JP2021098833A - Polyol liquid of fruit pomace, polyurethane with liquid of fruit pomace, polyurethane foam with liquid of fruit pomace, and manufacturing method of polyol liquid containing fruit pomace - Google Patents

Abstract

To obtain a high performance polymer material having effective use of a resource, at the same time, less-expensive practicability, by converting to polyol by liquefying fruit pomace discharged as an industrial waste. and by furthermore forming polyurethane.SOLUTION: The polyol liquid of the fruit pomace of the present invention is polyol liquid in which the fruit pomace is converted to polyol by heating dry fruit pomace, polyol, and a catalyst to dissolve the fruit pomace in polyol, in which a content of dry fruit pomace dissolved in the polyol is 1 to 60 mass% of a total amount of the dry fruit pomace and the polyol.SELECTED DRAWING: None

Description

The present invention relates to a polyol liquefied of fruit pomace, a polyurethane containing a liquefied fruit pomace, a polyurethane foam containing a liquefied fruit pomace, and a polyol liquefied containing fruit pomace. Regarding the manufacturing method of goods.

So far, biomass polyurethanes made from various industrial wastes such as "polyurethaneization of various lignins (Patent Document 1)", "polyurethaneization of sugar honey", and "polyurethaneization of okara" have been developed and obtained. Polyurethane is known to have excellent physical properties. The basis for the successful development of biomass polyurethane is the discovery that phenolic polymers such as lignin cannot be reduced in molecular weight by hydrolysis, but are soluble in polyethylene glycol (Patent Documents). 2).

On the other hand, one of the industrial wastes is fruit squeezed residue. Although the pomace of the fruit contains lignin, it is solid and cannot be used as it is for the production of biomass polyurethane. To make polyurethane using fruit pomace, it must be liquefied.

However, liquefaction of fruit pomace and polyurethaneization using liquefied pomace have not yet been attempted. That is, it is unclear whether the pomace of dried fruits can be liquefied, and if it can be liquefied, the liquefied product can be made into polyurethane. Under such circumstances, it is expected to develop an inexpensive polyurethane having excellent physical characteristics by incorporating a liquefied product of fruit pomace into the molecular chain of polyurethane. If the urethane is developed, it will be possible to effectively use the pomace of fruits, which is meaningful from the viewpoint of building a resource-recycling society.

Japanese Unexamined Patent Publication No. 2003-64147 Japanese Patent Application Laid-Open No. 1-289823

The present invention makes fruit pomace such as apple and tangerine into a liquefied product, and uses the liquefied product to enable the production of a polyurethane in which the pomace of fruit pomace is incorporated in a molecular chain. The purpose is to contribute to the construction of a resource-recycling society by making effective use of the pomace.

According to the present invention, the following polyol liquefied fruit pomace, polyurethane incorporating fruit pomace liquefied, polyurethane foam incorporating fruit pomace liquefied, and fruit pomace A method for producing a polyol liquid containing the above is provided.
[1] Dried fruit squeezed residue, a polyol, and a catalyst are heated to dissolve the fruit squeezed residue in the polyol, so that the fruit squeezed residue is a liquefied product obtained by converting the fruit squeezed residue into a polyol. A polyol liquefied of fruit squeezed fruit, characterized in that the content of the squeezed fruit of the dried fruit dissolved in is 1 to 60% by weight of the total of the squeezed fruit of the dried fruit and the polyol.
[2] The polyol liquefied of the fruit pomace according to 1 above, wherein the moisture content of the dried fruit pomace is 30% by weight or less.
[3] The catalyst is sulfuric acid, and the amount of the sulfuric acid added is 0.5 to 8.0% by weight based on the total amount of the polyol and the sulfuric acid when the dried fruit is squeezed, and is contained in a pressurized container. The polyol liquefied of the fruit squeezed residue according to 1 above, wherein the fruit squeezed residue is dissolved in the polyol by heating to 120 ° C. to 260 ° C.
[4] The liquefied fruit pomace according to any one of 1 to 3 above, wherein the fruit is any of apple, tangerine or grape.
[5] The liquefied fruit pomace according to any one of 1 to 4, wherein the polyol is polyethylene glycol.
[6] A polyurethane incorporating a liquefied fruit pomace, which is obtained by polycondensing an isocyanate with the liquefied fruit pomace according to any one of 1 to 5 above. ..
[7] A liquefied fruit pomace obtained by polycondensing an isocyanate with the liquefied fruit pomace according to any one of 1 to 6 above in the presence of water. Polyurethane foam incorporated.
[8] A method for producing a liquefied product in which fruit squeezed residue is converted into a polyol by heating the dried fruit squeezed residue in the presence of a catalyst and dissolving it in a polyol, which is dissolved in the polyol. A method for producing a polyol liquefied containing fruit squeezed residue, wherein the content of the dried fruit squeezed residue is 1 to 60% by weight in the total of the dried fruit squeezed residue and the polyol. ..
[9] The method for producing a polyol liquefied containing fruit pomace according to 8 above, wherein the moisture content of the dried fruit pomace is 30% by weight or less.
[10] The catalyst is sulfuric acid, and the amount of the sulfuric acid added is 0.5 to 8.0% by weight based on the total amount of the polyol and the sulfuric acid when the pomace of the dried fruit is added, and is contained in a pressurized container. 8. The method for producing a polyol liquefied containing fruit pomace according to 8 or 9, wherein the fruit pomace is dissolved in a polyol by heating to 120 ° C. to 260 ° C.

