JPH0327570B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a urethane composition for integrally molding a slush vinyl chloride foam and a rigid urethane foam. <Prior Art> Conventionally, it has been known to integrally mold a slush polyvinyl chloride foam and a hard urethane foam to make a footwear stand, etc., as disclosed in Japanese Patent Laid-Open No. 51-37951. <Problems to be Solved by the Invention> However, in the above-mentioned prior art, the adhesion between the slush PVC foam and the hard urethane foam is poor, and in order to obtain a practical integrated product, surface treatment of the slush PVC surface layer is required. This was essential, making the process complicated, and improvements were desired. <Means for Solving the Problems> As a result of intensive research aimed at improving the adhesion of both of these foams, the present inventors have found that the above problems can be solved by using a urethane composition containing a specific polyol component. The inventors have discovered that the problem can be solved, leading to the present invention. That is, the present invention provides (a) diphenylmethane diisocyanate or a polyisocyanate component mainly composed of diphenylmethane diisocyanate, (b) polyester polyol and/or OH
Consisting of polyester polyol with terminal urethane and other active hydrogen-containing polyfunctional compounds, the OH value is
200 to 800, and a polyol component in which the polyester polyol and/or the OH-terminated urethanized polyester polyol contains more than 30% by weight of ε-caprolactone or ε-oxycaprolactonic acid ester moiety; (c) a catalyst; (d) a blowing agent; This is a urethane composition for integral molding of a slush PVC rigid urethane, which contains additive components mainly consisting of a foam stabilizer and a stabilizer. The polyester polyol used in the present invention includes a condensed polyester polyol obtained by reacting a polyol, dicarboxylic acid (or dicarboxylic anhydride and alkylene oxide) with ε-caprolactone or ε-oxycaproic acid, and ε- caprolactone or ε-
Examples include polyester polyols obtained by ring-opening polymerization of oxycaproic acid. Examples of the above-mentioned polyols include low-molecular polyols, such as diols such as ethylene glycol, propylene glycol, 1,6 hexanediol, diethylene glycol, neopentyl glycol, bis(hydroxymethyl)cyclohexane, and bis(hydroxyethyl)benzene; trimethylolpropane, glycerin, etc. ; polyether polyols (such as polyalkylene glycols) and mixtures thereof. Dicarboxylic acids include succinic acid, glutamic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, terephthalic acid, dimer acid,
and mixtures thereof. The molecular weight of the polyester polyol can be varied within the range that provides a rigid urethane foam when used in combination with other active hydrogen-containing polyfunctional compounds, that is, the mixed OH value of all polyol components is in the range of 200 to 800, but it is usually 500 to 10,000. , preferably 1000~
It is 3000. The average number of functional groups is usually 2 to 4, preferably 2 to 3. OH equivalent is usually 200~
3000, preferably 500-1500. The OH-terminated urethanized polyester used in the present invention includes a reaction product of the above-mentioned polyester polyol and an insufficient amount of polyisocyanate. As the polyisocyanate, the polyisocyanates mentioned below can be used, but tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and modified, liquefied
MDI is preferred. The molecular weight of OH-terminated urethanized polyester is
It can be used in combination with other active hydrogen-containing polyfunctional compounds to provide a hard urethane foam, but it is usually 2000 to 15000, preferably 3000.
~10000. The average number of functional groups is usually 2 to 3,
Preferably it is 2. OH equivalent is usually 1000~
7000, preferably 2000-5000. When the OH equivalent of the polyester polyol and the OH-terminated urethanized polyester becomes high, the viscosity becomes high and workability deteriorates, which is not preferable. If the OH equivalent is low, the adhesiveness will deteriorate, which is not preferable. Polyester polyols and OH-terminated urethanized polyols are ε-caprolactone or ε-caprolactone.
- Use one containing more than 30% by weight of ester moieties based on caproic acid. If less than this,
Adhesion development is slow. Other active hydrogen-containing polyfunctional compounds used in the present invention include low-molecular polyols, oxyalkylated polyhydric alcohols (polyether polyols), nitrogen atom-containing polyols, phosphorus-containing polyols, etc. Specific examples of these include: Japanese Patent Application No. 1983-113095, Japanese Patent Application No. 143114-1972, and Japanese Patent Application No. 1987-143114
