JP2019203053A - Polyol composition for producing rigid polyurethane foam - Google Patents

Abstract

To provide a polyol composition for producing rigid polyurethane foam, comprising HFO-1336 mzz-Z and an aromatic polyester polyol, which does not phase separate for a long term without a need for stirring to keep a uniform state.SOLUTION: Provided are: a polyol composition for producing rigid polyurethane foam, comprising Component A: a polyol containing 50 mass% or more of an aromatic polyester polyol (Component A-1) having a hydroxyl value of 100 mgKOH/g to 500 mgKOH/g, Component B: a blowing agent containing 50 mass% or more of cis-1,1,1,4,4,4-hexafluoro-2-butene (Component B-1), and Component C: a compound represented by formula (I): RO-(CHCHO)n-H (I), wherein a content of the Component B-1 is 28 pts.mass to 50 pts.mass relative to 100 pts.mass of the Component A; and a method for producing rigid polyurethane foam using the polyol composition.SELECTED DRAWING: None

Description

  The present invention relates to a polyol composition for producing rigid polyurethane foam. More specifically, a polyol composition for producing rigid polyurethane foam that can be suitably used as a building material, an electric refrigerator, a refrigerator / freezer warehouse, a heat insulating material such as a bathtub, piping, a dew condensation prevention material for a detached house, an apartment, an industrial piping, etc. And a method for producing a rigid polyurethane foam using the polyol composition.

  Rigid polyurethane foams (including polyisocyanurate foams containing isocyanurate rings; the same applies below) are used as heat insulating materials for building materials, electric refrigerators, refrigerators / freezer warehouses, bathtubs, piping, etc. ing.

  For example, when the rigid polyurethane foam is used as a heat insulating material such as a house or building building material, a component mainly composed of polyol and a component mainly composed of polyisocyanate are foamed with a high-pressure foaming machine, etc. A method of mixing in the presence of a catalyst, a foam stabilizer and other auxiliary agents if necessary, pouring into a mold and foaming and curing, and spraying onto a target site such as a wall or ceiling at a construction site It is manufactured by the method of foaming and curing above, the method of cutting after foaming and curing, and the like.

  Conventionally, fluorocarbons such as 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365mfc), which are hydrofluorocarbons, are used as blowing agents. A foaming agent is used, and the fluorocarbon foaming agent has not only good heat insulation properties but also relatively good compatibility with the components constituting the polyol composition.

  In recent years, trans-1,3,3,3-tetrafluoro-1-propene (HFO-1234ze-E) has been used as a foaming agent from the viewpoint of protecting the global environment by avoiding destruction of the ozone layer and global warming in the stratosphere. ), 2,3,3,3-tetrafluoro-1-propene (HFO-1234yf), trans-1-chloro-3,3,3-trifluoro-1-propene (HCFO-1233zd-E), trans- 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E) and cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz) Hydrohaloolefins such as -Z) have been investigated. Although these foaming agents are fluorine-based compounds, the ozone depletion coefficient is substantially zero and the global warming coefficient is very small as 10 or less. Therefore, hydrophobing agents such as HFC-245fa and HFC-365mfc are used. Expected to replace fluorocarbons.

  In addition, hard polyurethane foams are particularly used for heat insulating materials as described above, but when used in the building materials field, in addition to the heat insulating properties of foaming agents, the heat resistance and flame retardancy of the resin itself are improved. More demanded. Attempts have been made to use aromatic polyester polyol as a raw material as a method for improving heat resistance and flame retardancy, but the polyol is the main component due to low compatibility with some foaming agents. There is a problem that the components are easily phase-separated, and foaming unevenness occurs when reacting with the polyisocyanate, so that a homogeneous foam cannot be obtained.

  As an example of using a hydrohaloolefin having a small ozone depletion coefficient and a small global warming coefficient as a blowing agent, Patent Document 1 discloses that there is substantially no ozone depletion coefficient (ODP) and a global warming coefficient ( Cis-1,1,1 for use in the production of foams that provide low flammability, good thermal insulation and high dimensional stability by using blowing agents that have no GWP) or very low GWP , 4, 4, 4-hexafluoro-2-butene and a low compatible active hydrogen-containing compound having two or more active hydrogens are disclosed.

  Patent Document 2 discloses a composition suitable for the production of polyurethane foam in order to achieve solubilization between a polyol system and a foaming agent, comprising at least one polyol component, at least one foaming agent, and A catalyst that exhibits a catalytic action on the formation of a urethane or isocyanurate bond, a silicon-containing foam stabilizer, other additives as optional components, and an isocyanate component as an optional component, and comprising at least one kind The surfactant in the composition further comprises an unsaturated halogenated hydrocarbon as a blowing agent, and further comprising at least one surfactant TD that has no silicon atom and has an HLB value of less than 10. The composition characterized by the total ratio of TD being 0.05-20 mass parts with respect to 100 mass parts of the said polyol component is disclosed.