According to the present invention, the pomace of fruits such as apples and tangerines can be made into a polyol liquefied product. Further, the obtained polyol liquefied product can be used to produce a polyurethane in which a liquefied product of fruit pomace is incorporated in a molecular chain. According to the present invention, it is possible to make effective use of fruit pomace and contribute to the construction of a resource-recycling society. That is, according to the present invention, a polyol necessary for synthesizing an inexpensive and excellent polyurethane in which a liquefied fruit squeezed residue is incorporated in a molecular chain of polyurethane is provided, and a polyurethane using the polyol is further provided. Provided. The present invention, which enables liquefaction and polyurethane conversion of fruits, is the utilization of local special products such as Aomori Prefecture, and it is considered that the effect obtained by the region is great from the viewpoint of building a resource-recycling society.

Hereinafter, a method for producing a polyol liquefied from fruit pomace of the present invention, a polyurethane containing a liquefied fruit pomace, a polyurethane foam, and a polyol liquefied containing fruit pomace will be described.

The polyol liquefied of the fruit pomace of the present invention can be obtained by the method described below. In the method, a polyol liquefied product can be obtained by heating the dried fruit pomace, the polyol, and the catalyst to dissolve them in the polyol.

There are no restrictions on the fruit squeezed residue used in the present invention, for example, apple (apple), mandarin orange (tangerine), grape (grape), mango, banana, black sardine, red sardine, guzberry, tomato, eggplant, guaba, lucuma ( lucuma), capsicum, pomegranate, kiwi fruit, table grape, pumpkin, uri, cucumber, melon, orange, lemon, lime, grapefruit, banana, cranberry, blueberry, blackberry, raspberry, boysenberry, hedge apple, Examples include pineapples, figs, mulberry, apricots, peaches, cherries, sunflower seeds, berries and plums. Among these, apples (apples), mandarins (mandarins), grapes (grape), and mangoes, which are used in large amounts and whose pomace is easily available, are preferably used.
However, the present invention is not limited to the above-mentioned fruits, and any fruit or vegetable containing lignin can be used.

As the pomace of the fruit of the present invention, a dried one is used. If the drying is insufficient, the water content in the polyol increases, so that the liquefaction may not be successful. As for the degree of drying, it is desirable that the moisture content of the dried pomace measured by thermogravimetric analysis is 30% by weight or less, more preferably 20% by weight or less, 15% by weight or less, and further preferably 10% by weight or less. , Particularly preferably 8% by weight or less.

Examples of the polyol used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, trimethylolpropane, glycerin, triethanolamine, and sorbitol. Low molecular weight polyols: Polyethylene glycols, polypropylene glycols, polytetramethylene glycols, polyether polyols such as ethylene oxide / propylene oxide copolymers: polycaprolactones, poly-β-methyl-δ-petitrolactones, polyesters from diols and dibasic acids, etc. Can be mentioned. In addition, hydroxyl group-containing liquid polybutadiene, polycarbonate diol, acrylic polyol and the like can be mentioned.

Among the above, polyethylene glycol, which is easily available and easy to handle, is preferable. When polyethylene glycol is used, it is liquid at room temperature and the polyolification reaction easily occurs. Therefore, the number average molecular weight thereof is preferably 100 to 800, more preferably 100 to 600, and further preferably 150 to 400. Is.

