WO2006070503A1 - Polyester polyol, and polyurethane and polyurethane foam using the same - Google Patents

Abstract

This invention provides a polyester polyol that, when used as a starting polyol for polyurethane, particularly a polyurethane foam, has low viscosity and is easy to handle, and has high compatibility with foaming agents, particularly HFC foaming agents such as HFC-245fa, HC foaming agents such as pentane and cyclopentane, and water, and, at the same time, can improve the strength of bonding to adherends. A polyester polyol produced by an esterification reaction of a carboxylic acid component and an alcohol component. In this case, succinic acid is used as at least a part of the carboxylic acid component, and triethylene glycol is used as at least a part of the alcohol component.

Description

 Polyester polyol, polyurethane and polyurethane foam using the same

 Technical field

 [0001] The present invention relates to a polyester polyol. Specifically, low viscosity and easy handling

Polyurethane, in particular, a polyester polyol that exhibits excellent compatibility with a foaming agent when used as a raw material for polyurethane foam and can improve the adhesive strength between the obtained polyurethane foam and an adherend. Is.

 Background art

 [0002] Polyurethane foam has excellent heat insulation properties, and is therefore widely used in refrigerators, refrigerators, freezer rooms, freezers, heat insulating materials for general buildings, and the like. Polyurethane foam is generally a mixture of a polyisocyanate component liquid (hereinafter abbreviated as A liquid), polyether polyol and Z or polyester polyol, foaming agent, and if necessary, a catalyst or foam stabilizer. A liquid (hereinafter abbreviated as B liquid) is prepared, and A liquid and B liquid are mixed, and foamed and hardened in a short time. For this reason, polyester polyols are required to have low viscosity and easy handling in addition to high compatibility with foaming agents.

 [0003] As the foaming agent, a low-boiling nonpolar organic solvent is generally used. Specifically, in addition to the HCFC-based foaming agent, HC-based foaming agents such as pentane and cyclopentane are used. In addition, depending on the application and the production conditions of polyurethane foam, there are practical problems with HC foaming agents having a low flash point and explosive properties, and HCFC foaming agents are frequently used.

 [0004] On the other hand, CFC-based blowing agents that have been widely used since the ozone layer devastation became a problem, especially HCFC-based blowing agents with a low ozone depletion potential, especially HCFC-14 lb Is currently being used as an alternative! However, this HCFC-14 lb also has a zero ozone destruction factor, and its use has been restricted since the end of 2003. As an alternative, HFC-based foaming agents, especially HFC-245fa, are envisaged. Agents and water are also promising blowing agents.

[0005] As a common problem when using these blowing agents that are expected to be used now and in the future Thus, the compatibility between the polyether polyol and the polyol component, which are the main components of the B liquid, and the polyol component such as Z or polyester polyol is poor. In particular, HFC foaming agents such as HFC-245fa, poor compatibility with HC foaming agents such as pentane and cyclopentane, and water, which are assumed as substitutes for HCFC foaming agents. This is a limitation of the configuration.

 [0006] Furthermore, the foaming formulation using a foaming agent such as an HFC-based foaming agent, HC-based foaming agent, water, etc. is more effective than the conventional foaming formulation using an HCFC-based foaming agent. Compatibility. Due to low dispersibility, reactivity and foaming efficiency decrease (densification), surface finish of molded product, poor foam strength, reduced foam strength, dimensional stability, especially adhesion It tends to cause a decrease in adhesion strength with the member. Also, in areas where heat insulation performance is required, thermal conductivity deteriorates due to cell roughening, and in low-temperature spraying construction, adhesion strength decreases, delamination, and dripping easily occur due to poor compatibility. . This tendency is particularly noticeable when only water is used as the blowing agent.

 [0007] On the other hand, prescriptions using HFC-based foaming agents and HC-based foaming agents are also being studied for formulations that incorporate a large amount of water for environmental considerations and cost reduction. Water and polyisocyanate The increase in urea groups generated by reaction with the components increases the flyability of polyurethane foam, and further causes a decrease in adhesive strength.

 [0008] Various studies have been made so far in order to solve these problems, particularly the poor compatibility with the foaming agent and the decrease in the adhesive strength with the adherend. For example, various compatibilizers (Patent Document 1) having a certain surface active effect for improving compatibility have recently been proposed. However, since most of these compatibilizers are usually compounds that do not have a hydroxyl group, even if they contribute to improving the compatibility with the foaming agent as an auxiliary component of the liquid B, the urethanization reaction Therefore, it may be present in the polyurethane foam as it is, and its physical properties, particularly strength, heat resistance, adhesive strength, etc. may be significantly deteriorated. Therefore, in order to solve the low compatibility between the blowing agent and the liquid B, it is extremely important in practice to be a compound that functions as a polyol having a hydroxyl group in the molecule as well as improving the compatibility. Conceivable.

[0009] Further, methods for improving the adhesive strength and dimensional stability with the adherend have been studied, for example, A method using polyether polyol in which ethylenediamine / propylene oxide is added to tolylenediamine, triethanolamine, glycerin, ethylenediamine as an initiator (Patent Document 2), or dialkylene of oxyethylene and Z or oxypropylene glycol There is a method (Patent Document 3) using an auxiliary agent having no hydroxyl group such as ether.

