Composition for manufacturing polyurethane foam, and polyurethane foam

Abstract

To provide a technique that can improve reactivity in the production of polyurethane foam, even when using an aliphatic isocyanate or an alicyclic isocyanate.SOLUTION: The present technique provides a composition for the production of polyurethane foam that comprises a polyol, an aliphatic isocyanate and / or an alicyclic isocyanate, and a primary amine. The present technique also provides a polyurethane foam that is synthesized from a composition for the production of polyurethane foam.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present technology relates to a composition for producing polyurethane foam and polyurethane foam.

Background Art

[0002] Polyurethane foam is widely used in various fields, including furniture such as sofas and chairs, bedding such as mattresses and pillows, clothing such as underwear, daily necessities such as tableware and cleaning sponges, products for vehicle and aircraft interiors such as car seats, toys, and miscellaneous goods. And, various developments are being made to improve quality and赋予 new functions according to each field and purpose.

[0003] For example, Patent Document 1 contains a strength improver (A) for producing polyurethane foam having a specific structure and a polyol (P), and (1) the hydroxyl value (mgKOH / g) of the strength improver (A) is 0 to 500, (2) the aromatic polycarboxylic acid (C) is an aromatic polycarboxylic acid (C) having a trivalent or higher valence, and the content (weight %) of the structure of Y based on the weight of the polyol composition is 0.1 to 60 weight %, (3) the ester group concentration (mmol / g) of the polyol composition is from 0.005 to 3.8 mmol / g, whereby a polyol composition for producing a soft polyurethane foam that is less likely to yellow and does not reduce mechanical properties such as tensile and tear strength even when an aliphatic / alicyclic isocyanate is used is disclosed.

[0004] Also, for example, Patent Document 2 discloses a method for producing polyurethane foam by reacting an isocyanate with a compound having at least two hydrogen atoms reactive with an isocyanate group. When the isocyanate used is a (cyclic) aliphatic isocyanate and the reaction is carried out in the presence of a substance that forms a frame structure in the polyurethane foam, a polyurethane foam having good mechanical performance and light stability that can be produced using conventional starting materials in polyurethane chemistry is disclosed.

Prior Art Documents

[0005] [Patent Document 1] Japanese Patent Publication No. 2013-1777 [Patent Document 2] Japanese Patent Publication No. 2001-226448 [Overview of the project] [Problems that the invention aims to solve]

[0006] Polyurethane foam is obtained by mixing isocyanates and polyols together with catalysts, blowing agents, foam stabilizers, etc., and allowing resinification and foaming reactions to proceed. However, it is known that the properties during and after production differ depending on the type of isocyanate and polyol used. For example, aliphatic and alicyclic isocyanates have the characteristic of being highly biodegradable, and are therefore often preferred over poorly biodegradable aromatic isocyanates in situations where environmental considerations are important. On the other hand, when manufacturing polyurethane foam using aliphatic or alicyclic isocyanates, there is a problem of poor reactivity during production compared to when aromatic isocyanates are used.

[0007] Therefore, the main objective of this technology is to provide a technique that can improve the reactivity during the manufacturing process, even when using aliphatic isocyanates or alicyclic isocyanates to produce polyurethane foam. [Means for solving the problem]

[0008] In this technology, first, a polyol and Aliphatic isocyanates and / or alicyclic isocyanates, Primary amines and, A composition for manufacturing polyurethane foam containing [the specified ingredient] is provided. In the polyurethane foam manufacturing composition according to this technology, the primary amine can be contained in 1 to 20 parts by mass per 100 parts by mass of the total of the polyol and the primary amine. As the polyol used in the polyurethane foam manufacturing composition related to this technology, a biodegradable polyol can be used.

[0009] This technology then provides a polyurethane foam manufactured from a polyurethane foam manufacturing composition related to this technology. [Brief explanation of the drawing]

[0010] [Figure 1] This graph shows the cream time and rise time in the example. [Modes for carrying out the invention]

[0011] The following describes preferred embodiments for implementing this technology. The embodiments described below are examples of typical embodiments of this technology, and any combination of these embodiments is possible. Furthermore, this does not mean that the scope of this technology will be narrowed.

[0012] 1. Composition for the manufacture of polyurethane foam The polyurethane foam manufacturing composition according to this technology contains a polyol, an aliphatic isocyanate and / or an alicyclic isocyanate, and a primary amine. Furthermore, if necessary, the polyurethane foam manufacturing composition according to this technology may also contain a blowing agent, a catalyst, a foam stabilizer, etc. Each component will be described in detail below.