  In US Pat. No. 6,057,049, a polyol premix composition is treated with a polyisocyanate due to the reaction of some amine catalysts with some hydrohaloolefins such as 1234ze, 1233zd, 1336mzzm, and / or combinations thereof. Hydrohaloolefin blowing agents, polyols, silicone surfactants, and alone, which solves the problem that foams will be of lower quality if they change over time prior to the formation and collapse during foam formation A polyol premix composition comprising a combination of non-amine catalysts used in combination with an amine catalyst is disclosed.

Special Table 2010-534253 Special table 2017-504678 gazette Special table 2013-514442 gazette

  HFO-1336mzz-Z as a foaming agent has advantages of being friendly to the global environment and exhibiting excellent heat insulation properties, but has a lower compatibility with aromatic polyester polyols than HCFO-1233zd-E, and is aromatic. When HFO-1336mzz-Z is used as a foaming agent for the polyester polyol, it is necessary to vigorously stir in the storage tank as a pre-process of foaming and curing reaction, and workability is significantly reduced. Furthermore, since the foaming agent is easily separated, the reaction with the polyisocyanate becomes inhomogeneous, and voids and cell turbulence occur in the manufactured rigid polyurethane foam, making it difficult to obtain a homogeneous rigid polyurethane foam. is there.

  The present invention relates to a polyol composition for producing a rigid polyurethane foam containing HFO-1336mzz-Z and an aromatic polyester polyol that does not require phase separation for a long time without requiring stirring to maintain a uniform state, and the polyol The present invention relates to a method for producing a rigid polyurethane foam using the composition.

The present invention
[1] Component A: a polyol containing 50% by mass or more of an aromatic polyester polyol (component A-1) having a hydroxyl value of 100 mgKOH / g or more and 500 mgKOH / g or less,
Component B: foaming agent containing 50% by mass or more of cis-1,1,1,4,4,4-hexafluoro-2-butene (component B-1), and component C: Formula (I):
^{_{R 1 O- (CH 2 CH 2}} O) n-H (I)
(In the formula, R ¹ is an alkyl group having 8 to 12 carbon atoms, and n is an average added mole number of CH ₂ CH ₂ O, and is 0 to 3)
A hard polyurethane foam-producing polyol composition containing a compound represented by: wherein the content of component B-1 is 28 to 50 parts by mass with respect to 100 parts by mass of component A The present invention relates to a polyol composition for producing a polyurethane foam, and [2] a method for producing a rigid polyurethane foam comprising a step of mixing the polyol composition described in [1] above with a polyisocyanate.

  Even if HFO-1336mzz-Z and an aromatic polyester polyol are used in combination, the polyol composition for producing a rigid polyurethane foam of the present invention does not require stirring to maintain a uniform state for a long period of time. There is an excellent effect of not.

  The polyol composition for producing a rigid polyurethane foam according to the present invention has a cis-1,1,1,1 having an ozone depletion coefficient of substantially zero, an extremely low global warming coefficient of 10 or less, and excellent heat insulating properties. It contains 4,4,4-hexafluoro-2-butene (HFO-1336mzz-Z) as a foaming agent, and further contains a compound represented by the formula (I) described later. Thereby, a stable polyol composition that does not phase-separate for a long period of time can be easily obtained even when an aromatic polyester polyol having high flame retardancy but low compatibility with HFO-1336mzz-Z is blended as a polyol component. By using this polyol composition, it is possible to easily produce a rigid polyurethane foam having high heat insulating properties, flame retardancy, and heat resistance.

The details of the reason why the effects of the present invention are manifested by the polyol composition of the present invention are not clear, but are considered as follows.
The aromatic polyester polyol typified by the phthalic polyester polyol used as the raw material for the rigid polyurethane foam is equimolar or slightly less than the equimolar amount with respect to 1 mole of the aromatic polyvalent carboxylic acid molecule. Since it is a low molecular weight polyester polyol having a hydroxyl group at the end, reacted with a polyhydric alcohol in the number of moles, aromatic rings in each molecular structure are relatively strongly bonded between the polyester polyol molecules, and more hydroxyl groups are bonded. High polarity by containing. Therefore, it is estimated that HFO-1336mzz-Z having greatly different polarities and solubility parameters cannot enter between the polyester polyol molecules, and the compatibility between the two is low. On the other hand, in the present invention, the compound represented by the formula (I) having high compatibility with the aromatic polyester polyol enters between the molecules of the aromatic polyester polyol, so that there is a gap where HFO-1336mzz-Z enters. It is presumed that the polyester polyol and HFO-1336mzz-Z are formed and become stable for a long time.

<Polyol (component A)>
Any polyol can be used as the polyol (component A) in the present invention as long as it is a normal polyol used in the production of rigid polyurethane foams. The aromatic polyester has a hydroxyl value of 100 mgKOH / g or more and 500 mgKOH / g or less. It contains 50% by mass or more of polyol (component A-1).

