resulting in molding defects. Moreover, it is not preferable to use a large amount of expensive polyester polyol. Crosslinking agents used in the present invention include ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, triethanolamine, diethanolamine, and/or propylene oxide adducts, ethylene oxide adducts, propylene oxide-ethylene oxide Blocks and/or random adducts with 200 to 1500 hydroxyl groups
and/or propylene oxide adducts, ethylene oxide adducts, propylene oxide-ethylene oxide block and/or random adducts of ethylene diamine, propylene diamine, and diethylene triamine with a hydroxyl value of 200 to 1,000. The total hydroxyl value of the polyether polyol, polyester polyol, and crosslinking agent in component A is usually 50 to 200. Total hydroxyl value
If it is less than 50, the obtained urethane foam will be too soft, and if it exceeds 200, the obtained urethane foam will be too hard, making it difficult to obtain the semi-rigid urethane foam integrally molded with the skin material, which is the object of the present invention. Water and/or other blowing agents used in component A include, in addition to water, trichloromonofluoromethane, methylene chloride, and the like.
The amounts used for these may be those used for foaming general urethane foam. As the catalyst, known amine catalysts and metal catalysts used for foaming urethane foam can be used. For example, triethylamine, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylhexamethylenediamine,
Examples include tetramethylpropylenediamine, pentamethyldiethylenetriamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, dimethylethanolamine, stannath octate, dibutyltin dilaurate, and the like. The amount used may be the same as that used for foaming general urethane foam. Further, other auxiliary agents such as flame retardants such as trischloroethyl phosphate, pigments such as carbon black, and foam stabilizers may also be used. Examples of the organic polyisocyanate used as component B include polymeric diphenylmethane diisocyanate, a mixture of polymeric diphenylmethane diisocyanate and toluene diisocyanate, a mixture of polymeric diphenylmethane diisocyanate and pure diphenylmethane diisocyanate, and a mixture of polymeric diphenylmethane diisocyanate and toluene diisocyanate. N.C.O.
Examples include terminal prepolymers, NCO-terminated prepolymers of pure diphenylmethane diisocyanate, and the like. Component A and component B may be reacted by a known method for producing ordinary semi-rigid urethane foam. For example, the NCO/OH ratio can be 0.8 to 1.2, the raw material temperature can be 10 to 40°C, and the mold temperature can be 30 to 60°C. PVC skin material used in the present invention or
PVC/ABS skin materials include general PVC skin materials used as automobile interior materials or PVC/ABS skin materials.
ABS skin material should be used. These skin materials are usually molded and used by a vacuum molding method or a slush molding method. As an example, a blending example of PVC (plastisol) for slush molding is shown. Examples of formulations for slush molding Zeon 121 80 (PVC resin, Nippon Zeon product) Zeon 103ZX 20 (PVC resin, Nippon Zeon product) DOP 70 (Plasticizer) DAP 30 (Diallyl phthalate, Osaka Soda product) Calcium carbonate 10 TMF-500 2 (Stabilizer, Tokyo Fine Chemical product) [Examples] The present invention will be explained in more detail with reference to Examples below. Examples 1 to 3, Comparative Example 1 With the foaming formulation shown in Table 1, soft PVC was added inside.
Using a mold equipped with a skin material (molded using the slush molding method), the soft PVC skin material and semi-rigid urethane foam were integrally foamed, and the physical properties of the foam were measured. The amount of each raw material used in the foaming formulation is expressed in parts by weight.

〔Effect of the invention〕

As shown in the Examples above, the peel strength of the foam molded product using the polyester polyol of the present invention with the soft PVC skin material (slush molded product) was a good value. On the other hand, in a comparative example that does not use polyester polyol, soft PVC
The interface with the skin material peeled off, making it practically unusable.

Claims (1)

[Claims] 1. In a mold with a PVC skin material or a PVC/ABS skin material installed inside, component A containing polyol, crosslinking agent, water and/or other blowing agent, and catalyst as main components and organic polyester PVC skin material or
When manufacturing a semi-rigid polyurethane foam that is integrally foamed with a PVC/ABS skin material, the polyol is bifunctional and has a molecular weight of 200% per 1 functionality per 100 parts by weight of polyether polyol.
~2000 ~ 0.2~20 polyester polyol
A method for manufacturing semi-rigid polyurethane foam that is integrally foamed with PVC skin material or PVC/ABS skin material. 2. The manufacturing method according to claim 1, wherein the polyester polyol is liquid at 25°C.