JP2006022293A - Polyester polyurethane molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester polyurethane molded article having few total volatile organic compound content and scarcely polluting surrounding environment and a contacting substance. <P>SOLUTION: The polyester polyurethane molded article scarcely having total volatile organic compound is obtained by using a polyester polyol obtained by carrying out condensation reaction of a polyhydric alcohol component containing ≥30 mass% dialcohol having ≤3C main chain with a polyhydric carboxylic acid component containing ≥30 mass% either one or a plurality of dimer acid, isophthalic acid, terephthalic acid and succinic acid and having ≤100 ppm (in terms of toluene calibration curve) volatile by-product. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a polyester polyurethane molded article having a small total amount of volatile organic compounds.

Polyurethane molded products are excellent in high elasticity, flexibility, wear resistance, etc., and are widely used as materials for foam, elastomers, films, synthetic leather, adhesives, paints and the like.

Polyurethane molded products are mainly reacted with polyhydroxy compounds such as polyester polyols and polyether polyols by adding polyisocyanates and, if necessary, chain extenders, foaming agents, foam stabilizers, aggregates, etc., to obtain desired films, sheets, foams, etc. Molded into shape. Among these, as a polyhydroxy compound, those using polyester polyol are characterized in that they are superior in mechanical properties, wear resistance, oil resistance, and solvent resistance compared to those using polyether polyol. Of the polyester polyols, adipic acid polyester polyols that are inexpensive and have the highest versatility are often used. However, since adipic acid-based polyester polyols have many volatile by-products such as cyclic esters and these do not participate in the urethane reaction and remain in the polyester urethane molded product as they are, they can be obtained from such polyester polyols. Polyester polyurethane molded articles have a large amount of volatile organic compounds, and their use is often limited due to the disadvantage that the organic compounds that have volatilized contaminate the surrounding environment and the substances they come into contact with. Research has been conducted to eliminate these disadvantages.

For example, in JP-A-6-107759, in order to reduce the volatilization amount of volatile components causing fogging, vacuum distillation is performed at a temperature of 160 to 250 ° C. and a pressure of 0.05 to 10 mbar for 2 to 600 seconds after synthesis. A method for producing a polyester urethane foam characterized by using a polyester polyol that has been produced has been proposed, but this method cannot sufficiently remove volatile components. Moreover, since the hydroxyl value of the polyester polyol is reduced by distillation under reduced pressure, it is necessary to add extra polyhydric alcohol in advance to obtain the desired hydroxyl value. In addition, the addition of an inert solvent during the distillation process has also been shown to increase the effect of vacuum distillation, but the method of adding this inert solvent does not allow sufficient recovery of the inert solvent and itself is a volatile component. There is a risk of being contained.

An object of the present invention is to provide a polyester polyurethane molded article which has a small total amount of volatile organic compounds and hardly pollutes the surrounding environment and a substance to be contacted.

In order to solve the above problems, it is essential to use a polyester polyol having a small amount of volatile by-products. As a result of intensive studies, the present inventors have found a specific polyhydric alcohol and a polycarboxylic acid component. Polyester polyols that have been subjected to condensation reaction using a fixed amount have been found to have less volatile by-products, and polyester polyurethane moldings using them have a low total volatile organic compound content, and the surrounding environment and materials that come into contact with it. As a result, the present invention has been completed.

That is, in the present invention, the polyhydric alcohol component containing 30% by mass or more of the dialcohol having 3 or less carbon atoms in the main chain and any one or more of dimer acid, isophthalic acid, terephthalic acid, and succinic acid is 30% by mass or more. A total volatile organic compound obtained by using a polyester polyol obtained by subjecting a polyvalent carboxylic acid component to a condensation reaction to a polyester polyol having a volatile by-product of 100 ppm or less in terms of a toluene calibration curve The present invention relates to a polyester polyurethane molded product with a small amount.

If the polyester polyurethane molded product of the present invention is used, the total amount of volatile organic compounds can be reduced, so that it is difficult to contaminate the surrounding environment and the substance to be contacted, and can be used in many industrial fields such as automobile interior parts and clean room members. .

BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the dialcohol may be a compound having 3 or less carbon atoms in the main chain, such as ethylene glycol, 1,3-propanediol, 1,2-propylene glycol, 2-methyl-1,3-propane. Diol, 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, neopentyl glycol, 2-normalbutyl-2-ethyl-1,3-propanediol, and the like. It can be used alone or in combination of two or more.

The above-mentioned dialcohol having 3 or less carbon atoms in the main chain needs to be 30% by mass or more in the total polyhydric alcohol component. If the amount is less than 30% by mass, the amount of volatile by-products in the obtained polyester polyol increases, and the total amount of volatile organic compounds in the polyester polyurethane molded product using the obtained polyester polyol increases. . As the polyhydric alcohol component, other polyhydric alcohols can be used in combination as long as the effects of the present invention are not impaired.

Other polyhydric alcohols that can be used in combination may be those generally used for polyester polyols, such as 1,4-butylene glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, Examples include dialcohols such as dimer diol, and polyfunctional alcohols such as glycerin, trimethylolpropane, and pentaerythritol.

In the present invention, by using 30% by mass or more of any one or more of dimer acid, isophthalic acid, terephthalic acid, and succinic acid as the constituent polyvalent carboxylic acid component, the amount of volatile by-products generated is reduced. As the polyvalent carboxylic acid component, other polyvalent carboxylic acids used in general polyester polyols can be used in combination as long as the effects of the present invention are not impaired.

The dimer acid used in the present invention is a carboxylic acid obtained by polymerization of vegetable fatty acids obtained from sap or cereal. As the vegetable fatty acid, a mixture of an unsaturated acid such as oleic acid or linoleic acid and stearic acid is used. The carboxylic acid obtained by polymerization is mainly composed of a dibasic acid having 36 carbon atoms, and a small amount of monobasic acid (monomer acid) having 18 carbon atoms and tribasic acid having 54 carbon atoms (trimer acid). Although it contains, the ratio of these components will not be specifically limited if the effect of this invention is achieved. It is also possible to use hydrogenated dimer acid obtained by further hydrogenation of dimer acid.

Examples of other polycarboxylic acids that can be used in combination include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and 1,4-cyclohexane. And dicarboxylic acid. In addition, aromatic dicarboxylic acids include, for example, orthophthalic acid, naphthalenedicarboxylic acid and the like, but it is of course possible to use anhydrides or various derivatives thereof, and these may be used alone or as a mixture of two or more. .

There is no restriction | limiting in particular about the manufacturing method of polyester polyol, The conventionally well-known manufacturing method of polyester polyol can be used. For example, a method of esterifying the above-mentioned polyhydric alcohol and polyvalent carboxylic acid under normal pressure, a method of performing an esterification reaction under vacuum, an esterification reaction in the presence of an inert solvent such as toluene, and condensation. A method of removing water out of the reaction system by azeotropic distillation with a solvent can be used.

The above esterification reaction can be carried out even in the absence of a catalyst, but usually the polycondensation catalyst includes antimony, germanium, tin, titanium, zinc, aluminum, magnesium, calcium, in order to make the esterification reaction proceed smoothly. Further, a metal compound such as manganese or cobalt, or an organic sulfonic acid compound such as sulfosalicylic acid can be appropriately selected and used. In this case, the amount of the catalyst added is in the range of about 0.0001% by mass to 2% by mass, preferably about 0.0005% by mass to 1.0% by mass, based on the total mass of the raw materials used. Is within the range. The reaction temperature is preferably 160 ° C to 250 ° C.

The number average molecular weight of the polyester polyol of the present invention is preferably in the range of 500 to 4000, particularly preferably in the range of 700 to 3000. When the number average molecular weight of the polyester polyol is 500 to 4,000, the synthesis of the polyester polyol itself is easy, and it has a merit that it has a moderate viscosity and is excellent in workability, resulting in a uniform polyester polyurethane molded product. .