Examples include those described in the specification of No.-39568. Preferred among these are oxyalkylated polyhydric alcohols and nitrogen atom-containing polyols, which can be used alone or in combination. The OH value of the other active hydrogen-containing polyfunctional compound can be freely changed as long as a rigid urethane foam can be formed, but it is generally 25 or more, preferably 50 to 1200, more preferably 200 to 800. The weight ratio of the polyester polyol and/or the OH-terminated urethanized polyester to the other active hydrogen-containing compound is usually 5:95 to 50:50, preferably 5:95 to 30:70. If the amount is too low, the adhesion will deteriorate, which is not preferable. If the amount is too large, the viscosity becomes high and the price becomes high, which is not preferable. The OH number of the mixture of polyester polyol and/or OH-terminated urethanized polyester polyol and other active hydrogen-containing polyfunctional compound can be varied within the range that can form a rigid urethane foam, but is generally 200 to 800, preferably 250. -600, more preferably 300-500. In the present invention, as the polyisocyanate component, diphenylmethane diisocyanate (MDI) or a product mainly composed of diphenylmethane diisocyanate (MDI) is used. In the case of toluene diisocyanate, the vapor pressure is high and the working environment is poor. Polyisocyanates mainly composed of MDI include 50% by weight or more of MDI and other polyisocyanates [triphenylmethane triisocyanate, phenyltolylmethane diisocyanate: polyols (low-molecular polyols, polyethers, etc.) and polyisocyanates (MDI, trilene diisocyanate, etc.] NCO-terminated prepolymers] and NCO-terminated prepolymers]. Such MDI-based polyisocyanates include crude MDI [crude diaminodiphenylmethane {a condensation product of formaldehyde and an aromatic amine or a mixture thereof: diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight) of 3
A phosgene compound (polyallylmethane polyisocyanate) (a mixture with a polyamine of higher than functional level) and modified, liquefied MDI (carbodiimide modified, trihydrocarbyl phosphate modified, etc.) can be used. Among these, the preferred one is crude
It is MDI. Although polyisocyanate can be foamed by a prepolymer method or a semi-prepolymer method, it is preferable to foam it by a one shot method. The isocyanate index is usually 70 to 150, preferably 90 to 120, more preferably 100 to 110, but it is also possible to form an isocyanate foam by using a large excess of isocyanate (index of 150 or more). In this case an isocyanate trimerization catalyst must be used. Blowing agents in the present invention include water and/or fluorocarbons (e.g. trichloromonofluoromethane, dichlorodifluoromethane),
Methylene chloride and the like can be used. The amount of water used is usually 0.1 to 3% by weight, preferably 0.2 to 1% by weight, based on the total amount of the polyol component and the isocyanate component. The amount of fluorocarbon used is usually 0 to 10, based on the total amount of polyol component and isocyanate component.
% by weight, preferably 2-5% by weight. Water and fluorocarbons can be used alone or in combination. The density of rigid urethane foam molded products can be varied depending on the purpose by selecting the amount of blowing agent used and the amount filled into the mold, but it is usually 0.1 to 0.8 g/
cm ³ , preferably 0.2 to 0.5 g/cm ³ . Examples of catalysts include tin-based catalysts (stannas octoate, dibutyltin dilaurate, etc.), amine-based catalysts [triethylenediamine, DBU (product of Sunabott Co., Ltd.), organic acid salts of DBU, etc.], organic acid salts (potassium acetate, sodium acetate, etc.). In addition to the polyisocyanate component, polyol component, and blowing agent, if necessary, a foam stabilizer such as a silicone surfactant, other surfactants, and fillers (such as granular fillers such as calcined vermiculite, perlite, shirasu balloons, and glass balloons) are added. inorganic porous bodies; inorganic powders such as calcium carbonate, talc, barium sulfate, bentonite;
Sand; granular or crushed synthetic resin foam such as styrene beads), flame retardants (e.g. phosphorus compounds), hydrophobic plasticizers, stabilizers (e.g. anti-aging agents, antioxidants, antibacterial agents) ), and various other auxiliaries and additives commonly used in urethane foams. As the slush PVC foam to which the urethane composition of the present invention is applied, the following can be used without any adhesion improvement treatment.