 Patent Document 1: JP 2004-107439

 Patent Document 2: JP-A-6-316621

 Patent Document 3: JP 2002-363241

 Disclosure of the invention

 Problems to be solved by the invention

 [0010] However, with these methods, the effect of improving the adhesive strength is small if the addition amount is small, and the cost is disadvantageous if the addition amount is large, and the flame retardancy of the polyurethane foam is reduced. Adverse effects occur.

 [0011] Therefore, instead of using these additives, a polyester polyol having a hydroxyl group, having a stronger cohesive force between molecules than polyether polyol, and causing no reduction in flame retardancy, If it is possible to provide a polyester polyol that has good compatibility with the polyurethane foam and improves the adhesive strength between the polyurethane foam and the adherend, an appropriate amount of it can be used as a part of the polyol component to obtain a liquid B with good uniform stability. In addition, it is expected that a polyurethane foam having excellent physical properties can be obtained.

 Means for solving the problem

 [0012] As a result of intensive studies by the present inventors to solve these problems, succinic acid is used as at least a part of the carboxylic acid component, which is a raw material for producing polyester polyol, as at least a part of the alcohol component. By using a specific amount of each of triethylene glycol, it was found that a polyester polyol having good compatibility with the blowing agent and improving the adhesive strength between the polyurethane foam and the adherend was obtained. It was.

[0013] The polyester polyol obtained by the present invention is incorporated into the polyurethane molecule as one component of the polyurethane, similarly to the conventionally used polyester polyol, so that the physical properties of the polyurethane are not impaired. Demonstrate the above characteristics Can do.

 That is, this invention has the summary characterized by the following.

 (1) A polyester polyol obtained by subjecting a carboxylic acid component and an alcohol component to an esterification reaction, using succinic acid as at least a part of the carboxylic acid component, and triethylene glycol as at least a part of the alcohol component. A polyester polyol characterized by being used.

 (2) The above-mentioned (1) characterized in that the amount of succinic acid used is 30% by weight or more in the full strength rubonic acid component, and the amount of tritendendralol used is 30% by weight or more in all alcohol components. ) Polyester polyols.

 (3) The above-mentioned (2) characterized in that the amount of succinic acid used is 50% by weight or more in the full strength rubonic acid component, and the amount of tritendender alcohol used is 50% by weight or more in all alcohol components. ) Polyester polyols.

 (4) The polyester polyol according to any one of (1) to (3) above, wherein the viscosity is 30000 mPa · s or less.

 (5) The polyester polyol according to any one of the above (1) to (4), wherein the acid value is 1 OmgKOHZg or less.

 (6) A polyurethane obtained by reacting a polyol component containing the polyester polyol according to any one of (1) to (5) above and a polyisocyanate component.

 (7) A polyurethane obtained by reacting a polyol component containing the polyester polyol according to any one of (1) to (5) above and a polyisocyanate component in the presence of a foaming agent. Form.

 (8) The above (6) is characterized in that the amount of the polyester polyol described in any one of (1) to (5) is 1% by weight or more and 50% by weight or less in the total polyol component. The polyurethane described in the above or the polyurethane foam described in (7) above.

 (9) The polyurethane foam as described in (7) or (8) above, wherein a foaming agent having an ozone depletion coefficient of 0.8 or less is used.

(10) The polyurethane foam according to (7), (8) or (9), wherein the foaming agent is one or more foaming agents selected from the group consisting of HFC foaming agents, HC foaming agents and hydraulic power. . The invention's effect

 [0015] According to the present invention, as a raw material polyol for polyurethane, particularly polyurethane foam, in addition to low viscosity and easy handling, blowing agents, particularly HFC-based blowing agents such as HFC-245fa, pentane, cyclohexane It is possible to provide a polyester polyol capable of improving the adhesive strength between a polyurethane foam obtained by increasing compatibility with water and an HC foaming agent such as pentane and water and an adherend. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. The polyester polyol in the present invention is preferably a polyester polyol used for polyurethane, particularly a polyurethane foam, and is a polyester polyol obtained from a carboxylic acid component and an alcohol component.

 In the present invention, it is essential to use succinic acid as at least a part of the carboxylic acid component that is a raw material of the polyester polyol. The amount of succinic acid used is usually 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more of the total carboxylic acid component, and the total amount of the carboxylic acid component may be succinic acid. If the amount of succinic acid used is less than 30% by weight of the total carboxylic acid component, the effect of improving the compatibility with the foaming agent and improving the adhesive strength with the adherend is small. The succinic acid of the present invention includes succinic anhydride, and instead of succinic acid, methanol, ethanol,

For example, dimethyl succinic acid or the like esterified with a monoalcohol having 1 to 8 carbon atoms such as 2-ethylhexanol may be used. The amount used in these cases shall be calculated based on the weight converted to succinic acid.

