JP2022064050A - Composition for forming polyurethane foam, polyurethane foam, and thermal insulating material - Google Patents

Abstract

To provide a composition for forming a polyurethane foam having excellent surface quality, particularly smoothness, of a formed article.SOLUTION: A composition for forming a polyurethane foam comprises a hydrofluoroolefin as a foaming agent and the composition comprises 0.2 to 6 pts.mass of at least one compound represented by Formula 1 relative to 100 pts.mass of the composition: RO(CH2CH2O)nR (Formula 1) where R is a C1 to C3 linear or branched alkyl, and n is an integer of 1 or more.SELECTED DRAWING: None

Description

The present invention relates to a composition for forming a polyurethane foam, a polyurethane foam formed from the composition, and a heat insulating material composed of the foam, and more specifically, a polyurethane foam having excellent surface quality, particularly smoothness, of a molded product. It is about a composition for forming.

Among the resin-based foams, polyurethane foams, particularly rigid polyurethane foams, are widely used as foam-based heat insulating materials because they have excellent heat insulating performance. Polyurethane foam is usually produced by mixing a polyol and a polyisocyanate together with a catalyst, a foaming agent, a foaming agent, etc., which are appropriately blended as needed, and foaming the polyurethane foam.

Conventionally, hydrofluorocarbon (HFC) -based foaming agents such as HFC-134a, HFC-245fa, and HFC-365mfc have been used as foaming agents for rigid polyurethane foams. However, although this hydrofluorocarbon-based foaming agent is recognized as an alternative CFC with little or no ozone depletion, it has a high global warming potential due to its chemical stability, and the use of HFC-based foaming agents is global warming. There is concern that it will lead to the conversion to CFCs, and gradual reductions are being promoted by the Montreal Protocol (Kigari revision).

Therefore, in recent years, instead of these HFC-based foaming agents, halogenated hydroolefin-based foaming agents called hydrofluoroolefins (HFOs), which have a low global warming potential due to their chemical instability, have begun to be used. ..

Japanese Patent Application Laid-Open No. 2016-74886 (Patent Document 1) describes a polyol composition for rigid polyurethane foam containing 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) as an essential component as a foaming agent component. Inventions relating to objects are described. The invention described in Patent Document 1 provides a polyol composition for a rigid polyurethane foam, which has good stock solution storage stability even when HFO-1233zd is used as a foaming agent component, and can suppress deterioration of the physical properties of the rigid polyurethane foam. The present invention is characterized by containing ethyldiglycolacetate as a compatibilizer for HFO-1233zd.

Further, although it is not characterized by the use of HFO as a foaming agent, in Japanese Patent Application Laid-Open No. 2019-533754 (Patent Document 2), the polyol composition used as a raw material for polyurethane foam tends to undergo phase separation over time. In order to solve the above-mentioned problems, it is an object of the present invention to provide a polyol composition that is stable in all conditions, specifically, a polyol composition that is stable for at least 24 hours, and in some cases, for more than 6 months. The polyol composition described in Patent Document 2, together with two or more kinds of polyols, has a formula: RO (CH ₂ CH ₂ O) _n H [in the formula, R is C1 to C31 linear or branched alkyl. , N is an integer of 1 or more] and is characterized by containing an ethoxylated alcohol having a hydrophilic-lipophilic balance (HLB) value of about 3.7 or more.

Japanese Unexamined Patent Publication No. 2016-74886 Special Table 2019-533754 Gazette

The present inventor examined the use of hydrofluoroolefin (HFO) as a foaming agent for polyurethane foam, and found that when the polyurethane foam was integrally molded with the face material, the smoothness of the face material of the obtained molded product was other than that. It was found that it was inferior to the case of the foaming agent and had a problem of deteriorating the surface quality.

Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art and to provide a composition for forming a polyurethane foam having excellent surface quality, particularly smoothness, of a molded product. Another object of the present invention is to provide a polyurethane foam formed from the composition and a heat insulating material made of the foam.

The present inventor has confirmed that the use of hydrofluoroolefin (HFO) as a foaming agent causes shrinkage of the polyurethane foam, and believes that this shrinkage tends to reduce the smoothness of the face material.