The GC / MS measurement specified in the present invention is performed by a heat desorption-GC / MS apparatus, and a test piece (0.030 g weighed) placed in a sample tube is heated at 120 ° C. for 30 minutes by the heat desorption apparatus, and the generated volatilization occurs. After concentrating the organic compound in the trap adsorption tube, it is introduced into the analytical column of the GC-MS apparatus and measured. As the heat desorption apparatus, TurboMatrix ATD manufactured by PerkinElmer is used. Moreover, as a GC / MS apparatus, what corresponds to JISK0123 may be used, but a micropolar column (5% diphenyl 95% dimethylpolysiloxane) is used as an analytical column.

As conditions for the thermal desorption apparatus, Tenax-TA is used as the trap adsorbent, the trap temperature is −30 ° C., and the desorption temperature is 300 ° C. As conditions for the GC / MS apparatus, the mass range is m / z 33 to 400, the oven temperature is maintained at 80 ° C. for 5 minutes, the temperature is increased to 260 ° C. at a temperature increase rate of 10 ° C./minute, and then maintained for 10 minutes.

In the present invention, the volatile by-product is a by-product generated in the production process of polyester polyol, and reacts with isocyanate among organic compounds detected by volatilization from polyester polyol under the GC / MS measurement conditions specified in the present invention. Thus, the starting material for forming the polyester polyurethane molded product is obtained by removing the polyhydric alcohol and the low molecular polyol. Examples of these volatile by-products include low molecular weight cyclic esters, polyhydric alcohol decomposition products, and cyclic ethers. Further, the volatile organic compound is an organic compound detected by volatilization from a polyester polyurethane molded product under the GC / MS measurement conditions specified in the present invention, and the above-mentioned volatile by-product contained in the polyester polyol, and The volatile by-product etc. which arise in the manufacturing process of the polyester polyurethane molded article obtained using this polyester polyol are mentioned.

In the present invention, the amount of volatile by-products excludes polyhydric alcohol and low molecular weight polyol as starting materials from signals of total ion chromatogram detected from polyester polyol under the GC / MS measurement conditions specified in the present invention. This is a value obtained by converting the total signal area using a toluene calibration curve. On the other hand, the total amount of volatile organic compounds is a value obtained by converting the sum of the signal areas of the total ion chromatogram detected from the polyester polyurethane molded product under the GC / MS measurement conditions defined in the present invention into a toluene calibration curve. A calibration curve for toluene was prepared from a total ion chromatogram obtained when GC / MS measurement was performed by injecting toluene diluted with methanol into a sample tube filled with glass wool.

The polyester polyol of the present invention needs to have a volatile by-product amount of 100 ppm or less in terms of a toluene calibration curve. When the amount of volatile by-products is 100 ppm or less in terms of a toluene calibration curve, the total amount of volatile organic compounds in the obtained polyester polyurethane molded product is reduced.

The polyester polyurethane molded product of the present invention is a polyisocyanate and, if necessary, a chain extender, a foaming agent, a foam stabilizer, a catalyst, a surfactant, a pigment, a dye, a flame retardant, a stabilizer, and a filler. It is obtained by adding an agent, a plasticizer, an aggregate and the like to react and forming into a desired shape such as a film, a sheet, or a foam.

Examples of the polyisocyanate that can be used in the present invention include 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate or a mixture thereof, m- or p-phenylene diisocyanate, p-xylene diisocyanate, ethylene diisocyanate, tetramethylene. -1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 4,4′-biphenylene diisocyanate or 1,5-naphthalene diisocyanate, tolidine diisocyanate, Ifosolone diisocyanate, cyclohexane diisocyanate, toluidine diisocyanate, crude diphenylmethane diisocyanate, diphenylmethane diisocyanate, tri It is E methane triisocyanate and these various derivatives.

These polyisocyanates may be used in combination, and are not limited thereto. These polyisocyanates are selected according to the desired physical properties of the molded product.

Polyester urethane molded articles may be produced by various methods such as a one-shot method and a prepolymer method using the above raw materials. The one-shot method is a method in which a polyol component and polyisocyanate are reacted in the presence of other additives such as a catalyst, a foaming agent, and a foam stabilizer. In the prepolymer method, a polyol component and a polyisocyanate are reacted in advance to obtain a kind of prepolymer, and then, for example, when a urethane foam is produced, this is reacted in the presence of a foaming agent, a catalyst, a foam stabilizer and other additives. When the elastomer is produced, a chain extender or a polyol component is added to the prepolymer to cause a crosslinking reaction.