[0013] (1) Polyol As long as the purpose and effects of this technology are not impaired, one or more polyols that can be used in the manufacture of polyurethane foam can be freely selected and used. Examples include polyester polyols, polycarbonate polyols, polyether polyols, and polyester ether polyols. For example, polyols with 2 to 4 functional groups and a molecular weight of 800 to 8000 can be cited.

[0014] Examples of polyester polyols include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aliphatic carboxylic acids such as ricinoleic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; or acid esters or acid anhydrides thereof, and ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, and 1,3-butylene glycol. Examples include polyester polyols such as polypropylene glycol obtained by dehydration condensation reactions with benzodiols, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, etc., or mixtures thereof; and polylactone polyols and polycaprolactone polyols obtained by ring-opening polymerization of lactone monomers such as ε-caprolactone and methylvalerolactone.

[0015] Examples of polycarbonate polyols include those obtained by reacting at least one polyhydric alcohol, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, or diethylene glycol, with diethylene carbonate, dimethyl carbonate, diethyl carbonate, or the like.

[0016] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and their copolyethers, which are obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide, and tetrahydrofuran, respectively. They can also be obtained by polymerizing the above-mentioned cyclic ethers using polyhydric alcohols such as glycerin and trimethylolethane.

[0017] Examples of polyester ether polyols include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid; or those obtained by dehydration condensation reactions of these acid esters or acid anhydrides with glycols such as diethylene glycol or propylene oxide adducts, or mixtures thereof.

[0018] In this technology, it is preferable to use biodegradable polyols for environmental reasons. When using biodegradable polyols to manufacture polyurethane foam, their low reactivity has sometimes been a problem. However, in this technology, by using primary amines as described later, the reactivity during polyurethane foam manufacturing can be improved even when using biodegradable polyols.

[0019] As the biodegradable polyol that can be used in the present technology, as long as the object and effects of the present technology are not impaired, one or more biodegradable polyols that can be used in the production of polyurethane foam can be freely selected and used. For example, polyglycolic acid (PGA), polylactic acid (PLA), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polycaprolactone (PCL), polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyhydroxyalkanoic acid (PHA), cellulose, cellulose acetate, chitosan, starch, modified starch, xylitol, sorbitol, mannitol, maltitol, natural ester such as castor oil-based polyol, etc. may be mentioned. Among these, in the present technology, it is preferable to select natural esters such as polycaprolactone (PCL) represented by the following chemical formula (1) and castor oil-based polyol represented by the following chemical formula (2).

[0020]

Chemical formula

[0021]

Chemical formula

[0022] (2) Aliphatic isocyanate and / or alicyclic isocyanate In the present technology, as the isocyanate, it is characterized in that an aliphatic isocyanate and / or an alicyclic isocyanate is used. When producing a polyurethane foam using an aliphatic isocyanate or an alicyclic isocyanate, there were cases where the low reactivity during production was a problem compared to the case of using an aromatic isocyanate. However, in the present technology, by using the primary amine described later, even when an aliphatic isocyanate or an alicyclic isocyanate is used, the reactivity during the production of the polyurethane foam can be improved.

[0023] As for the aliphatic isocyanates and / or alicyclic isocyanates that can be used in this technology, one or more aliphatic isocyanates and / or alicyclic isocyanates that can be used in the manufacture of polyurethane foam can be freely selected and used, as long as they do not impair the purpose and effects of this technology.

[0024] Examples of aliphatic isocyanates include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2 Examples include ,4,-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capeate, lysine diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, trimethylhexamethylene diisocyanate, 1,5-pentamethylene diisocyanate (PDI), decamethylene diisocyanate, and derivatives thereof.

[0025] Alicyclic isocyanates include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), dimer acid diisocyanate, and transcyclohexane 1,4-diiso Examples include monocyclic alicyclic isocyanates such as cyanates, hydrogenated tolylene diisocyanate (hydrogenated TDI), and hydrogenated tetramethylxylylene diisocyanate (hydrated TMXDI); cross-linked alicyclic isocyanates such as norbornene diisocyanate, norbornane diisocyanate methyl, bicycloheptane triisocyanate, cyisocyanate methylbicycloheptane, and di(diisocyanate methyl)tricyclodecane, as well as derivatives thereof.