[0018] Examples of the carboxylic acid used when the total amount of the carboxylic acid component is not succinic acid include aliphatic dicarboxylic acids other than succinic acid, and aliphatic polycarboxylic acids such as aliphatic tricarboxylic acids. Suitable aliphatic polycarboxylic acid components include dartaric acid, adipic acid, fumaric acid, maleic acid, and acid anhydrides thereof. Aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid may be used as carboxylic acids other than these aliphatic polycarboxylic acids. Of these carboxylic acid components other than succinic acid, phthalic acid and adipic acid are particularly preferred. These carboxylic acids are Those obtained by esterification with a monoalcohol having 1 to 8 carbon atoms such as ethanol, ethanol and 2-ethylhexanol, such as dimethyl terephthalic acid, may be used. These carboxylic acid components used in addition to succinic acid can be used alone or in admixture of two or more.

 In the present invention, it is essential to use triethylene glycol as at least a part of the alcohol component that is a raw material of the polyester polyol. The amount of triethylene glycol used is usually 30% by weight or more of the total alcohol component, preferably 40% by weight or more, and more preferably 50% by weight or more. The total amount of the alcohol component may be triethylene glycol. If the amount of triethylene glycol used is less than 30% by weight of the total alcohol component, the effect of improving the compatibility with the foaming agent and the adhesive strength with the adherend will be small, and the adverse effect such as a marked increase in viscosity will be caused. Since it may occur, it is not preferable.

 [0020] The alcohol used when the total amount of the alcohol component is not triethylene glycol is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2 butanediol, 1,3 butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, dioxane such as cyclohexanedimethanol, and triols such as glycerin and trimethylolpropane . Other usable alcohol components include long-chain polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxyethylene Z-oxypropylene copolymer dallicol, and polytetramethylene ether dallicol. These alcohol components other than triethylene glycol can be used alone or in admixture of two or more.

[0021] The viscosity of the polyester polyol is preferably 30000 mPa's or less, particularly 2500 OmPa · s or less! / ヽ. As a method for lowering the viscosity of the polyester polyol to 30000 mPa · s or less, monools such as methanol, ethanol, isopropanol, 2-ethylhexanol and the like can be used. However, when these monools are used, they may be distilled out of the reaction system in the synthesis of polyester polyols, resulting in poor yields and adversely affecting the strength and heat resistance of polyurethane. Practical questions It is preferred to use in a range, not the subject.

[0022] In the esterification reaction in the present invention, an esterification catalyst is usually used.

In general, an acid catalyst is often used as the catalyst. Examples of the Lewis acid include orthotitanate esters such as tetraisopropyl titanate and tetra _n -butyl titanate, tin compounds such as jetyl tin oxide and dibutyl tin oxide, and metal compounds such as zinc oxide. In addition to the Lewis acid, a Bronsted acid such as p-toluenesulfonic acid may be used.

[0023] On the other hand, the obtained polyester polyol has a urethane reaction with the polyisocyanate component to form a polyurethane. At this time, the catalytic force used in the synthesis of the polyester polyol has an influence on the reaction behavior of the urethane reaction. Preferably not. Therefore, among the esterification catalysts described above, the preferred amount of orthotitanate used is usually 1.0% by weight or less, preferably with respect to the total of the carboxylic acid component and alcohol component used as raw materials. Is not more than 0.2% by weight, usually not less than 0.01% by weight, preferably not less than 0.03% by weight. Depending on the use of polyurethane, the reaction may be performed without using these ester catalysts.

In the production of the polyester polyol of the present invention, the ratio of the carboxylic acid component and the alcohol component used depends on the hydroxyl value, viscosity, number average molecular weight, etc. of the target polyester polyol. The equivalent of the hydroxyl group of the alcohol component to 1 equivalent of the group is usually 1.05 equivalent or more, preferably 1.1 equivalent or more, more preferably 1.2 equivalent or more, usually 4.0 equivalent or less, preferably 3. 0 equivalent or less, more preferably 2.5 equivalent or less. If this value is too small, the hydroxyl groups in the polyester polyol are significantly reduced, and there is a risk that the polyurethane foam obtained by urethanation with the polyisocyanate component will have a significant adverse effect on the strength and heat resistance of the polyurethane foam. . On the other hand, if this value is too large, a large amount of free alcohol components that have not been subjected to esterification reaction remain in the polyester polyol. If the polyester polyol obtained in this way is used, the strength and heat resistance of the rigid polyurethane foam obtained by further reacting with the polyisocyanate component and urethane can be significantly affected. is there. [0025] The reaction temperature in the production of the polyester polyol of the present invention is usually 150 ° C or higher, preferably 180 ° C or higher, and usually 250 ° C or lower, preferably 230 ° C or lower. For example, the reaction is easy to control if the reaction is started at 150 ° C and the temperature is gradually raised to 230 ° C as the reaction proceeds. On the other hand, the reaction pressure may be normal pressure, but it may be gradually reduced as the reaction proceeds to remove by-product water out of the system and complete the reaction quickly. However, if the degree of pressure reduction during the reaction is insufficient, the degree of completion of the esterification reaction is lowered, and a polyester polyol having a high acid value is produced. On the other hand, if the pressure is excessively reduced during the reaction, the alcohol component is distilled out of the system and the yield is deteriorated. A high-molecular weight polyester polyol is formed, the viscosity of the resulting polyester polyol is remarkably increased, and foaming is performed. It may also show a tendency to reduce compatibility with the agent. Accordingly, the appropriate ultimate reaction pressure varies depending on the reaction temperature.For example, when the reaction temperature is 200 ° C, the pressure is usually 2 kPa or more, preferably 5 kPa or more, and usually 50 kPa or less, preferably 30 kPa. Although it is as follows, the reaction may be performed under conditions other than the above pressure range depending on the viscosity and hydroxyl value of the target polyester polyol, the type of alcohol used, and the amount used. Instead of reducing the pressure, a small amount of an organic solvent such as toluene or xylene may be used in combination, and the by-produced water may be removed azeotropically from the system.