In the present invention, the use of a catalyst promotes the hydrolysis reaction between fruit pomace and polyol. Examples of the catalyst include sulfuric acid, sulfate, hydrochloric acid, hydrochloride, nitric acid, nitrate and the like.
Of these, sulfuric acid, which is easy to obtain, inexpensive and easy to use, and has an excellent hydrolysis effect, is preferable.

When sulfuric acid is used as the catalyst, the amount of the sulfuric acid added is preferably 0.5 to 8.0% by weight based on the squeezed residue of the dried fruit and the total amount of the polyol and the sulfuric acid. When the addition amount is within this range, the effect of accelerating the reaction can be obtained. Further, it is possible to prevent the occurrence of reactions other than hydrolysis due to the excessive amount of the addition, and it is possible to prevent the occurrence of a phenomenon such as an increase in the insoluble portion. From this point of view, the lower limit of the addition amount is preferably 1.0% by weight, more preferably 1.5% by weight. The upper limit of the addition amount is preferably 6.0% by weight, more preferably 5.0% by weight, still more preferably 4.0% by weight, and particularly preferably 3.0% by weight.

In the present invention, the dried fruit pomace and the polyol are hydrolyzed to form a liquefied product, whereby the pomace of the fruit is dissolved in the polyol. This reaction is preferably carried out in a pressurized vessel. Since the progress rate of the hydrolysis reaction is slow at normal pressure, the hydrolysis is promoted by using a pressurized vessel.

In the obtained polyol liquefied product, the content of the pomace of the dried fruit dissolved in the polyol is 1 to 60% by weight in the total of the pomace of the dried fruit and the polyol.
If the content is too small, the effect of treating fruit pomace as industrial waste cannot be expected. If the content is too large, it becomes difficult to produce polyurethane having good physical properties.
From this point of view, the lower limit of the content is preferably 1% by weight, more preferably 5% by weight, still more preferably 10% by weight. The upper limit thereof is preferably 50% by weight, more preferably 40% by weight, still more preferably 30% by weight, and particularly preferably 20% by weight.
The fruit pomace liquefied in the polyol liquefied is obtained by hydrolyzing the pomace and dissolving it in the polyol.

In the present invention, the content (% by weight) of the pomace (pomace hydrolyzate) of the dried fruit is determined by the following formula (1).
Content of dried fruit squeezed waste =
[Weight of dried fruit pomace dissolved in polyol / (Weight of dried fruit pomace + Weight of polyol)] × 100 ・ ・ ・ (1)

The polyolization is preferably carried out by heating to a temperature of 120 ° C. to 260 ° C. When the temperature is within this range, the hydrolysis reaction of the pomace of the fruit is prevented from being delayed, and the dissolution in the polyol can be effectively promoted. In addition, it is possible to prevent decomposition and carbonization of fruit pomace due to the temperature being too high.
From this point of view, the lower limit of the temperature is preferably 140 ° C, more preferably 160 ° C. The upper limit is preferably 240 ° C., more preferably 220 ° C., and even more preferably 200 ° C.

The time required for the polyolization reaction of fruit pomace should be set based on the fact that almost all of the charged dry pomace is dissolved in the polyol. Specifically, it is preferably 1 to 10 hours, more preferably 2 to 8 hours, and even more preferably 3 to 6 hours. If the time is within this range, the production efficiency is ensured, and a sufficient time can be taken for the reaction, so that the stability of the reaction is ensured.
Almost all of the charged dry pomace means 90% by weight or more of the charged dry pomace, preferably 95% by weight or more, more preferably 97% by weight or more, and particularly preferably 99% by weight or more. ..

Since the obtained polyol liquefied has strong acidity, it is better to adjust the pH by adding 1 to 5% aqueous sodium hydroxide solution or the like. Specifically, it is preferable to adjust the pH to 4 to 8. Further, since the polyol liquefied contains water, it is preferable to concentrate it to adjust the water content within the range of 1 to 10% by weight. The moisture content can be adjusted by whether or not to foam during the production of polyurethane. When foaming, foaming is performed at a low foaming ratio (apparent density 0.2 to 0.9 g / cm ³ ) or a high foaming ratio (apparent density 0). It is performed on the basis of whether to foam to 0.01 g / cm ³ or more and less than 0.2 g / cm ^3. When not foaming, it is usually adjusted to 0 to 1% by weight, when foaming to a low foaming ratio, it is usually adjusted to 2 to 6% by weight, and when foaming to a high foaming ratio, it is usually adjusted to 8 to 15% by weight.