[0026] Furthermore, trimers (nurates) of the above-mentioned aliphatic diisocyanates or alicyclic diisocyanates are also included.

[0027] Among these, in this technology, it is preferable to select HDI isocyanurate represented by the following chemical formula (3), which is a derivative of hexamethylene diisocyanate (HDI) (HDI trimer, 2,4,6-trioxo-1,3,5-triazine-1,3,5-triyltris(6,1-hexanediyl)triisocyanate), or 1,5-PDI isocyanurate represented by the following chemical formula (4), which is a derivative of 1,5-pentamethylene diisocyanate (PDI).

[0028] [ka]

[0029] [ka]

[0030] The amount of aliphatic isocyanate and / or alicyclic isocyanate, or trimers thereof, used in the polyurethane foam manufacturing composition according to this technology can be freely set as long as the purpose and effects of this technology are not impaired. In this technology, the lower limit of the content of aliphatic isocyanate and / or alicyclic isocyanate, or trimers thereof, in the polyurethane foam manufacturing composition is, for example, 20 parts by mass or more, preferably 40 parts by mass or more, and more preferably 60 parts by mass or more, based on 100 parts by mass of the total of the polyol and the primary amine described later. If the amount of aliphatic isocyanate and / or alicyclic isocyanate, or trimers thereof, is too small compared to the amount of polyol, the strength of the manufactured polyurethane foam will decrease, and bleeding or discoloration of the polyurethane foam may occur.

[0031] In this technology, the upper limit of the content of aliphatic isocyanates and / or alicyclic isocyanates, or their trimers, in the polyurethane foam manufacturing composition is, for example, 200 parts by mass or less, preferably 150 parts by mass or less, and more preferably 120 parts by mass or less, based on 100 parts by mass of the total of the polyol and the primary amine described later. Setting the upper limit of the content of aliphatic isocyanates and / or alicyclic isocyanates, or their trimers, in the polyurethane foam manufacturing composition within this range offers the advantage of cost reduction. However, as mentioned above, if the amount of aliphatic isocyanates and / or alicyclic isocyanates, or their trimers, is too high relative to the amount of polyol, the hardness of the polyurethane foam may become too hard, making it brittle and impairing its flexibility, and it may become impossible to ensure the elasticity of the soft polyurethane foam.

[0032] Furthermore, this technology can also utilize aromatic isocyanates, and within the limits that do not impair the purpose or effects of this technology, it is possible to freely select one or more aromatic isocyanates that can be used in the manufacture of polyurethane foam and use them in combination with aliphatic isocyanates and / or alicyclic isocyanates.

[0033] (3) Primary amines This technology is characterized by the use of a primary amine. In particular, this technology can use a primary amine having at least one primary amino group and containing 2 to 4 functional groups, including active hydrogen groups such as hydroxyl groups.

[0034] When manufacturing polyurethane foam, the balance between the resinification reaction and the foaming reaction is extremely important. For example, if the resinification reaction is slower than the foaming reaction, the thickening of the polyurethane foam manufacturing composition will also be slow, making it easier for the gas generated in the foaming reaction to escape, resulting in unstable foaming behavior. In addition, the curing time will be longer, making it unsuitable for general mold molding, resulting in poor mass production and poor design quality of the manufactured polyurethane foam. However, this technology uses primary amines to accelerate the initial thickening (cream time), promote internal heat generation, improve the reactivity of the resinification reaction, and also increase the reactivity of the foaming reaction, thereby shortening the rise time. As a result, even when using raw materials with low reactivity during manufacturing, such as aliphatic isocyanates and / or alicyclic isocyanates or biodegradable polyols, a good balance between the resinification reaction and the foaming reaction can be maintained.

[0035] Furthermore, when manufacturing polyurethane foam using raw materials with low reactivity during production, there is a method of increasing the amount of catalyst to enhance reactivity. However, increasing the amount of catalyst destabilizes the resinification and foaming reactions. Another method involves using a prepolymer, which is a polyol and / or isocyanate that has been reacted with a portion of the raw material in advance, to shorten the reaction time. However, because the prepolymer has high viscosity, there is a problem of reduced stirability due to the increased viscosity of the raw material mixture. However, in this technology, by using a primary amine, there is no need to increase the amount of catalyst, thus stabilizing the resinification and foaming reactions. In addition, because the reactivity is high even without using a prepolymer, it is possible to suppress the increase in viscosity of the raw material mixture and prevent a decrease in stirability.