  As a polyol, what is conventionally used when manufacturing a rigid polyurethane foam is illustrated. Representative examples of polyols include, for example, polyester polyols, polyether polyols, polymer polyols, and phenolic resins described in “Polyurethane Resin Handbook” edited by Keiji Iwata (published on September 25, 1987, published by Nikkan Kogyo Shimbun). Examples thereof include a system polyol and a Mannich polyol. These can be used alone or in admixture of two or more.

  Examples of the polyester polyol include aromatic polyester polyol and aliphatic polyester polyol. These can be produced by a condensation reaction of a polybasic acid and a polyhydric alcohol. An aromatic polybasic acid is used for the aromatic polyester polyol, and an aliphatic polybasic acid is used for the aliphatic polyester polyol. Moreover, the polyester polyol manufactured by the condensation reaction of the mixture of an aromatic polybasic acid and an aliphatic polybasic acid, and a polyhydric alcohol is also mentioned as an example.

  Examples of the polybasic acid include linear saturated aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; and cyclic saturated aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid; halogen-containing aromatic dicarboxylic acids such as tetrabromophthalic acid; Ester-forming derivatives of these; and acid anhydrides thereof. These can be used alone or in combination of two or more. The polybasic acid may optionally contain a tribasic or higher polybasic acid such as trimellitic acid and pyromellitic acid in addition to the dicarboxylic acid and derivatives thereof.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1 , 6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, diglycerin, dextrose, sorbitol and the like. These can be used alone or in combination of two or more.

  Examples of the polyether polyol include polyoxyalkylene polyols.

  Polyoxyalkylene polyols are ring-opening additions of alkylene oxides starting from compounds with two or more functional groups selected from hydroxyl groups, primary amino groups, secondary amino groups, and other active hydrogen-containing groups. For example, it can be produced by addition reaction of an alkylene oxide with a polyvalent amine, polyhydric alcohol, alkanolamine, polyhydric phenol or the like. The two or more functional groups may be the same or different.

  Examples of the polyvalent amine include ethylenediamine, tolylenediamine, diethyltoluenediamine, diethylenetriamine, and triethylenetetramine. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, pentaerythritol, diglycerin, sucrose, dextrose, sorbitol and the like. Examples of the alkanolamine include ethanolamine, diethanolamine, triethanolamine, and methyldiethanolamine. Bisphenol A etc. are illustrated as a polyhydric phenol. These may be modified products, and each can be used alone or in combination of two or more.

  Examples of the alkylene oxide include ethylene oxide and propylene oxide. These can be used alone or in combination of two or more.

  Examples of the polymer polyol include those in which polymer fine particles such as polyacrylonitrile fine particles and polystyrene fine particles are dispersed in the polyoxyalkylene-based polyol.

  The phenolic resin-based polyol is a compound having two or more active hydrogen-containing groups determined by the Zerebitinov method in the molecule. Specifically, including novolac type phenol resin polyol, resol type phenol resin polyol, benzylic ether type phenol resin polyol and the like obtained by condensation reaction of phenols and aldehydes in the presence of a catalyst, Examples thereof include modified phenolic resin-based polyols obtained by ring-opening addition of alkylene oxide or alkylene carbonate to some or all phenolic hydroxyl groups of a phenol resin.

  Examples of Mannich polyols include those obtained by condensation reaction of phenols, aldehydes, alkanolamines and the like, and those obtained by performing ring-opening addition reaction of alkylene oxides such as ethylene oxide and propylene oxide as necessary. .

  Further, the number of functional groups (number of hydroxyl groups in one molecule) of the above-mentioned polyol varies depending on the desired physical properties of the rigid polyurethane foam and cannot be determined unconditionally, but is usually 2-8.

<Aromatic polyester polyol (component A-1)>
The aromatic polyester polyol (component A-1) is mainly composed of one or more selected from the group consisting of phthalic acid, terephthalic acid, and isophthalic acid from the viewpoint of improving the flame retardancy and heat resistance of the rigid polyurethane foam. Phthalic acid produced by a condensation reaction of an aromatic dicarboxylic acid as a component and a polyhydric alcohol containing as a main component one or more selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol Polyester polyols are preferred, and phthalic polyester polyols are more preferred. In addition, as the terephthalic acid polyester polyol, those produced by subjecting polyethylene terephthalate recovered as a used PET product to glycolysis with a polyhydric alcohol such as ethylene glycol or diethylene glycol can be suitably used. .

  The content of the phthalic polyester polyol in Component A-1 is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and 100% by mass or less.

  From the viewpoint of improving the strength of the rigid polyurethane foam, the hydroxyl value of the aromatic polyester polyol (component A-1) is 100 mgKOH / g or more, preferably 150 mgKOH / g or more, more preferably 200 mgKOH / g or more, From the viewpoint of improving the flame retardancy and heat resistance of the rigid polyurethane foam, it is 500 mgKOH / g or less, preferably 450 mgKOH / g or less, more preferably 400 mgKOH / g or less. Here, the hydroxyl value of component A-1 means the hydroxyl value of the component A-1 when there is only one kind of polyol. When there are two or more polyols constituting Component A-1, it means a weighted average hydroxyl value, and if the weighted average hydroxyl value falls within the above range, a polyol having no hydroxyl value is included. Also good. In the present specification, the hydroxyl value is a value obtained based on JIS K1557.