As described above, according to the present invention, by drying the pomace of the fruit, heating the polyol and the catalyst, and causing a hydrolysis reaction, almost all the pomace of the fruit is converted into a polyol. It can be dissolved to make the pomace of the fruit into a polyolized liquefied product. This finding was found by the present inventors for the first time in trying to solve the problem of liquefaction of fruit pomace.

The present inventors have further attempted to produce polyurethane using a polyol liquefied product of fruit pomace, and confirmed that the polyol liquefied product can be made into polyurethane.

Next, polyurethane and polyurethane foam produced by using the obtained polyol liquid will be described.
The polyurethane of the present invention can be obtained by polycondensing a polyisocyanate with the polyol liquefied product. In this case, polyurethane foam can be obtained by allowing water to be present in the reaction system.

The pomace of the fruit is liquefied in the polyol and hydrolyzed to saccharides, lignin, etc. to form a molecular form, which is present in the solution. Hydroxy groups in these sugars, lignins and polyols react with isocyanates to form urethane bonds, resulting in polyurethane.

The polyisocyanate used for producing the polyurethane of the present invention includes aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and modified products thereof. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate, and examples of the alicyclic polyisocyanate include isophorone diisocyanate. Examples of the aromatic polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polypeptide diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate and the like. Examples of the polyisocyanate modified product include urethane prepolymer, hexamethylene diisocyanate burette, hexamethylene diisocyanate, trimmer, isophorone diisocyanate trimmer and the like.

The polycondensation reaction is carried out in the presence of a catalyst. As the catalyst in this case, a conventionally known catalyst for urethanization reaction, usually a tin-based or amine-based catalyst is used. The reaction temperature may be room temperature, but it can also be heated if necessary.

The polyol liquefied product can be used as it is as a raw material for polyurethane, but when the content of the liquefied product is too high, it is preferable to dilute it with a polyol such as polyethylene glycol in order to adjust the physical characteristics of polyurethane. .. Too little amount of polyol for dilution can result in polyurethane that is too hard. Too much polyol for dilution can result in too soft polyurethane.

The ratio of polyisocyanate to the polyol liquefied is 0.8 to 2 times the equivalent number of all hydroxyl groups contained in the hydroxyl group component, preferably 1 to 1.5 times the equivalent number of isocyanate groups. It is a double equivalent.

In the production of the polyurethane of the present invention, lignin sulfonic acid or a partially neutralized salt thereof, if necessary, molasses or a sugar compound can be added to the polyol liquefied product. In this case, the ratio of lignin sulfonic acid, molasses, etc. used is 0.1 to 50% by weight, preferably 1 to 45% by weight, based on the total hydroxyl group components of the polyol liquefied product.

The proportion of the pomace of the dried fruit dissolved in the polyol is preferably 1 to 60% by weight, preferably 2 to 40% by weight, and more preferably 5 to 20% by weight in the total polyurethane. By using a polyol liquefied containing a hydrolyzate of such fruit pomace as a reaction component, polyurethane having excellent biodegradability and excellent mechanical strength can be obtained.

The polyurethane of the present invention can be a polyurethane foam. In this case, the apparent density (weight / volume) can be adjusted by the amount of water (foaming agent) added to the reaction raw material, and the amount of water is 0.001 to 0 per mole of polyisocyanate. It is about 3 mol, preferably about 0.005 to 0.05 mol. In this polyurethane foam, its apparent density (weight / volume of polyurethane foam) is 0.01 to 0.9 g / cm ³ , preferably 0.05 to 0.5 g / cm ³ .

The polyurethane of the present invention can be used as a sheet, film or the like in a solid state, and as an adhesive or the like in a liquid state. Further, the polyurethane foam of the present invention can be used as a heat insulating material for buildings, home appliances, vehicles and the like. Further, it can be used as a cushion material for furniture and packaging materials.

Next, the social necessity behind the present invention will be described.
Fruit pomace is one of the plant-derived industrial wastes. As described above, the pomace of the fruit includes apples, tangerines, grapes, mangoes, etc., and a large amount of these pomace is generated.
For example, apples are mass-produced throughout Japan, including Aomori Prefecture. However, many apples are not suitable for raw food and are used for processing, and are processed into apple juice and the like. As a result, a large amount of squeezed waste is discharged from apple processing plants, and although some of them are used for feed and fertilizer, most of them are treated as industrial waste. Effective utilization of apple resources, including squeezed slag discharged from apple processing factories, is extremely useful for revitalizing local industries and local residents, including Aomori Prefecture.