Furthermore, in addition to the bulk polymerization method in which various components are reacted in a molten state, the urethane reaction can be carried out by using dimethylformamide, diethylformamide, dimethylsulfoxide, dimethylacetamide, tetrahydrofuran, cyclohexanone, methyl ethyl ketone, isopropanol, toluene, xylene, ethyl cellosolve, trichlene, etc. A solution polymerization method carried out in a solvent comprising two or more species can also be used.

In obtaining the polyester polyurethane molded article of the present invention, other polyester polyols, polycaprolactone polyols, polyether polyols, polycarbonate polyols, etc. may be combined with the polyester polyol shown in claim 1 as long as the effects of the present invention are not impaired. You may use together. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of the polycarbonate polyol include polycarbonate polyol obtained by deethanol condensation reaction of polyhydric alcohol and diethyl carbonate, dephenol condensation reaction of polyhydric alcohol and diphenyl carbonate, or deethylene glycol reaction of polyhydric alcohol and ethylene carbonate. .

In producing the polyester polyurethane molded article of the present invention, a catalyst, a filler, an antistatic agent, a colorant, a flame retardant and the like can be added according to the required performance.

Since the present invention can provide a polyester polyurethane molded product having a greatly reduced total volatile organic compound amount compared to conventional polyester polyurethane molded products, it is an industry that is disliked with contamination of building materials, automobile interior parts, clean room members, etc. Can be used in the field.

Next, although the synthesis example and Example of this invention are demonstrated, it is not limited to these. In the text, “part” and “%” are based on mass.

<Quantification of volatile by-products and total volatile organic compounds>
The amount of volatile by-products of the polyester polyol and the total amount of volatile organic compounds of the polyester polyurethane molded product were measured under the GC / MS measurement conditions specified in the present invention. At this time, the amount of volatile by-products is obtained as a toluene calibration curve equivalent of the total signal area excluding the polyhydric alcohol and low-molecular polyol as starting materials from the signals of the obtained total ion chromatogram. For the total amount of volatile organic compounds, the total signal area of the obtained total ion chromatogram is obtained as a toluene calibration curve equivalent.
Thermal desorption-GC / MS analyzer:
PerkinElmer TurboMatrix ATD-
Shimadzu Corporation GC / MS-QP5050A
[TurboMatrix ATD condition]
Sample tube heating temperature: 120 ° C. Sample tube heating time: 30 minutes Desorption flow rate: 20 mL / min Inlet split: 20 mL / min Trap adsorbent: Tenax-TA Trap temperature: −30 ° C.
Trap desorption temperature: 300 ° C. Outlet split: 10 mL / min [GC / MS-QP5050A conditions]
Column: 0.25 mm × 60 m × 0.25 μm GL Science Co. TC-5
(5% diphenyl 95% dimethylpolysiloxane)
Oven temperature: 80 ° C (5 minutes)-(10 ° C / minute)-260 ° C (10 minutes)
Mass range: m / z 40-350

Synthesis Example 1 344 parts of 2-methyl-1,3-propanediol, 1757 parts of dimer acid and 0.05 part of tetrabutyl titanate as a catalyst were charged, and condensed water was allowed to flow out at about 200 ° C. while passing nitrogen gas under normal pressure. The polyester polyol having an acid value of 0.3 mgKOH / g, a hydroxyl value of 56.2 mgKOH / g, and a volatile by-product amount of 10 ppm was obtained.

Synthesis Example 2 439 parts of 2-methyl-1,3-propanediol, 720 parts of terephthalic acid and 0.05 part of tetrabutyl titanate as a catalyst were charged, and a polyester polyol was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 3 Polyester polyol was obtained in the same manner as in Synthesis Example 1, except that 439 parts of 2-methyl-1,3-propanediol, 720 parts of isophthalic acid, and 0.05 part of tetrabutyl titanate as a catalyst were charged.