  As the aromatic polyester polyol (component A-1), for example, Maximol series manufactured by Kawasaki Chemical Industry Co., Ltd. is commercially available. As phthalic anhydride-based polyester polyols, Maximol RDK-121 (hydroxyl value: 260 mgKOH / g), RDK-133 (hydroxyl value: 315 mgKOH / g), RDK-142 (hydroxyl value: 400 mgKOH / g), RDK-342 ( Hydroxyl value: 420 mgKOH / g) As terephthalic acid-based polyester polyols, Maximol RFK-505 (hydroxyl value: 250 mgKOH / g), RFK-509 (hydroxyl value: 200 mgKOH / g), RFK-556 (hydroxyl value: 250 mgKOH / g) g), RLK-035 (hydroxyl value: 150 mgKOH / g), RLK-085 (hydroxyl value: 200 mgKOH / g), RLK-087 (hydroxyl value: 200 mgKOH / g), and the like.

  Content of aromatic polyester polyol (component A-1) is 50 mass% or more in component A, Preferably it is 60 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, more More preferably, it is 90 mass% or more and 100 mass% or less.

  From the viewpoint of improving the strength of the rigid polyurethane foam, the content of component A in the polyol composition of the present invention is preferably 50% by mass or more, and more preferably 55% by mass or more. Moreover, 77 mass% or less is preferable from a viewpoint of the flame retardance and heat resistance improvement of rigid polyurethane foam, and a density reduction, and 72 mass% or less is more preferable. In the present specification, the content of component A means the total amount thereof when component A contains a plurality of polyols.

<Foaming agent (component B)>
The foaming agent (component B) in the present invention contains cis-1,1,1,4,4,4-hexafluoro-2-butene (component B-1). From the viewpoint of improving the heat insulation of the rigid polyurethane foam and from the viewpoint of protecting the global environment, cis-1,1,1,4,4,4-hexafluoro-2-butene (component B-) in the foaming agent (component B) is used. The content of 1) is 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and 100% by mass or less. is there.

  Any foaming agent other than Component B-1 can be used as long as it is a normal foaming agent used in the production of rigid polyurethane foam, but the ozone depletion coefficient is substantially zero from the viewpoint of protecting the global environment. And hydrohaloolefins having a global warming potential of 20 or less, and from the viewpoint of easy handling and foaming characteristics of polyurethane foam, trans-1-chloro-3,3,3-trifluoro-1-propene (HCFO-1233zd-E) or trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz-E) is preferred, and trans-1,1,1,4,4, 4-hexafluoro-2-butene (HFO-1336mzz-E) is more preferred. In addition, as other foaming agents, water (that is, carbon dioxide is generated by the reaction of water and isocyanate to become foaming agents) can be used together, and gases such as nitrogen, air, carbon dioxide, normal butane, isobutane, Low-boiling point aliphatic hydrocarbons such as normal pentane, neopentane, isopentane, cyclopentane, normal hexane, cyclohexane, methylcyclopentane, methylcyclohexane, 1,1,1,3,3-pentafluoropropane, 1,1,1, Hydrofluorocarbons such as 3,3-pentafluorobutane may be used in combination. Hydrofluoroolefins having a global warming potential of 20 or less are also preferable, for example, trans-1,3,3,3-tetrafluoro-1-propene, 2,3,3,3-tetrafluoro-1-propene, etc. May be used in combination.

  The content of Component B in the polyol composition of the present invention depends on the density of the rigid polyurethane foam and the type and combination of the foaming agent, but from the viewpoint of improving the heat insulation of the rigid polyurethane foam, the content of Component B is 100 parts by mass. 28 parts by mass or more, preferably 30 parts by mass or more, and more preferably 32 parts by mass or more. Further, from the viewpoint of maintaining the strength properties of the rigid polyurethane foam and improving the flame retardancy and heat resistance, it is 50 parts by mass or less, preferably 45 parts by mass or less, and preferably 40 parts by mass or less with respect to 100 parts by mass of Component A. Is more preferable. In the present specification, the content of component B means the total amount thereof when component B contains a plurality of blowing agents.

  In addition, the content of Component B-1 in the polyol composition of the present invention is preferably 28 parts by mass or more, and 30 parts by mass or more with respect to 100 parts by mass of Component A, from the viewpoint of improving the heat insulation of the rigid polyurethane foam. Is more preferable, and 32 mass parts or more is still more preferable. Further, from the viewpoint of maintaining the strength properties of the rigid polyurethane foam and improving the flame retardancy and heat resistance, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and 40 parts by mass with respect to 100 parts by mass of Component A. The following is more preferable.

<Compound of Formula (I) (Component C)>
Component C in the present invention has the formula (I):
^{_{R 1 O- (CH 2 CH 2}} O) n-H (I)
(In the formula, R ¹ is an alkyl group having 8 to 12 carbon atoms, and n is an average added mole number of CH ₂ CH ₂ O, and is 0 to 3)
It is a compound represented by these.