In addition, juice, which is the juice of fruits, is drunk all over the world, and typical juices are apple and orange juices. Some of the apple and tangerine (Japanese orange) pomace discharged in the juice processing process is used for feed and fertilizer, but most of it is treated as industrial waste. In addition, wine is produced from grape juice. The pomace is also not used effectively. The present invention paves the way for effective utilization of industrial waste. That is, the present inventors have succeeded in developing a polyol liquefied product of fruit pomace, and further succeeded in synthesizing polyurethane using the polyol liquefied product. The obtained polyurethane has saccharides and lignin, which are hydrolysates of fruit pomace, incorporated in the molecular chain, and is inexpensive, has excellent physical characteristics, and is biodegradable. Therefore, the present invention makes it possible to utilize waste generated from local special products such as Aomori Prefecture, and it is considered that the effect obtained by the local community is great from the viewpoint of building a resource-recycling society.

Next, the present invention will be described in more detail with reference to Examples.

Example 1
Preparation of polyol liquefied from apple pomace Dried pomace pomace (moisture content 8% by weight) is crushed, and 1 part by weight of the crushed pomace is placed in a pressurized container (autoclave) with 5 parts by weight of polyethylene. It was mixed with glycol 200 (molecular weight 200), and 2% by weight of sulfuric acid was added to the total of pomace and polyethylene glycol. A polyol liquefied of apple pomace was prepared by heating at 180 ° C. for 4 hours.
The obtained polyol liquefied was prepared with an aqueous sodium hydroxide solution so as to have a pH of 5, and concentrated to adjust the water content to 3% by weight.
The content of the hydrolyzate of apple pomace in the polyol liquefied was 16.7% by weight.
The moisture content was measured by thermogravimetric analysis. The content of the hydrolyzate was determined by the above formula (1).

Example 2
Preparation of polyol liquefaction of tangerine pomace Dried pomace pomace (moisture content 3%) is crushed, and 1 part by weight of the crushed pomace is placed in a pressurized container (autoclave) with 5 parts by weight of polyethylene. It was mixed with glycol 200 (molecular weight 200), and 2% by weight of sulfuric acid was added to the total of pomace and polyethylene glycol. A polyol liquefied of tangerine pomace was prepared by heating at 180 ° C. for 4 hours.
The obtained polyol liquefied was adjusted to pH 5 with an aqueous sodium hydroxide solution and concentrated to adjust the water content to 3% by weight.
The content of the hydrolyzate of tangerine pomace in the polyol liquefied was 16.7% by weight.
The moisture content was measured by thermogravimetric analysis. The content of the hydrolyzate was determined by the above formula (1).

Example 3
The polyol liquefied (APL) of apple squeezed residue (APLres) obtained in Example 1 and polyethylene glycol 200 (molecular weight 200) were mixed at a weight ratio of 1: 1 to prepare a polyol mixture (APLP).
Next, a catalytic amount of a tin-based catalyst, water and a silicon foam stabilizer were added to this APPL and stirred well, and further diphenylmethane diisocyanate (MDI) was added and vigorously stirred at room temperature to obtain a polyurethane foam. Table 1 shows the pyrolysis temperature (Td) of the obtained foam, and the pyrolysis residues (m ₅₀₀ , m _{600) at 500 ° C. and 600 ° C.}

In Table 1, APLres (% by weight) and APL (% by weight) have the following meanings.
APLres (% by weight): The content (% by weight) of apple pomace (APLres) in the polyol liquefied product (APL).
APL (% by weight): The content (% by weight) of the liquefied apple pomace (APL) in the total polyol mixture (APLP).

Example 4
The polyol liquefied (ORL) of the tangerine squeezed residue (ORres) obtained in Example 2 and polyethylene glycol 200 were mixed at a weight ratio of 1: 1 to prepare a polyol mixture (ORLP).
Next, a catalytic amount of a tin-based catalyst, water and a silicon foam stabilizer were added to the ORLP and stirred well, and diphenylmethane diisocyanate (MDI) was further added and vigorously stirred at room temperature to obtain a polyurethane foam. Table 1 shows the pyrolysis temperature (Td) of the obtained foam, and the pyrolysis residues (m ₅₀₀ , m _{600) at 500 ° C. and 600 ° C.}

In Table 1, ORres (% by weight) and ORL (% by weight) have the following meanings.
ORres (% by weight): The content (% by weight) of tangerine pomace (ORres) in the polyol liquefied product (ORL).
ORL (% by weight): The content (% by weight) of the tangerine pomace liquid (ORL) in the total polyol mixture (ORLP).