Synthesis Example 4 548 parts of 2-methyl-1,3-propanediol, 655 parts of succinic acid, and 0.05 part of tetrabutyl titanate as a catalyst were charged, and a polyester polyol was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 5 Synthesis of 416 parts of 2-methyl-1,3-propanediol, 184 parts of dimer acid, 184 parts of terephthalic acid, 184 parts of isophthalic acid, 184 parts of succinic acid, and 0.05 part of tetrabutyl titanate as a catalyst A polyester polyol was obtained in the same manner as in Example 1.

Synthesis Example 6 392 parts of 2-methyl-1,3-propanediol, 374 parts of dimer acid, 374 parts of succinic acid, and 0.05 part of tetrabutyl titanate as a catalyst were added, and polyester polyol was prepared in the same manner as in Synthesis Example 1. Obtained.

Synthesis Example 7 478 parts of 2-methyl-1,3-propanediol, 697 parts of adipic acid and 0.05 part of tetrabutyl titanate as a catalyst were charged, and a polyester polyol was obtained in the same manner as in Synthesis Example 1.

Synthesis Example 8 Polyester polyol was obtained in the same manner as in Synthesis Example 1, except that 384 parts of 2-methyl-1,3-propanediol, 753 parts of sebacic acid and 0.05 of tetrabutyl titanate were added as a catalyst.

Synthesis Example 9 462 parts of 3-methyl-1,5-pentanediol, 332 parts of dimer acid, 332 parts of succinic acid, and 0.05 part of tetrabutyl titanate as a catalyst were added, and polyester polyol was prepared in the same manner as in Synthesis Example 1. Got.

Example 1 10 parts of TDI-80 was added to 100 parts of the polyester polyol obtained in Synthesis Example 1, and after stirring, put in a mold and aged at 80 ° C. for 24 hours to produce a polyurethane cured product of 30 mm × 30 mm × 30 mm. A test piece was prepared from the central portion of the obtained polyurethane cured product, and the total amount of volatile organic compounds was determined.

Example 2 Total volatile organic compounds were quantified in the same manner as in Example 1 except that 100 parts of the polyester polyol obtained in Synthesis Example 2 was used as the polyol.

Example 3 Total volatile organic compounds were quantified in the same manner as in Example 1 except that 100 parts of the polyester polyol obtained in Synthesis Example 3 was used as the polyol.

Example 4 Total volatile organic compounds were quantified in the same manner as in Example 1 except that 100 parts of the polyester polyol obtained in Synthesis Example 4 was used as the polyol.

Example 5 Total volatile organic compounds were quantified in the same manner as in Example 1 except that 100 parts of the polyester polyol obtained in Synthesis Example 5 was used as the polyol.

Example 6 Total volatile organic compounds were quantified in the same manner as in Example 1 except that 100 parts of the polyester polyol obtained in Synthesis Example 6 was used as the polyol.

Comparative Example 1 The total volatile organic compounds were quantified in the same manner as in Example 1 except that 100 parts of the polyester polyol obtained in Synthesis Example 7 was used as the polyol.

Comparative Example 2 Total volatile organic compounds were quantified in the same manner as in Example 1 except that 100 parts of the polyester polyol obtained in Synthesis Example 8 was used as the polyol.

Comparative Example 3 Total volatile organic compounds were quantified in the same manner as in Example 1 except that 100 parts of the polyester polyol obtained in Synthesis Example 9 was used as the polyol.

Synthesis Examples 1 to 6 which are polyester polyols corresponding to claim 1 have a small amount of volatile by-products, and Examples 1 to 6 which are polyester polyurethane molded articles obtained using these are total volatile organic compounds. It was confirmed that the amount was small.

Claims (1)

Polyhydric alcohol component containing 30% by mass or more of a dialcohol having 3 or less carbon atoms in the main chain and dimeric acid, isophthalic acid, terephthalic acid, or succinic acid alone or more than 30% by mass Polyester polyurethane having a low total volatile organic compound content obtained by using a polyester polyol which is a polyester polyol obtained by a condensation reaction with an acid component and has a volatile by-product of 100 ppm or less in terms of a toluene calibration curve Molding.