 [0026] The end point of the reaction in the production of the polyester polyol of the present invention is usually determined by the amount of unreacted carboxyl groups of the polyvalent carboxylic acid used in the case of polyester polyol. On the other hand, in the use of polyurethane, the presence of an acid in many cases is not preferable, such as a decrease in reactivity, with respect to a urethanization reaction with a polyisocyanate component. Therefore, it is preferable for the polyester polyol that the amount of unreacted carboxylic acid, that is, the acid value is as low as possible. In the use of rigid polyurethane foam, the acid value is usually 10 mgKOHZg or less, preferably 5 mgKOHZg or less, more preferably 3 mgKOHZg or less. Also, under severe urethane reaction conditions, lmgKOHZg or less may be desired.

[0027] The polyester polyol obtained as described above is usually an ester compound having a structure having a carboxylic acid component and an alcohol component, and an unreacted alcohol component. And become mosquitoes. In the polyester polyol obtained in the present invention, the average number of functional groups of the ester compound is usually 1.0 or more, preferably 1.5 or more, and more preferably 2.0 or more. If the average number of functional groups of the ester compound is too small, the degree of polymerization of the polyurethane obtained by urethanation reaction with the polyisocyanate component is further reduced. For example, in the case of polyurethane foam, strength and heat resistance are remarkably increased. May be exacerbated.

 [0028] Also, in order to keep the average number of functional groups of the ester compound at a constant target value and to keep Z or the average molecular weight constant, an alcohol component that is in an equilibrium state with the transesterification reaction during the esterification reaction is added. It is important not to distill out of the reaction system as much as possible. If the alcohol component is distilled too much, the average number of functional groups of the ester compound will differ from the original product design, the average molecular weight will increase, and the resulting polyester polyol will have a significant viscosity. It is not desirable to grow large. Therefore, the amount of the alcohol component distilled out of the system during the esterification reaction is usually 5% or less, preferably 3% or less, more preferably 1% or less, based on the total alcohol components. However, depending on the viscosity and hydroxyl value of the target polyester polyol and the amount of alcohol component used, the alcohol component may be distilled out beyond the above range. The desirable number average molecular weight of the polyester polyol of the present invention is generally in the range of 300 to 3000, more preferably in the range of 500 to 2000, depending on the intended use.

 [0029] At the start of the reaction, it is preferable to replace the space of the reaction vessel with nitrogen in order to prevent coloring of the produced polyester polyol, and also to remove dissolved oxygen in the reaction solution. Further, after completion of the reaction, the physical properties and performance of the polyester polyol may be adjusted by distilling off the unreacted free alcohol component outside the system under an appropriate reduced pressure condition.

 [0030] The reaction mode of the polyester polyol in the present invention is a force that can be applied to normal batch equipment or continuous equipment. The reaction time takes a long time, and the viscosity of the obtained polyester polyol is compared with the alcohol component used as a raw material. Therefore, the reaction by notch equipment is preferable.

[0031] The polyester polyol obtained according to the present invention is preferably used in a polyurethane obtained by reacting a polyol and a polyisocyanate component, particularly in a polyurethane foam. In addition to low viscosity and easy handling, foaming agents with an ozone depletion coefficient of 0.8 or less, especially HFC-based foaming agents such as HFC-245fa to be used in the future, and HC-based systems such as pentane and cyclopentane It is useful as a polyester polyol having high compatibility with a foaming agent such as a foaming agent and water.

 [0032] The polyurethane foam is composed of a liquid A composed of a polyisocyanate component, a polyol component such as polyether polyol and Z or polyester polyol, a foaming agent, a catalyst and a foam stabilizer, and other components as necessary. Manufactured by mixing, foaming, and curing the liquid B containing additives and auxiliaries in a short time.

 [0033] The polyisocyanate component is not particularly limited as long as it is an organic compound having two or more isocyanate groups in one molecule. Examples thereof include aliphatic, alicyclic or aromatic polyisocyanates and modified products thereof. Specifically, examples of the aliphatic or alicyclic polyisocyanate include hexamethylene diisocyanate and isophorone diisocyanate. Examples of aromatic polyisocyanates include tolylene diisocyanate, diphenylmethane diisocyanate, and polyphenylene-polymethylene polyisocyanate, and also include modified products such as these carpositimide modified products and prepolymers. .