【table】

[Table] The urethane composition for integral molding of slush vinyl chloride foam and rigid urethane foam of the present invention is RIM
It can be applied to various methods such as integral molding using a method, injection using a low-pressure and high-pressure foaming machine, and a spray method.
An example of molding by the injection method is shown below, and examples of manufacturing slush PVC and slush PVC foam (hereinafter abbreviated as slush PVC and foam) molded products to which the composition of the present invention is applied are also shown. [A] Manufacture of slush PVC and its foam (1) PVC powder having the surface layer composition listed in Table 1 is poured into a reversible mold heated to 200 to 300°C, and the PVC powder is stuck to the mold. melts the epidermis,
The mold is turned upside down, the excess PVC powder is collected, and the mold is returned to its original position. A slush PVC surface layer consisting of a hard (solid) skin is formed while sticking to the inner surface of the mold. (2) Next, pour PVC foam powder with a foaming composition onto the surface layer of the slush PVC in the mold and let it stick, and in the same way as in (1) above, invert the mold and collect the excess foam layer powder. Put the mold back into place. By blowing hot air at a desired temperature into the mold or by maintaining the mold temperature at a desired temperature, the PVC powder is foamed to form a slush PVC foam. After foaming is completed, the mold is cooled with water and demolded, or the mold is directly moved to the next step. The obtained slush PVC molded product consists of two layers: a hard surface layer of slush PVC and a foam layer of slush PVC foam. [B] Method for manufacturing a slush PVC rigid urethane molded product Put the slush PVC molded product into the same mold as above, or remove the mold and put it into a hard urethane mold, and keep the liquid temperature at about 10-60°C, preferably 20-20°C. The urethane composition (isocyanate, polyester, catalyst, etc.) for integrally molding the slush PVC rigid urethane of the present invention at 40°C is injected at a discharge pressure of, for example, about 170 to 195 kg/ ^cm2 , and the mold temperature is set to 20 to 80°C, preferably 30 to After curing the urethane for a desired period of time (usually about 4 minutes) while maintaining the temperature at 60°C, the urethane is cured by reaction, and then removed from the mold to form a rigid PVC slush in which the three layers of the PVC slush, the same foam, and the hard urethane are integrally formed. A urethane integrally molded product is obtained. The packing ratio (ratio of molded product density to free foam density) is generally 1 to 10 times, preferably 2 to 5 times. These conditions can be selected as appropriate when manufacturing the integrally molded product. <Example> The present invention will be described below with reference to Examples, but the present invention is not limited thereto. Note that the parts shown in the examples represent parts by weight. Example 1 After obtaining a slush PVC and foam molded product from the raw materials listed in Table 2 using an up-and-down reversible mold, this was pasted onto a urethane mold, and
The polyol component, isocyanate component, etc. listed in Table 1(1) were injected and reacted and cured under the following conditions. After a predetermined time, the urethane molded product is removed from the mold.
The adhesion between the PVC foam and urethane was checked using a push pull gauge. The results are shown in Table 1(2). Molding conditions: Mixing time 15 seconds Demolding time 7 minutes Mold 20cm x 20cm x 1cm (thickness) Mold temperature 50℃