[0036] The amount of primary amine used in the polyurethane foam manufacturing composition according to this technology can be freely set as long as it does not impair the purpose and effects of this technology. In this technology, the lower limit of the primary amine content in the polyurethane foam manufacturing composition is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and more preferably 4 parts by mass or more, per 100 parts by mass of the total of the polyol and primary amine. By setting the lower limit of the primary amine content in the polyurethane foam manufacturing composition within this range, the reactivity of the resinification reaction and the foaming reaction can be improved. As a result, even when raw materials with poor reactivity in production, such as aliphatic isocyanates and / or alicyclic isocyanates or biodegradable polyols, a good balance between the resinification reaction and the foaming reaction can be maintained, and consequently, polyurethane foam with excellent mechanical properties and design appeal can be obtained.

[0037] In this technology, the upper limit of the primary amine content in the polyurethane foam manufacturing composition is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 7 parts by mass or less, per 100 parts by mass of the total of the polyol and primary amine. By setting the upper limit of the primary amine content in the polyurethane foam manufacturing composition within this range, it is possible to prevent destabilization of the resinification reaction and foaming reaction due to excessively high reactivity during manufacturing, and to prevent a decrease in stirability due to an increase in viscosity during prepolymerization. Furthermore, if the resinification reaction proceeds too quickly compared to the foaming reaction, hardening will proceed before the foaming reaction can progress, which may result in uneven foaming, uneven hardness, or foaming defects. However, by setting the upper limit of the primary amine content in the polyurethane foam manufacturing composition within this range, it is possible to maintain a good balance between the resinification reaction and the foaming reaction, thereby preventing uneven foaming, uneven hardness, and foaming defects.

[0038] The number-average molecular weight of the primary amine that can be used in this technology is not particularly limited, as long as it does not impair the purpose or effects of this technology. A lower limit for the number-average molecular weight of the primary amine that can be used in this technology is, for example, 800 or more, preferably 1800 or more, and more preferably 2400 or more. Furthermore, the weight-average molecular weight of the primary amine that can be used in this technology is not particularly limited, as long as it does not impair the purpose or effects of this technology. A lower limit for the weight-average molecular weight of the primary amine that can be used in this technology is, for example, 800 or more, preferably 1800 or more, and more preferably 2400 or more. By setting the lower limit of the number-average molecular weight and / or weight-average molecular weight of the primary amine that can be used in this technology within this range, it is possible to prevent destabilization of the resinification and foaming reactions due to excessively high reactivity during production, and to prevent a decrease in stirability due to increased viscosity during prepolymerization. In addition, a good balance between the resinification and foaming reactions can be maintained, preventing uneven foaming, uneven hardness, and poor foaming.

[0039] The upper limit for the number-average molecular weight of the primary amine that can be used in this technology is, for example, 12,000 or less, preferably 8,000 or less, and more preferably 6,000 or less. Similarly, the upper limit for the weight-average molecular weight of the primary amine that can be used in this technology is, for example, 12,000 or less, preferably 8,000 or less, and more preferably 6,000 or less. By setting the upper limits for the number-average molecular weight and / or weight-average molecular weight of the primary amine that can be used in this technology within this range, the reactivity during production can be improved. As a result, even when using raw materials with low reactivity during production, such as aliphatic isocyanates and / or alicyclic isocyanates or biodegradable polyols, a good balance between the resinification reaction and the foaming reaction can be maintained, and consequently, polyurethane foam with excellent mechanical properties and design appeal can be obtained.

[0040] The number of oxyalkylene repeating units in the primary amine that can be used in this technology is not particularly limited, as long as it does not impair the purpose or effects of this technology. The lower limit of the number of oxyalkylene repeating units in the primary amine that can be used in this technology is, for example, 10 or more, preferably 20 or more, more preferably 30 or more, and even more preferably 40 or more. By setting the lower limit of the number of oxyalkylene repeating units in the primary amine that can be used in this technology to this range, it is possible to prevent destabilization of the resinification reaction and foaming reaction due to excessively high reactivity during production, and to prevent a decrease in stirability due to an increase in viscosity during prepolymerization. In addition, it is possible to maintain a good balance between the resinification reaction and the foaming reaction, and to prevent uneven foaming, uneven hardness, and foaming defects.