 [0034] Preferably, the polyisocyanate component in the present invention is an aromatic polyisocyanate or a modified product thereof, particularly preferably diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate. , Tolylene diisocyanate, and modified products thereof. These may be used alone or in combination. As the polyphenylene-polymethylene polyisocyanate, those having an isocyanate group content of usually 29 to 32% by weight and a viscosity of usually 250 mPa's (25 ° C.) or less are used. Among these modified products, the carbodiimide modified product is a product obtained by introducing a carbopositimide bond using a known phosphorus catalyst or the like. Prepolymers are those obtained by reacting the above polyisocyanate with a polyol, leaving an isocyanate group at the end. As the polyol used at that time, the polyol used in the production of polyurethane can be usually used.

[0035] In addition to these polyisocyanates, additives and auxiliaries may be mixed with the polyisocyanate component and used depending on the application. For example, for the purpose of improving the mixing with B liquid In some cases, the foam stabilizer used in the B liquid is also used as a compatibilizer. In that case, normally, a silicone surfactant is often used as a nonionic surfactant is preferred. Moreover, a flame retardant may be used together for the purpose of improving flame retardancy and adjusting viscosity. In the use of polyurethane foam, black mouth alkyl phosphates, for example, tris (betachloroethinore) phosphate, tris (beta black mouth propinore) phosphate, etc. are often used. Additives and auxiliaries other than those mentioned above are not particularly limited, but are used for the purpose of improving physical properties and operability in ordinary rosin, and have an adverse effect on the urethane reaction. Otherwise, you can use anything.

 [0036] On the other hand, as the polyol component, generally, polyether polyols and polyester polyols having a hydroxyl value of usually 50 to 800 and a functional group power of 2 to 8 can be used. You may mix and use above.

 [0037] The polyether polyol may be a trifunctional or higher functional group such as ethylene oxide, propylene oxide, 1,2-butylene oxide, tetrahydrofuran, or a single alkylene oxide polymer, sucrose, sorbitol, glycerin or the like. And adducts of the above-mentioned polyhydric alcohols and the above-mentioned alkylenoxides, amines such as aliphatic amines and aromatic amines, and adducts of the above-mentioned alkylenoxides.

 [0038] As the polyester polyol, aromatic carboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid, and glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin and trimethylolpropane, Examples thereof include polyester polyols having a hydroxyl value of usually 200 to 400 and an average functional group number of usually about 2 to 3, which are obtained by esterification reaction, either alone or in combination.

[0039] In the present invention, it is important to use the above-described polyester polyol having the succinic acid and triethylene glycol power of the present invention in combination with these polyether polyols and polyester polyols. Succinic acid and triethylene glycol of the present invention The amount of the polyester polyol obtained is usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more, usually 50% in the total polyol component. % By weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. The

 [0040] In addition, compounds having two or more active hydrogens in one molecule such as alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerol, and alkanolamines such as triethanolamine are also used in combination. can do.

 [0041] As the foaming agent used in the polyurethane foam of the present invention, an ozone depleting coefficient is usually 0.8 or less, for example, in addition to HCFC-141b, HFC-based foaming agents such as HFC-245fa, pentane, HC foaming agents such as cyclopentane and foaming agents used in the future such as water can be preferably used because the compatibility of the polyester polyol of the present invention with these foaming agents is improved. These foaming agents may be used alone or in combination.

 [0042] As the catalyst used in the polyurethane foam of the present invention, known catalysts used for the production of ordinary urethane foams can be used. For example, in addition to amine catalysts such as triethylamine and N, N-dimethylhexylamine, metal catalysts such as tin catalysts such as dibutyltin dilaurate and tin octylate and lead catalysts such as lead octylate and the like can be mentioned.

 [0043] As the foam stabilizer used in the polyurethane foam of the present invention, a non-ionic surfactant, a ionic surfactant, or a force thione surfactant can be used, and a nonionic surfactant is particularly preferred. Silicone surfactants are often used. In addition, depending on the application, it may be used together as various compound strength additives and auxiliaries. For example, a flame retardant is mentioned as a typical additive. In the use of polyurethane foam, chloroalkyl phosphates such as tris (betachloroethyl) phosphate or tris (betaclopropylpropyl) phosphate are usually used. Additives and auxiliaries other than those mentioned above are not particularly limited and are used for the purpose of improving physical properties and operability in ordinary greaves. It can be used as long as it is not.

[0044] The specific procedure of the method for producing the polyurethane foam in the present invention is as follows. The above-mentioned polyisocyanate component is liquid A, the above-mentioned polyol component is liquid B, and a foaming agent, a catalyst, a foam stabilizer, other additives, etc. In this method, the liquid A is mixed with the liquid A and the liquid Z or B as appropriate, and the two liquids are mixed, foamed, and cured using an apparatus described later. In addition, foaming agent, touch It is better to mix the medium and foam stabilizer with B liquid.