【table】

【table】

[Table] The polyols in Table-1 are as follows. Polyether 1: PO of sugar and glycerin mixture
An adduct, a polyether polyol with an OH value of 450. Polyether 2: Polyether polyol with an OH value of 750, which is a PO adduct of ethylenediamine. Polyether 3: PO in propylene glycol
A polyether polyol with an OH value of 48, with 23% by weight of EO added to the end. Polyester 1: A polyester polyol with an OH value of 56 synthesized by dehydration condensation from adipic acid, neopentyl glycol, and polycaprolactone ester with a MW (molecular weight) of 300. The weight percent of caprolactone ester is 50%. Polyester 2: A polyester polyol obtained by reacting a polycaprolactone ester with a MW of 2,000 with a condensed ester of a MW of 2,500 using ethylene glycol, 1,4-butanediol, and adipic acid using TDI. The OH value is 24 and the weight percent of caprolactone ester is 40%. Polyester 3: ethylene glycol, 1,4
-MW with butanediol, adipic acid = 2500
condensed ester of It is a polyester polyol with an OH value of 44.

[Table] Example 2 Using the foaming formulation shown in Table 3, integral molding with PVC foam was carried out in the same manner as in Example 1. Molding conditions: Mixing time 10 seconds Demolding time 4 minutes Mold 20cm x 20cm x 0.7cm (thickness) Mold temperature 50℃

【table】

【table】

[Table] The polyols in Table 3 are as follows. Polyether 4: PO adduct of glycerin,
Polyether polyol with an OH value of 400. Polyether 5: triethanolamine,
PO adduct of TDA mixture, polyether polyol with OH number 500. Polyether 6: PO adduct of glycerin,
Polyether polyol with an OH value of 670. Polyester 4: Polyester polyol 1 and
A polyester polyol with an OH value of 13, which is a reactant of TDI. <Effects of the Invention> When the urethane composition according to the present invention is brought into contact with a slush vinyl chloride foam to foam a rigid urethane foam, a product with good adhesion between the two can be obtained, and in practical use, an integrally molded product with no fear of layer separation can be obtained. is obtained. In addition, by using a polyester polyol containing more than 30% by weight of ε-caprolactone or ε-oxycaproic acid ester moieties and/or an OH-terminated urethanized polyester polyol, adhesiveness can be developed quickly, and foam-molded urethane The heat resistance of the foam is improved. By utilizing the above effects, decorative panels,
It can be applied to furniture, electrical appliances, automobile interior materials, etc. Conventionally, when integrally molding a slush vinyl chloride foam and a hard urethane foam, the slush vinyl chloride foam required primer treatment, which caused problems such as an increase in work steps and an increase in cost due to pretreatment.However, the composition of the present invention Using this eliminates the need for pretreatment and eliminates this problem.

Claims (1)

[Claims] 1 (a) diphenylmethane diisocyanate or a polyisocyanate component mainly composed of diphenylmethane diisocyanate, (b) polyester polyol and/or OH
It consists of a polyester polyol with a terminal urethane and another active hydrogen-containing polyfunctional compound, and has an OH value of 200 to 800, and the polyester polyol and/or the polyester polyol with an OH terminal is ε-caprolactone or ε-caprolactone.
- A slush PVC rigid urethane component whose essential components are a polyol component containing more than 30% by weight of oxycaproic acid ester moieties, (c) a catalyst, and (d) an additive component mainly consisting of a blowing agent, a foam stabilizer, and a stabilizer. Urethane composition for molding. 2 Polyester polyol and/or OH
2. The urethane composition according to claim 1, wherein the weight ratio of the urethane-terminated polyester to the other active hydrogen-containing polyfunctional compound is from 5:95 to 50:50. 3 Polyester polyol and/or OH
The molecular weight of polyester with terminal urethane is 500~
15,000, the urethane composition according to claim 1 or 2.