[0041] The upper limit for the number of oxyalkylene repeating units in the primary amine that can be used in this technology is, for example, 200 or less, preferably 160 or less, more preferably 120 or less, and even more preferably 100 or less. By setting the upper limit for the number of oxyalkylene repeating units in the primary amine that can be used in this technology to this range, the reactivity during production can be improved. As a result, even when using raw materials with poor reactivity during production, such as aliphatic isocyanates and / or alicyclic isocyanates or biodegradable polyols, a good balance between the resinification reaction and the foaming reaction can be maintained, and consequently, polyurethane foam with excellent mechanical properties and design appeal can be obtained.

[0042] The kinematic viscosity of the primary amine that can be used in this technology is not particularly limited, as long as it does not impair the purpose or effects of this technology. The lower limit of the kinematic viscosity of the primary amine that can be used in this technology is, for example, 100 cSt or more, preferably 200 cSt or more, and more preferably 300 cSt or more, at 25°C.

[0043] The upper limit of the kinematic viscosity of the primary amine that can be used in this technology is, for example, 2000 cSt or less, preferably 1500 cSt or less, and more preferably 1000 cSt or less, at 25°C.

[0044] The amine hydrogen equivalent (AHEW) of the primary amine that can be used in this technology is not particularly limited as long as it does not impair the purpose or effects of this technology. The lower limit of the amine hydrogen equivalent (AHEW) of the primary amine that can be used in this technology is, for example, 100 or more, preferably 200 or more, and more preferably 300 or more. By setting the lower limit of the amine hydrogen equivalent (AHEW) of the primary amine that can be used in this technology within this range, it is possible to prevent destabilization of the resinification reaction due to excessively high reactivity during the resinification reaction, and to prevent a decrease in stirability due to an increase in viscosity during prepolymerization. In addition, it is possible to maintain a good balance between the resinification reaction and the foaming reaction, and to prevent uneven foaming, uneven hardness, and foaming defects.

[0045] The upper limit of the amine hydrogen equivalent (AHEW) of the primary amine that can be used in this technology is, for example, 2000 or less, preferably 1500 or less, and more preferably 1000 or less. By setting the upper limit of the amine hydrogen equivalent (AHEW) of the primary amine that can be used in this technology to this range, the reactivity of the resinification reaction can be improved. As a result, even when using raw materials with low reactivity during the resinification reaction, such as aliphatic isocyanates and / or alicyclic isocyanates or biodegradable polyols, a good balance between the resinification reaction and the foaming reaction can be maintained, and consequently, polyurethane foam with excellent mechanical properties can be obtained.

[0046] In this technology, the amine hydrogen equivalent weight (AHEW) of a primary amine is defined as the molecular weight of the polyetheramine divided by the number of active amine hydrogens per molecule. The amine hydrogen equivalent weight (AHEW) of a primary amine can be calculated according to the methods known to those skilled in the art and prior art, but preferably it can be calculated by determining the amine group nitrogen content using the procedure described in ISO 9702.

[0047] Specific examples of primary amines that can be used in this technology include, for example, one or more primary amines selected from polyester primary amines and polyether primary amines such as polyethertriamines obtained by addition polymerization of oxyalkylenes represented by the following chemical formula (5), poly(propylene glycol)triamine, polyoxypropylenediamine, etc., and one or more of these primary amines can be freely selected and used.

[0048] [ka] (x, y, and z are integers greater than or equal to 1)

[0049] Furthermore, in addition to primary amines, secondary and tertiary amines may also be used in the polyurethane foam manufacturing composition related to this technology, as long as they do not impair the purpose and effects of this technology. In this case, the proportion of primary amines in the total amines is preferably 90% or more, and more preferably 94% or more. By setting the proportion of primary amines in the total amines within this range, the reactivity of the resinification reaction can be improved. As a result, even when using raw materials with poor reactivity during the resinification reaction, such as aliphatic isocyanates and / or alicyclic isocyanates or biodegradable polyols, a good balance between the resinification reaction and the foaming reaction can be maintained, and consequently, polyurethane foam with excellent mechanical properties can be obtained.

[0050] (4) Foaming agent A foaming agent can be used in the polyurethane foam manufacturing composition related to this technology. As for the foaming agent that can be used in this technology, one or more foaming agents that can be used in the manufacture of polyurethane foam can be freely selected and used, as long as they do not impair the purpose or effects of this technology.