 [0045] The polyurethane foam obtained by the present invention has a chemical bond such as a urethane bond or urea bond. Depending on the production conditions, an isocyanurate group can be generated during foaming. The isocyanurate group is generated by trimerizing the isocyanate group with a catalyst, and can improve mechanical strength and heat resistance.

 [0046] In the present invention! /, Preferred! /, Isocyanate index (number of moles of all isocyanate groups in the polyisocyanate component Z number of moles of all active hydrogen groups in the polyol X 100) is In the case of a so-called urethane foam, it is usually 70 or more, preferably 80 or more, more preferably 90 or more, usually 150 or less, preferably 140 or less, more preferably 130 or less. In the case of the so-called isocyanurate foam used, it is usually 150 or more, preferably 160 or more, more preferably 170 or more, and usually 800 or less, preferably 700 or less, more preferably 600 or less. If the isocyanate index is less than 70 for urethane foam and less than 150 for isocyanurate foam, the resulting foam may not have sufficient strength and is likely to shrink. If it exceeds 150 in this case, and more than 800 in the case of isocyanurate foam, the brittleness of the resulting foam increases and the adhesive strength tends to decrease, such being undesirable.

 [0047] In producing the urethane foam, any apparatus can be used as long as the liquid A and the liquid B can be mixed uniformly. For example, low pressure or high pressure foaming machines for injection foaming, low pressure or high pressure foaming for slab foaming, low pressure or high pressure foaming for continuous lines, used in the production of small mixers and general urethane foam. And spray foaming machines for spraying work can be used. In producing the urethane foam, it is preferable to adjust the temperature of each of the liquids A and B to 20 to 60 ° C.

 [0048] Specific examples of the present invention will be described below in more detail with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. Unless otherwise specified, “parts” and “%” in the examples mean “parts by weight” and “% by weight”, respectively.

 [Synthesis of Polyester Polyol for Polyurethane Foam]

The polyester polyol is synthesized and evaluated by the following method. Table 1 shows. (Examples 1 to 5 and Comparative Example 1)

[0049] "Example 1"

 A glass reactor with a volume of 2 liters equipped with a stirrer, reflux condenser, thermometer, pressure gauge, heating device, etc. was charged with cono, succinic acid 500 g, diethylene glycol 320 g, and triethylene glycol 320 g. After the space in the reactor was replaced with nitrogen gas, heating of the reactor internal material was started. When the reactor internal temperature reached 150 ° C, 0.5 g of tetraisopropyl titanate was added as a catalyst to the reactor to start the reaction.

 Thereafter, the internal temperature was raised to 210 ° C over 3 hours, and this temperature was maintained until the end of the reaction. On the other hand, the pressure in the reactor was maintained at 88. OkPa from the time when the internal temperature reached 150 ° C until the internal temperature reached 210 ° C. Thereafter, the pressure was gradually reduced for 3 hours to 5.3 kPa, and this pressure was maintained until the reaction was completed. It was visually observed that the reaction mixture became a homogeneous solution as the reaction progressed. While the reaction was in progress, a part of the reaction mixture was withdrawn from the reactor, and the acid value of each sample was measured and used as an indicator for confirming the progress of the reaction. The reaction was completed when the acid value became 1.0 or less and the reaction mixture became a homogeneous solution. After completion of the reaction, heating was stopped and the system was cooled to around 100 ° C., the reaction product was extracted, and the acid value, hydroxyl value, and viscosity of the extracted sample were measured.

 Further, the solubility of the foaming agent (HFC-245fa, cyclopentane, water) in the obtained polyester polyol was measured. The polyester polyol obtained here was designated as “Polyol 1”.

[0050] "Example 2"

 The reaction was conducted in the same manner as in the raw material of Example 1, except that 260 g of succinic acid, 300 g of diethylene glycol, 300 g of triethylene glycol, and 260 g of phthalic anhydride were used. The polyester polyol obtained here was designated as “Polyol 2”.

[0051] "Example 3"

 The reaction was carried out in the same procedure except that diethylene glycol was not used in the charged raw material of Example 1, but 440 g of succinic acid and 690 g of triethylene glycol were used. The polyester polyol obtained here was designated as “Polyol 3”.

[0052] "Example 4" The reaction was carried out in the same procedure except that diethylene glycol was not used in the charged raw material of Example 1 and succinic acid was changed to 40 4 g and triethylene glycol 719 g. The polyester polyol obtained here was designated as “Polyol 4”.

[Example 5]

 The reaction was conducted in the same manner as in the raw material of Example 1, except that diethylene glycol was not used, 412 g of succinic acid, 640 g of triethylene glycol, and 74 g of glycerin were used. The polyester polyol obtained here was designated as “Polyol 5”.

[0054] "Comparative Example 1"

 The reaction was carried out in the same manner as in the raw material of Example 1, except that succinic acid and triethylene glycol were not used, 570 g of phthalic anhydride and 500 g of diethylene glycol were used. The polyester polyol obtained here was designated as “Polyol 6”.

[0055] The polyester polyol obtained was evaluated by the following method, and the results are shown in "Table 1".

 <Evaluation method>

 (1) Acid value

 Measured according to JIS K1557.