In the formula (I), the number of carbon atoms of the alkyl group represented by R ¹ is preferably 9 or more, more preferably 11 or less, and more preferably 10 from the viewpoint of improving the stability of the polyol composition. The alkyl group for R ¹ may be either a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of improving the stability of the polyol composition. The average added mole number n of CH ₂ CH ₂ O is preferably 2 or less, more preferably 1 or less, and still more preferably 0 from the viewpoint of improving the stability of the polyol composition.

  The content of Component C in the polyol composition of the present invention is preferably 3 parts by mass or more with respect to 100 parts by mass of Component A from the viewpoint of improving compatibility, although it depends on the type and combination of the polyol and foaming agent. 5 mass parts or more are more preferable, and 8 mass parts or more are still more preferable. Moreover, from a viewpoint of improving the flame retardance and heat resistance of a rigid polyurethane foam, 17 mass parts or less are preferable with respect to 100 mass parts of component A, 15 mass parts or less are more preferable, and 12 mass parts or less are still more preferable. In the present specification, the content of component C means the total amount thereof when component C includes a plurality of compounds.

<Catalyst (component D)>
The polyol composition of the present invention preferably contains a catalyst (component D) from the viewpoints of productivity of rigid polyurethane foam, flame retardancy, adhesion, and liquid flowability. As the catalyst (component D) in the present invention, any catalyst can be used as long as it is a normal catalyst used in the production of rigid polyurethane foam. For example, 1,4-diazabicyclo [2,2,2] octane, 2-methyl-1,4-diazabicyclo [2,2,2] octane, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-propanediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, tris (3-dimethylaminopropyl) amine, N, N-dimethylcyclohexylamine, N, N ′, N′-trimethylaminoethylpiperazine, N, N-dimethylpiperazine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ) Ether, N, N ′, N ″ -tris (3-dimethylaminopropyl) hexahydro-s-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, N -Methylmorpholine, N-ethylmorpholine, N- (dimethylaminoethyl) morpholine, dimorpholinodiethyl ether, N, N-dimethylbenzylamine, 1-methylimidazole, 1-isobutyl-2-methylimidazole, 1,2-dimethyl Imidazole, 6-dimethylamino-1-hexanol, 5-dimethylamino-3-methyl-1-pentanol, bis (3-dimethylaminopropyl) amine, N, N-bis (3-dimethylaminopropyl) isopropanolamine, N- (3-dimethylaminopropyl) -N-methylethanolamine, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) -1,3-propanediamine, N, N-dimethylaminopropyl Amine, dimethylethanolamine, 2- (2-dimethyl) Minoethoxy) ethanol, 2- [2- (2-dimethylaminoethoxy) ethoxy] ethanol, N- (2-dimethylaminoethyl) -N-methylethanolamine, N- [2- (2-dimethylaminoethoxy) ethyl] -N-methylethanolamine, N, N, N ', N "-tetramethyl-N"-(2-hydroxypropyl) -diethylenetriamine and N- [2- (2-dimethylaminoethoxy) ethyl] -N-methyl A tertiary amine catalyst such as -1,3-propanediamine, 3-dimethylaminopropyl) urea, 2-hydroxymethyl-1,4-diazabicyclo [2,2,2] octane, a derivative of the tertiary amine, And a salt of the tertiary amine and an acid such as carboxylic acid or carbonic acid; tin dibutyldiacetate, tin dibutyldilaurate, di (2-ethyl) Organotin compounds such as tin (xyl) dilaurate and di (2-ethylhexanoate) tin; organometallic catalysts such as tris (2-ethylhexanoate) bismuth and di (2-ethylhexanoate) lead; potassium acetate and octyl Examples include potassium salts such as potassium acid; isocyanuration catalysts such as quaternary ammonium salts, and these can be used alone or in combination of two or more. Among these, it is preferable to use a tertiary amine catalyst from the viewpoint of rapidly foaming and curing the rigid polyurethane foam and further ensuring the fluidity of the foam. In addition, when manufacturing rigid polyurethane foam with a spray formulation, it is preferable to use an organometallic catalyst from the viewpoint of improving reactivity through a synergistic effect with an amine catalyst, and rigid polyurethane foam is used for heat insulating building materials. In that case, it is preferable to use an isocyanurate-forming catalyst from the viewpoint of imparting flame retardancy.

  The content of component D in the polyol composition of the present invention may be appropriately determined depending on the reactivity with the polyol component and polyisocyanate used, the use of the rigid polyurethane foam, etc. From the viewpoint of improving (foamability, curability) and the function of the rigid polyurethane foam (flame retardancy, adhesiveness, liquid flowability, etc.), 0.5 parts by mass or more is preferable with respect to 100 parts by mass of Component A. More preferably 8 parts by mass or more, and still more preferably 1 part by mass or more. Moreover, from a viewpoint of improving the control of reactivity and the function of a rigid polyurethane foam, 15 mass parts or less are preferable with respect to 100 mass parts of component A, 10 mass parts or less are more preferable, and 8 mass parts or less are still more preferable. In addition, in this specification, content of the component D means the total amount, when the component D contains a some catalyst.