[0051] Examples of foaming agents include water, hydrocarbons, and halogenated compounds. Examples of hydrocarbons include cyclopentane, isopentane, and n-pentane. Examples of halogenated compounds include methylene chloride, trichlorofluoromethane, dichlorodifluoromethane, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, pentafluoroethyl methyl ether, and heptafluoroisopropyl methyl ether. In this technology, water is preferred as the foaming agent among these. The water may be deionized water, tap water, or distilled water.

[0052] The amount of blowing agent used in the polyurethane foam manufacturing composition according to this technology can be freely set as long as it does not impair the purpose and effects of this technology. In this technology, the lower limit of the blowing agent content in the polyurethane foam manufacturing composition is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of the total of the polyol and primary amine. By setting the lower limit of the blowing agent content in the polyurethane foam manufacturing composition within this range, foaming properties can be improved, and as a result, polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0053] In this technology, the upper limit of the foaming agent content in the polyurethane foam manufacturing composition is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the total of the polyol and primary amine. By setting the upper limit of the foaming agent content in the polyurethane foam manufacturing composition within this range, it is possible to suppress formation defects due to excessive foaming and also contribute to cost reduction.

[0054] (5) Catalyst A catalyst may be used in the polyurethane foam manufacturing composition related to this technology. As for the catalyst that can be used in this technology, one or more catalysts that can be used in the manufacture of polyurethane foam may be freely selected and used, as long as they do not impair the purpose or effects of this technology.

[0055] Examples of catalysts include tin catalysts such as dibutyltin dilaurate and stanus octoate, and metal catalysts (organometallic catalysts) such as phenylmercury propionate or lead octenoate. Also, triethylamine, triethylenediamine (TEDA), tetramethylguanidine, diethanolamine, bis(2-dimethylaminoethyl) ether, N,N,N′,N″,N″-pentamethyldiethylenetriamine, imidazole compounds, piperazine amines such as dimethylpiperazine, N-methyl-N'-(2-dimethylamino)ethylpiperazine, and N-methyl-N'-(2-hydroxyethyl)piperazine, morpholine amines such as N-methylmorpholine and N-ethylmorpholine, and 1,8-diazabicycline Amine catalysts such as amines referred to as DBU congeners, such as lo-[5,4,0]-undecene-7 (DBU), 1,5-diazabicyclo-[4,3,0]-nonene-5 (DBN), 1,8-diazabicyclo-[5,3,0]-decene-7 (DBD), and 1,4-diazabicyclo-[3,3,0]octene-4 (DBO), can also be used. Among these amine catalysts, tertiary amine catalysts and secondary amine catalysts are preferred, with a molecular weight of less than 700 being preferred, more preferably less than 500, and even more preferably less than 300.

[0056] The amount of catalyst used in the polyurethane foam manufacturing composition according to this technology can be freely set as long as it does not impair the purpose and effects of this technology. In this technology, the lower limit of the catalyst content in the polyurethane foam manufacturing composition is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of the total of the polyol and primary amine. By setting the lower limit of the catalyst content in the polyurethane foam manufacturing composition within this range, the resinification reaction and foaming reaction can be promoted, and as a result, polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0057] In this technology, the upper limit of the catalyst content in the polyurethane foam manufacturing composition is, for example, 20 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the total of the polyol and primary amine. By setting the upper limit of the catalyst content in the polyurethane foam manufacturing composition within this range, it is possible to prevent destabilization of the resinification reaction and foaming reaction, and to maintain a good balance between the resinification reaction and foaming reaction. As a result, polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0058] (6) Foam stabilizers A foam stabilizer may be used in the polyurethane foam manufacturing composition related to this technology. As for the foam stabilizer that can be used in this technology, one or more foam stabilizers that can be used in the manufacture of polyurethane foam may be freely selected and used, as long as they do not impair the purpose or effects of this technology.

[0059] Examples of foam stabilizers include silicone-based foam stabilizers, fluorine-containing compound-based foam stabilizers, and surfactants. Silicone-based foam stabilizers include those mainly composed of siloxane chains, those with a linear structure of siloxane chains and polyether chains, branched and segmented structures, and those in which polyether chains are modified into pendant-like structures of siloxane chains.

[0060] The amount of foam stabilizer used in the polyurethane foam manufacturing composition according to this technology can be freely set as long as it does not impair the purpose and effects of this technology. In this technology, the lower limit of the foam stabilizer content in the polyurethane foam manufacturing composition is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of the total of the polyol and primary amine. By setting the lower limit of the foam stabilizer content in the polyurethane foam manufacturing composition within this range, the foaming reaction can be stabilized, and as a result, polyurethane foam with excellent mechanical properties and appearance can be obtained.