Example 5
Preparation of Polyethylene Glycolate of Wine Pomace Dried (red) wine pomace (water content 1% by weight) is crushed, and 1 part by weight of the crushed pomace is placed in a pressurized container (autoclave) for 5 parts. It was mixed with parts of polyethylene glycol 200 (molecular weight 200) by weight, and 5% by weight of sulfuric acid was added to the total of pomace and polyethylene glycol. A polyol liquefied of wine pomace was prepared by heating at 180 ° C. for 4 hours.
The obtained polyol liquefied was adjusted to pH 5 with an aqueous sodium hydroxide solution and concentrated to adjust the water content to 3% by weight.
The content of the hydrolyzate of tangerine pomace in the polyol liquefied was 16.7% by weight.
The moisture content was measured by thermogravimetric analysis. The content of the hydrolyzate was determined by the above formula (1).

Example 6
The polyol liquefied (GRL) of wine granules (GRres) obtained in Example 5 and polyethylene glycol 200 were mixed at a weight ratio of 1: 1 to prepare a polyol mixture (GRLP).
Next, a catalytic amount of a tin-based catalyst, water and a silicon foam stabilizer were added to the GRLP and stirred well, and diphenylmethane diisocyanate (MDI) was further added and vigorously stirred at room temperature to obtain a polyurethane foam. Table 3 shows the thermal decomposition temperature (Td) of the obtained foam, and the thermal decomposition residues (m500, m600) at 500 ° C. and 600 ° C.

In Table 3, GRres (% by weight) and GRL (% by weight) have the following meanings.
GRres (% by weight): The content (% by weight) of wine pomace (GRres) in the polyol liquefied product (GRL).
GRL (% by weight): The content (% by weight) of the liquefied wine pomace (GRL) in the total polyol mixture (GRLP).

Claims (10)

By heating the dried fruit squeezed residue, the polyol, and the catalyst to dissolve the fruit squeezed residue in the polyol, the fruit squeezed residue is a liquefied product obtained by converting it into a polyol, which is dissolved in the polyol. A polyol liquefaction of fruit squeezed fruit, characterized in that the content of the dried fruit squeezed waste is 1 to 60% by weight in the total of the dried fruit squeezed waste and the polyol. The polyol liquefied of the fruit pomace according to claim 1, wherein the moisture content of the dried fruit pomace is 30% by weight or less.
The catalyst is sulfuric acid, and the amount of the sulfuric acid added is 0.5 to 8.0% by weight based on the total amount of the polyol and the sulfuric acid when the dried fruit is squeezed, and is 120 ° C. in a pressurized container. The polyol liquefied of fruit squeezed residue according to claim 1, wherein the fruit squeezed residue is dissolved in a polyol by heating to ~ 260 ° C.
The liquefied fruit pomace according to any one of claims 1 to 3, wherein the fruit is either an apple, a tangerine, or a grape.
The liquefied fruit pomace according to any one of claims 1 to 4, wherein the polyol is polyethylene glycol.
A polyurethane incorporating a liquefied fruit pomace, which is obtained by polycondensing an isocyanate with the liquefied fruit pomace according to any one of claims 1 to 5.
The liquefied fruit pomace according to any one of claims 1 to 6 is incorporated with the liquefied fruit pomace, which is obtained by polycondensing an isocyanate in the presence of water. Polyurethane foam.
A method for producing a liquefied product in which the fruit squeezed residue is converted into a polyol by heating the dried fruit squeezed residue in the presence of a catalyst and dissolving it in a polyol. A method for producing a polyol liquefied containing fruit squeezed residue, wherein the content of the squeezed residue is 1 to 60% by weight in the total of the dried fruit squeezed residue and the polyol.
The method for producing a polyol liquefied containing fruit pomace according to claim 8, wherein the moisture content of the dried fruit pomace is 30% by weight or less.
The catalyst is sulfuric acid, and the amount of the sulfuric acid added is 0.5 to 8.0% by weight based on the total amount of the polyol and the sulfuric acid when the pomace of the dried fruit is added, and the temperature is 120 ° C. in a pressurized container. The method for producing a polyol liquefied containing fruit pomace according to claim 8 or 9, wherein the fruit pomace is dissolved in a polyol by heating to ~ 260 ° C.