<Foam stabilizer (component E)>
The polyol composition of the present invention preferably contains a foam stabilizer (component E) from the viewpoint of securing the cell foam stability and the closed cell ratio. As the foam stabilizer (component E) in the present invention, any ordinary foam stabilizer used in the production of rigid polyurethane foams can be used. For example, polyoxyalkylene-polydimethylsiloxane copolymer, polydialkylsiloxane, silicone-based foam stabilizer such as polyoxyalkylene polyol-modified dimethylpolysiloxane, fatty acid salt, sulfate ester salt, phosphate ester salt, sulfonate salt, etc. Examples thereof include an anionic surfactant, and these can be used alone or in combination of two or more. In these, a silicone type foam stabilizer is preferable from a viewpoint of strong foam control power and dimensional stability, and a polyoxyalkylene-polydimethylsiloxane copolymer is more preferable.

  The content of component E in the polyol composition of the present invention depends on the production method of the rigid polyurethane foam, the density of the rigid polyurethane foam and the type and combination of the foaming agent, From a viewpoint of ensuring, 0.2 mass part or more is preferable with respect to 100 mass parts of component A, 0.5 mass part or more is more preferable, and 1.0 mass part or more is still more preferable. Further, from the same viewpoint, 4.0 parts by mass or less is preferable, 100 parts by mass or less is more preferable, 3.0 parts by mass or less is further preferable, and 2.0 parts by mass or less is preferable with respect to 100 parts by mass of Component A. Is even more preferable. In addition, in this specification, content of the component E means those total amounts, when the component E contains a several foam stabilizer.

<Flame retardant (component F)>
The polyol composition of the present invention preferably contains a flame retardant (component F) from the viewpoint of improving the flame retardancy of the rigid polyurethane foam. As the flame retardant (component F) in the present invention, any flame retardant used in the production of rigid polyurethane foam can be used. For example, halogen-based difficulties such as tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloroisopropyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate Non-halogen flame retardants such as a flame retardant and triethyl phosphate can be used, and these can be used alone or in combination of two or more. Of these, tris (2-chloroisopropyl) phosphate is preferred.

  The content of component F in the polyol composition of the present invention depends on the density and use of the rigid polyurethane foam, but from the viewpoint of improving flame retardancy without impairing the physical properties of the rigid polyurethane foam, On the other hand, 10 mass parts or more are preferable, 12 mass parts or more are more preferable, and 15 mass parts or more are still more preferable. Further, from the same viewpoint, the amount is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, and further preferably 30 parts by mass or less with respect to 100 parts by mass of Component A. In addition, in this specification, content of the component F means the total amount, when the component F contains a several flame retardant.

<Other ingredients>
The polyol composition of the present invention may contain other auxiliary agents as necessary in addition to the components A to F described above. Examples of other auxiliaries include auxiliaries generally used in the production of rigid polyurethane foams, such as cross-linking agents, pigments, and fillers. These auxiliaries can be used within a range that does not impair the object of the present invention, and the content thereof can be appropriately adjusted according to known techniques.

  The polyol composition of the present invention can be easily prepared by mixing the above-mentioned components A to E and other components as required.

  Although the polyol mixture of the present invention contains HFO-1336mzz-Z, which has a low compatibility with the aromatic polyester polyol and the aromatic polyester polyol, as a blowing agent, stirring is performed to maintain a uniform state. Even if not performed, both can be stored for a long time without separation. Therefore, by using the polyol composition of the present invention, stable production with good workability can be realized in the production of a rigid polyurethane foam, and therefore the polyol composition of the present invention produces a rigid polyurethane foam. As a raw material, it can be used more suitably.

<Method for producing rigid polyurethane foam>
The manufacturing method of the rigid polyurethane foam of this invention includes the process of mixing the said polyol composition and polyisocyanate, foaming and hardening reaction arise by mixing, and a rigid polyurethane foam is obtained.

  Examples of the polyisocyanate include those known in the field of the present invention. For example, aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthylene diisocyanate; urethane bond, carbodiimide bond, Examples of the modified polyisocyanate include one or more of a uretoimine bond, an allophanate bond, a urea bond, a burette bond, and an isocyanurate bond. These polyisocyanates may be used alone or in combination of two or more. Among the polyisocyanates, polymethylene polyphenylene polyisocyanate is preferable from the viewpoint of improving the strength, flame retardancy and heat resistance of the rigid polyurethane foam.

  The ratio of the polyol composition to the polyisocyanate is usually preferably an isocyanate index of 100 or more, more preferably 105 or more, still more preferably 110 or more, preferably 400 or less, more preferably 300 or less, and still more preferably 250. Adjust so that: Moreover, it is adjusted so that it is preferably 100 or more and 400 or less, more preferably 105 or more and 300 or less, and still more preferably 110 or more and 250 or less.