 1970

 (2) Hydroxyl value

 Measured according to JIS K1557.

 1970

 (3) Viscosity

 According to JIS K1557, a rotational viscometer (B-type viscometer) was used and measured at 25 ° C.

 1970

 (4) Solubility of blowing agent in polyester polyol

 In a 200 ml beaker, take 30 to 50 g of polyester polyol, and in a release system at room temperature and atmospheric pressure, add a foaming agent gradually while stirring at 400 rpm using a 30φ three-way swept blade, and visually check for 30 seconds. The solubility obtained by measuring the maximum addition amount capable of forming a transparent homogeneous phase within the range was used as an indicator of the compatibility between the polyester polyol and the blowing agent.

[0056] [Table 1] table 1

 * ,: Measurement was impossible due to high viscosity.

* 2 _: Measurement was impossible due to high viscosity, but almost no melting was observed.

[0057] "Examples 6 to 13 and Comparative Examples 2 to 7"

 [Preparation of polyol premix solution for polyurethane foam]

 Polyol premixes for polyurethane foam, “Premix 1 to 14” were prepared using the raw materials and blends shown in Tables 2 and 3.

[0058] [Table 2]

 Table 2

 * Number of parts by weight

[0059] [Table 3] Table 3

 * Each part by weight In the formulation examples in Table 2 and Table 3, the following raw materials were used. Polyol I:! ~ 6: The aforementioned polyester polyol

 Polyol—7: “MAXIMOL RFK—504” terephthalic acid-based polyester poly-olli 11 manufactured by Sasaki Chemical Co., Ltd.)

 Polyol— 8: “MAXIMOL RFK— 556” terephthalic acid-based polyester poly-olli 11 manufactured by Sasaki Chemical Co., Ltd.)

 Polyol 9: “GR-04” Ethylenediamine amine polyether polyol (Mitsui Takeda Chemical Co., Ltd.)

 Polyol 10: “GR-07” Ethylenediamine amine polyether polyol (Mitsui Takeda Chemical Co., Ltd.)

 Polyol 11: “MN-3050” Glycerin-based polyether polyol (Mitsui Takeda Chemical Co., Ltd.)

 Foaming agent—1: HCFC—141b (manufactured by Daikin Industries, Ltd.)

 Foaming agent 2: HFC—245fa (manufactured by Central Glass Co., Ltd.)

 Catalyst 1: “KAO Riser I Nol” Amine-based catalyst (manufactured by Kao Corporation)

Catalyst 2: “DABCO K-15” Fatty acid potassium catalyst (Air Products Japan Co., Ltd.) Foam stabilizer: “SZ—1717” Silicone foam stabilizer (manufactured by Toray 'Dow Corning' Silicone Co., Ltd.)

 Flame Retardant: Tris (Beta Black Propyl) Phosphate Phosphorus flame retardant (Daihachi Chemical Co., Ltd.)

 [0061] [Production of polyurethane foam]

 Polyurethane foams were produced and evaluated by the methods shown below.

 <Manufacturing method>

 After mixing the liquid A (polyisocyanate liquid) and the liquid B (polyol premix liquid) shown in Tables 2 and 3, the mixture was poured into an injection box for free foaming to produce a urethane foam. (Examples 6 to 13, Comparative Examples 2 to 7) The reactivity and evaluation results are shown in Table 4 and Table 5. The following polyisocyanate solution was used. The foaming conditions and reactivity were as follows.

 Polyisocyanate solution: "Millionate MR-200" Polymeric MDI (manufactured by Nippon Polyuretan Kogyo Co., Ltd.)

[0062] <Foaming conditions>

 Examples 6-10, Comparative Examples 2-4

 Isocyanate index: 110

 Room temperature: 24 ° C ± 1 ° C

 Liquid temperature: 20 ° C ± 1 ° C

 Stirring: 3000rpm x 7 seconds

 Injection box: Wooden 200mm X 200mm X 200mm Open top

 Demolding time: 1 hour Examples 11-13, Comparative Examples 5-7

 Isocyanate index: 170

 Room temperature: 24 ° C ± 1 ° C

 Liquid temperature: 15 ° C ± 1 ° C

Stirring: 3000rpmX for 5 seconds Injection box: Wooden 200mm X 200mm X 200mm Open top

 Demolding time: 1 hour

<Reactivity>

The time defined below was measured starting from the start of mixing the premix solution and isocyanate.

Cream time: Time until foaming height reaches 1%.

Gel time: The time it takes to draw a thread when a needle is inserted into the foam surface and pulled out.

Rise time: Time until foam height reaches 95%. The obtained polyurethane foam was evaluated by the following methods, and the results are shown in Table 4 and Table 5.

<Evaluation method>

 (1) Core density

 Measured according to JIS A9511.

 2003

 (2) Compressive strength

 Measured according to JIS A9511.

 2003

 (3) Adhesive strength

 After mixing A liquid (polyisocyanate liquid) and B liquid (polyol premix liquid), it is free-foamed on an aluminum plate adjusted to 10 ° C, and left in a constant temperature bath at 10 ° C for 1 day. The force when peeling urethane foam was relatively evaluated.