[0061] In this technology, the upper limit of the foam stabilizer content in the polyurethane foam manufacturing composition is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the total of the polyol and primary amine. By setting the upper limit of the foam stabilizer content in the polyurethane foam manufacturing composition within this range, cost reduction can be achieved.

[0062] (7) Biodegradation accelerators A biodegradation accelerator can be used in the polyurethane foam manufacturing composition according to this technology. By using a biodegradation accelerator, the biodegradability can be improved when biodegradable raw materials are used as raw materials for the polyurethane foam according to this technology.

[0063] As for the biodegradation accelerators that can be used in this technology, one or more biodegradation accelerators that can be used with polyurethane foam can be freely selected and used, as long as they do not impair the purpose or effects of this technology.

[0064] Examples of biodegradation accelerators include sugars such as glucose, xylose, galactose, maltose, sucrose, chitin, and cellulose; starches; amino acids; peptides; gums such as tamarind gum; and lignin.

[0065] The amount of biodegradation accelerator used in the polyurethane foam manufacturing composition according to this technology can be freely set as long as it does not impair the purpose and effects of this technology. In this technology, the lower limit of the biodegradation accelerator content in the polyurethane foam manufacturing composition is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of the total of the polyol and primary amine.

[0066] In this technology, the upper limit of the content of the biodegradation accelerator in the polyurethane foam manufacturing composition is, for example, 10 parts by mass or less, preferably 7 parts by mass or less, and more preferably 5 parts by mass or less, based on 100 parts by mass of the total of the polyol and primary amine.

[0067] (8) Others The polyurethane foam manufacturing composition relating to this technology may include, as long as it does not impair the purpose or effect of this technology, one or more other components that can be used in polyurethane foam manufacturing compositions may be freely selected and used depending on the purpose.

[0068] Examples of components that can be used in polyurethane foam manufacturing compositions related to this technology include flame retardants, stabilizers, plasticizers, colorants, antioxidants, crosslinking agents, antibacterial agents, dispersants, and ultraviolet absorbers.

[0069] 2. Polyurethane foam The polyurethane foam relating to this technology is manufactured using the polyurethane foam manufacturing composition relating to this technology described above.

[0070] The polyurethane foam used in this technology may be flexible polyurethane foam, rigid polyurethane foam, or semi-rigid polyurethane foam, but flexible polyurethane foam is particularly preferred. Specifically, foam with an elongation of 50% or more is preferred, and foam with an elongation of 90% or more is more preferred. Polyurethane foam having an elongation in this range is sufficiently flexible compared to semi-rigid and rigid polyurethane foams, and can be called flexible polyurethane foam.

[0071] For example, by using a primary amine with an average molecular weight of 1,000 to 20,000 as the primary amine used in the polyurethane foam manufacturing composition related to the aforementioned technology, the resinification reaction can be moderately enhanced, and hardening in the initial stages of manufacturing can be suppressed. As a result, a good flexible polyurethane foam can be obtained.

[0072] 3. Applications of polyurethane foam The polyurethane foam related to this technology can be used in a wide range of applications in a wide range of fields, thanks to its high quality. For example, it can be suitably used in furniture such as sofas and chairs, bedding such as mattresses and pillows, clothing such as underwear, daily necessities such as dishes and cleaning sponges, vehicle and aircraft interior products such as car seats, building joint materials, building cushioning materials, building sealants, home appliance sealants, soundproofing materials, packaging materials, vehicle insulation materials, condensation prevention materials, interior materials, home appliance insulation materials, pipe insulation materials, various covers, cushioning materials, toys, miscellaneous goods, and more.

[0073] 4. Method for manufacturing polyurethane foam The polyurethane foam according to this technology can be manufactured by mixing the components of the polyurethane foam manufacturing composition according to this technology described above to prepare a composition, and then proceeding with a resinification reaction and a foaming reaction. The resinification reaction and foaming reaction can be carried out using any combination of general methods, as long as they do not impair the purpose or effect of this technology.

[0074] In the polyurethane foam manufacturing method according to this technology, either slab foaming or mold foaming can be used for foaming. Slab foaming is a method in which a polyurethane foam manufacturing composition (raw material for polyurethane foam) is mixed and extruded onto a belt conveyor belt, and foamed at atmospheric pressure and room temperature. On the other hand, mold foaming is a method in which a polyurethane foam manufacturing composition (raw material for polyurethane foam) is mixed and injected into the cavity of a mold (metal mold), and foamed into the shape of the cavity.