  The rigid polyurethane foam can be obtained, for example, by mixing and stirring the polyol composition and polyisocyanate with a high-pressure foaming machine or the like, and then injecting into a mold or spraying on the adherend surface to cause foaming and curing reaction. it can. More specifically, for example, after adjusting the temperature of the polyol composition to 15 to 25 ° C. using a tank or the like, a foaming machine such as a spray type foaming machine, an automatic mixing injection type foaming machine, or an automatic mixing injection type foaming machine is used. A rigid polyurethane foam can be obtained by mixing a polyol composition and a polyisocyanate, and foaming and curing reaction.

  The obtained rigid polyurethane foam can be suitably used as, for example, a building material, an electric refrigerator, a refrigerator / freezer warehouse, a heat insulating material such as a bathtub, a pipe, a dew condensation prevention material for a detached house, an apartment, an industrial pipe, and the like. it can.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Examples 1-16 and Comparative Examples 1-8
(1) Manufacture of a polyol composition Each component other than Component B (excluding water) with the mass (g) shown in Tables 1 and 2 was put into a 300 mL polypropylene disposable cup. K. The mixture was stirred for 20 seconds at a rotational speed of 3000 r / min using a homodisper (L type, manufactured by Tokushu Kika Kogyo Co., Ltd.) and cooled to 15 ° C. It should be noted that the solid components at room temperature were heated and added in a liquid state. Next, component B was added and similarly stirred at a rotational speed of 3000 r / min for 20 seconds to obtain a polyol composition. After completion of stirring, the mixture was transferred to a 110 mL borosilicate glass screw tube bottle (screw tube No. 8, manufactured by Maruemu Co., Ltd.), and the state after standing at room temperature for 24 hours was visually observed and evaluated according to the following criteria. . The results are shown in Tables 1 and 2.
1: Transparent and uniform 2: Slight turbidity 3: Separation 4: Solidification

(2) Production of Rigid Polyurethane Foam In Example 16 and Comparative Example 8, a rigid polyurethane foam was produced by the following procedure using the obtained polyol composition.
100 g of the polyol composition collected from the obtained polyol composition, and a polymethylene polyphenylene polyisocyanate having a mass of 180 which is an isocyanate index calculated from the composition of the polyol composition shown in Table 2 as a polyisocyanate Urethane Co., Ltd., trade name: Sumijoule 44V20] at 15 ° C. K. Using a homodisper (L type, manufactured by Tokushu Kika Kogyo Co., Ltd.), the mold was stirred for 5 seconds at a rotational speed of 5000 r / min and immediately embedded with a polyethylene bag [inside dimensions: 150 mm × 150 mm × 300 mm (height )] Was injected to produce a free form, and the appearance and internal state were evaluated according to the following criteria. The results are shown in Table 2.

<Appearance>
The appearance of the free form taken out from the polyethylene bag was evaluated by visual observation. It is better for the foam to have a uniform appearance without generating voids (air pockets) due to non-uniform foaming agent.
1: Homogeneous 2: Void has occurred

<Internal state>
The free form was cut vertically at the center, and the cross section was evaluated by visual observation. It is better for the foam to have a uniform appearance without generating voids (air pockets) due to non-uniform foaming agent.
1: Homogeneous 2: Void has occurred

  In addition, the raw material used for each Example and each comparative example is as follows.

<Polyol (component A)>
RDK-133: phthalic anhydride-based polyester polyol [hydroxyl value: 315 mgKOH / g, number of functional groups: 2, manufactured by Kawasaki Kasei Kogyo Co., Ltd., trade name: Maximol RDK-133]
RFK-505: terephthalic acid-based polyester polyol [hydroxyl value: 250 mgKOH / g, number of functional groups: 2, manufactured by Kawasaki Kasei Kogyo Co., Ltd., trade name: Maximol RFK-505]
EDP-300: ethylenediamine-based polyether polyol [hydroxyl value: 768 mgKOH / g, hydroxyl number: 4, manufactured by ADEKA Corporation, trade name: ADEKA polyether EDP-300]

<Foaming agent (component B)>
HFO-1336mzz-Z: [cis-1,1,1,4,4,4-hexafluoro-2-butene, manufactured by Chemers, trade name: Opteon 1100]
HFO-1336mzz-E: [Trans-1,1,1,4,4,4-hexafluoro-2-butene, manufactured by Chemers, trade name: Opteon 1150]
HCFO-1233zd-E: [trans-1-chloro-3,3,3-trifluoro-1-propene, manufactured by Honeywell, trade name: Solstice LBA]
Water: Pure water of 1 μS / cm or less produced with a pure water apparatus G-10DSTSET manufactured by Organo Corporation