 ◎: Adhering with tension

 ◯: Urethane foam peels off when strong force is applied

 Δ: Weak, the urethane foam peels off with force

 (4) Brittleness

 The urethane foam was evaluated by qualitative observation.

A: There is almost no brittleness. A: There is some brittleness.

 Δ: brittle

 (5) Flame resistance

 The cut urethane foam was burned and evaluated by measuring the weight of the remaining carbide (carbide) relative to the weight of the original urethane foam.

 ◎: More than 30% by weight remains

 〇: More than 20% by weight of chia remains.

 △: Almost all the chia remains!

 (6) Self-extinguishing

 Measured according to JIS A9511.

 2003

 [0064] [Table 4]

 Table 4

[0065] [Table 5]

Table 5

From Table 1 to Table 5, the following is clear.

 (1) Comparison results of Examples 1 to 5 and Comparative Example 1

The amount of succinic acid used in the rubonic acid component is 50 to 100 weight. / _0, and 50 to the amount of triethylene glycol in the total alcohol components: LOO Weight _^0/0 is a case of Examples 1-5, succinic force of Comparative Example 1 ^ weight _^0/0, and tri ethylene glycol than that of 0 wt _^0/0, the solubility of the further blowing agent viscosity Teigu is higher polyester polyols obtained

(2) Example 6-: Comparison results of LO and Examples 11-13 and Comparative Examples 2, 3 and Comparative Examples 5 and 6 The amount of succinic acid used in the full strength rubonic acid component is 50 to 100% by weight, and the total the amount mosquito 50 of triethylene glycol in the alcohol component: for LOO weight _^0/0 examples 6-10 using a polyester polyol is and examples 11-13, succinic acid 0 weight _^0/0, Compared with Comparative Example 2 and Comparative Example 5 using polyester polyol with 0% by weight of triethylene glycol, and Comparative Example 3 and Comparative Example 6 using only terephthalic acid-based polyester polyol, adhesive strength and urethane foam The brittleness is improved. In addition, there is little decrease in compressive strength, flame retardancy, and self-extinguishing properties.

(3) Example 6 ~: Comparison results of LO and Examples 11-13 and Comparative Example 4 and Comparative Example 7 The amount of succinic acid used in the full strength rubonic acid component is 50 to 100% by weight, and in all alcohol components polyester poly amount of triethylene glycol is from 50 to 100 weight _^0/0 In Examples 6 to 10 and Examples 11 to 13 using oars, the improvement in adhesive strength and brittleness is equal to or greater than in Comparative Examples 4 and 7 using glycerin-based polyether polyol. Furthermore, compressive strength, flame retardancy and self-extinguishing properties were improved.

Industrial applicability

 The polyester polyol of the present invention has a low viscosity and is easy to handle, and also has a foaming agent, particularly an HFC foaming agent such as HFC-245fa, an HC foaming agent such as pentane and cyclopentane, and water. It is useful as a raw material polyol for polyurethane, particularly polyurethane foam, because it has high solubility and further improves the adhesive strength with the adherend. In addition, the specifications, claims and drawings of Japanese patent application 2004-377809 filed on December 27, 2004 and Japanese Patent Application 2005-056984 filed March 2, 2005 The entire contents of the abstract are cited herein and can be taken as the disclosure of the specification of the present invention.

Claims

The scope of the claims

 [1] A polyester polyol obtained by esterifying a carboxylic acid component and an alcohol component, using succinic acid as at least a part of the carboxylic acid component, and using triethylene glycol as at least a part of the alcohol component A polyester polyol characterized by this.

 [2] The amount of succinic acid used is 30% by weight or more in the total rubonic acid component, and the amount of triethylene glycol used is 30% by weight or more in the total alcohol component. The polyester polyol according to 1.

[3] The amount of succinic acid used is 50% by weight or more in the total rubonic acid component, and the amount of triethylene glycol used is 50% by weight or more in the total alcohol component. 2. The polyester polyol according to 2.

[4] The polyester polyol according to any one of claims 1 to 3, which has a viscosity of 30000 mPa's or less.

 [5] The polyester polyol according to any one of claims 1 to 4, which has an acid value of lOmgKOHZg or less.

 [6] A polyurethane obtained by reacting a polyol component containing the polyester polyol according to any one of claims 1 to 5 with a polyisocyanate component.

 [7] A polyurethane foam obtained by reacting a polyol component containing the polyester polyol according to any one of claims 1 to 5 with a polyisocyanate component in the presence of a blowing agent.

 [8] The polyurethane or the claim according to claim 6, wherein the amount of the polyester polyol according to any one of claims 1 to 5 is 1% by weight or more and 50% by weight or less in the total polyol component. Item 8. The polyurethane foam according to item 7.

 [9] The polyurethane foam according to claim 7 or 8, wherein a foaming agent having an ozone depletion coefficient of 0.8 or less is used.

 10. The polyurethane foam according to claim 7, 8 or 9, wherein the foaming agent is one or more foaming agents selected from the group consisting of HFC foaming agents, HC foaming agents and hydraulic power.