[0075] When manufacturing polyurethane foam using aliphatic isocyanates, the reactivity during manufacturing is poorer compared to using aromatic isocyanates, resulting in longer curing times and making general mold molding difficult. This led to problems such as poor mass production and poor design quality of the manufactured polyurethane foam. However, this technology uses primary amines to accelerate initial thickening (cream time), promote internal heat generation, improve the reactivity of the resinification reaction, and enhance the reactivity of the foaming reaction, thereby shortening the rise time. As a result, even when using raw materials with poor reactivity during manufacturing, such as aliphatic isocyanates and / or alicyclic isocyanates or biodegradable polyols, the curing time (cream time + rise time) can be shortened. Thus, using this technology, even when using environmentally friendly raw materials, it is possible to obtain polyurethane foam with high mass production potential, excellent mechanical properties, and superior design quality. [Examples]

[0076] The present technology will be described in more detail below based on the following examples. The examples described below are representative examples of the present technology and should not be interpreted as narrowing the scope of the present technology.

[0077] (1) Raw materials Polyol: A mixture of 50 parts of naturally derived ester polyol (refined castor oil: molecular weight 950, number of functional groups 2.7, hydroxyl value 160 mg / g) and 50 parts of sebacate ester polyol (molecular weight 2000, number of functional groups 2, hydroxyl value 56 mg / g). Primary amine: Polyether primary amine (weight-average molecular weight (Mw): 5000, number of functional groups: 3, viscosity: 819 cSt (25℃), amine hydrogen equivalent (AHEW): 952 g / eq, ratio of primary amine to total amine: 97% or more, x+y+z=85 in the above chemical formula (5)) Foam stabilizer: Silicone-based foam stabilizer Biodegradation accelerator: Maltose Foaming agent: Water Isocyanate: HDI isocyanurate (HDI trimmer)

[0078] (2) Manufacturing of polyurethane foam Each polyurethane foam was manufactured by mixing the raw materials shown in Table 1 below with a catalyst (2 parts by mass of tin catalyst and 4 parts by mass of tertiary amine catalyst (a mixture of molecular weights from 96 to 152)) to prepare a composition, and then transferring it to a mold and foaming it.

[0079] (3) Evaluation The reactivity during manufacturing was evaluated by measuring the cream time and rise time. The state of the manufactured polyurethane foam was also observed. Furthermore, the physical properties of the manufactured polyurethane foam were evaluated using the following methods.

[0080] [Tensile strength] [Elongation] Tensile strength and elongation were measured in accordance with JIS K6400-5.

[0081] [Rebound modulus] The rebound modulus was measured according to JIS K6255.

[0082] (4) Results The results are shown in Table 1 below. The cream time and rise time are also shown in the graph in Figure 1. [Table 1]

[0083] (5) Discussion As shown in Table 1 and Figure 1, Examples 1-4, which used primary amines, showed shorter cream time and rise time compared to Comparative Example 1, which did not use a primary amine. Furthermore, Examples 1-4 exhibited flexibility with elongation exceeding 50%. Tensile strength was also better in Examples 1-3, which used primary amines, compared to Comparative Example 1, which did not use a primary amine. Although not shown in the table, the foam condition was also better in Examples 1-3, which used primary amines, compared to Comparative Example 1, which did not use a primary amine. While Example 4 exhibited high reactivity, inhibiting good cell formation and resulting in lower tensile strength and elongation, the effect of this technology in improving reactivity was still fully demonstrated.

Claims

1. Polyols and, Aliphatic isocyanates and / or alicyclic isocyanates, Primary amines having 2 to 4 functional groups containing active hydrogen groups, It contains a foaming agent, The weight-average molecular weight of the aforementioned primary amine is 1800 to 8000. Composition for manufacturing polyurethane foam.

2. The polyurethane foam manufacturing composition according to claim 1, comprising 1 to 20 parts by mass of the primary amine with respect to a total of 100 parts by mass of the polyol and the primary amine.

3. The polyurethane foam manufacturing composition according to claim 1 or 2, wherein the polyol is a biodegradable polyol.

4. A polyurethane foam produced from the polyurethane foam production composition described in claim 1 or 2.

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