<Compound of Formula (I) (Component C)>
C-1: 1-octanol (R ¹ : n-octyl group, n: 0) [manufactured by Kao Corporation, trade name: Calcoal 0898]
C-2: 1-decanol (R ¹ : n-decyl group, n: 0) [manufactured by Kao Corporation, trade name: Calcoal 1098]
C-3: 1-dodecanol (R ¹ : n-dodecyl group, n: 0) [manufactured by Kao Corporation, trade name: Calcoal 2098]
C-4: polyoxyethylene (2.2) lauryl ether (R ¹ : n-dodecyl group, n: 2.2) [Aoki Yushi Kogyo Co., Ltd., trade name: BROWNON EL-1502.2]
C-5: polyoxyethylene (3) lauryl ether (R ¹ : n-dodecyl group, n: 3.0) [manufactured by Aoki Oil Industrial Co., Ltd., trade name: BROWNON EL-1503P]

<Catalyst (component D)>
KL-1: N, N, N ′, N′-tetramethyl-1,6-hexanediamine [manufactured by Kao Corporation, trade name: Kao Raiser No. 1]
KL-410: isocyanurate conversion catalyst [manufactured by Kao Corporation, trade name: Kao Raiser No. 410]

<Foam stabilizer (component E)>
・ Silicone-based foam stabilizer [made by Toray Dow Corning Co., Ltd., trade name: L-5340]

<Flame retardant (component F)>
-TMCPP: Tris (2-chloroisopropyl) phosphate [manufactured by Daihachi Chemical Industry Co., Ltd., trade name: TMCPP]

<Other ingredients>
G-1: 1-tetradecanol (R ¹ : n-tetradecyl group, n: 0) [manufactured by Tokyo Chemical Industry Co., Ltd.]
G-2: polyoxyethylene (5) lauryl ether (R ¹ : n-dodecyl group, n: 5.0) [manufactured by Aoki Yushi Kogyo Co., Ltd., trade name: BROWNON EL-1505P]
G-3: Diethylene glycol monohexyl ether (R ¹ : n-hexyl group, n: 2.0) [manufactured by Nippon Emulsifier Co., Ltd., hexyl diglycol]
G-4: Polyoxyethylene (2) cetyl ether (R ¹ : n-hexadecyl group, n: 2.0) [Aoki Yushi Kogyo Co., Ltd., trade name: BROWNON CH-302L]

From the above results, it can be seen that the polyol compositions of Examples 1 to 16 maintain stable properties even after 24 hours without separation of the blending components. In addition, the compounds of the formula (I) were used in combination with phthalic anhydride-based polyester polyol rather than terephthalic acid-based polyester polyol by comparing Examples 1, 2 and Examples 10, 11 with Comparative Examples 1, 2. It can be seen that the effect of is more prominent.
In contrast, in the polyol compositions of Comparative Examples 1 and 2 that did not contain the compound of Formula (I), the components were separated, and as in Comparative Examples 3 to 7, the compound of Formula (I) It can be seen that even when a compound having a similar structure is blended, separation cannot be suppressed or solidified.
Further, by comparing the compound of formula (I) by comparing Example 16 with Comparative Example 8, the foaming agent can be uniformly dispersed in the polyol composition, and a rigid polyurethane foam having a homogeneous structure is obtained. You can see that

  The rigid polyurethane foam obtained by using the polyol mixture of the present invention is suitable as a building material, an electric refrigerator, a refrigerator / freezer warehouse, a heat insulating material such as a bathtub, a pipe, a dew condensation preventing material for a detached house, an apartment, an industrial pipe, and the like. Can be used.

Claims (8)

Component A: a polyol containing 50% by mass or more of an aromatic polyester polyol (component A-1) having a hydroxyl value of 100 mgKOH / g or more and 500 mgKOH / g or less,
Component B: foaming agent containing 50% by mass or more of cis-1,1,1,4,4,4-hexafluoro-2-butene (component B-1), and component C: Formula (I):
^{_{R 1 O- (CH 2 CH 2}} O) n-H (I)
(In the formula, R ¹ is an alkyl group having 8 to 12 carbon atoms, and n is an average added mole number of CH ₂ CH ₂ O, and is 0 to 3)
A hard polyurethane foam-producing polyol composition containing a compound represented by: wherein the content of component B-1 is 28 to 50 parts by mass with respect to 100 parts by mass of component A Polyol composition for producing polyurethane foam.   The polyol composition according to claim 1, wherein Component A-1 contains 70% by mass or more of a phthalic polyester polyol.   The polyol composition according to claim 1 or 2, wherein the content of component B-1 in component B is 80% by mass or more.   The polyol composition according to any one of claims 1 to 3, wherein Component B further contains trans-1,1,1,4,4,4-hexafluoro-2-butene.   The polyol composition according to any one of claims 1 to 4, wherein the content of component C is 3 parts by mass or more and 17 parts by mass or less with respect to 100 parts by mass of component A.   Furthermore, the polyol composition in any one of Claims 1-5 containing a catalyst (component D) and / or a foam stabilizer (component E).   Furthermore, the polyol composition in any one of Claims 1-6 containing a flame retardant (component F).   The manufacturing method of a rigid polyurethane foam including the process of mixing the polyol composition and polyisocyanate in any one of Claims 1-7.