The process of forming polyurethane foam generally consists of (1) foaming due to the reaction between polyisocyanate and water, and (2) formation of urethane bonds due to the reaction between polyisocyanate and polyol, and the reaction starts in this order. When HFO is used as the foaming agent, it is considered that the HFO volatilizes before the bubbles are generated through the foaming of the above (1), and the polyurethane foam shrinks.

Therefore, as a result of diligent studies to achieve the above object, the present inventor has found that in a polyurethane foam forming composition containing HFO as a foaming agent, formula 1: RO (CH ₂ CH ₂ O) _n R [in the formula, R is a linear or branched alkyl of C1 to C3, and n is an integer of 1 or more. ], It has been found that a polyurethane foam having excellent smoothness of a face material can be formed by using a compound represented by [], and the present invention has been completed.

That is, the composition of the present invention is a composition for forming a polyurethane foam, which contains a hydrofluoroolefin as a foaming agent, and at least one compound represented by the following formula 1 is added to 100 parts by mass of the composition. It is a composition containing 0.2 to 6 parts by mass.
RO (CH ₂ CH ₂ O) _n R (Equation 1)
[In the formula, R is a linear or branched alkyl of C1 to C3, and n is an integer of 1 or more. ]

In a preferred example of the composition of the present invention, 25 parts by mass or more of the polyether polyol is contained with respect to 100 parts by mass of the composition.

In another preferred example of the composition of the present invention, the isocyanate index is 150 or less.

In another preferred example of the composition of the present invention, the viscosity of the polyol contained in the composition is 500 mPas (25 ° C.) or higher.

Further, the polyurethane foam of the present invention is a polyurethane foam obtained by foaming the above composition.

A preferred example of the polyurethane foam of the present invention is a polyurethane foam with a face material.

Further, the heat insulating material of the present invention is a heat insulating material made of the above-mentioned polyurethane foam.

According to the composition of the present invention, it is possible to provide a composition for forming a polyurethane foam having excellent surface quality, particularly smoothness, of a molded product. Further, according to the polyurethane foam of the present invention, a polyurethane foam formed from such a composition can be provided, and according to the heat insulating material of the present invention, a heat insulating material made of such a polyurethane foam can be provided.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention is a polyurethane foam forming composition. Such a composition contains a polyol, a polyisocyanate and a foaming agent, and by mixing these, the reaction between the polyol and the polyisocyanate proceeds, and it is possible to form a polyurethane foam. In the present specification, the composition for forming a polyurethane foam of the present invention is also referred to as the composition of the present invention.

The polyol is a compound having a plurality of hydroxyl groups, and is preferably a polyol of a polymer. Specific examples of the polyol include a polyether polyol, a polyester polyol, a polycarbonate polyol, a polylactone polyol, a polybutadiene polyol, a polymer polyol, a Mannig polyol, and the like.

In the composition of the present invention, the amount of the polyol is appropriately adjusted according to the amount of the polyisocyanate, and is, for example, 25 to 40 parts by mass with respect to 100 parts by mass of the composition. The polyol may be used alone or in combination of two or more.

A typical example of the polyether polyol is a polyoxyalkylene-based polyol, and the polyoxyalkylene-based polyol is a compound having two or more hydroxyl groups, a primary amino group, a secondary amino group, and other active hydrogen-containing groups. Can be produced by subjecting alkylene oxide to a ring-opening addition reaction using the above as a starting material.

Starting materials for polyoxyalkylene-based polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, and pentaerythritol. Polyhydric alcohols such as diglycerin, mannose, sucrose, fructose, dextrose, sorbitol, alkanolamines such as ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, ethylenediamine, tolylenediamine, diethyltoluenediamine, 1,3-propane. Polyvalent amines such as diamine, 1,6-hexanediamine, isophoronediamine, diethylenetriamine, triethylenepentamine, polyhydric phenols such as bisphenol A, bisphenol F, resorcinol, hydroquinone, and modified products thereof can be mentioned. The raw materials may be used alone or in combination of two or more.

Examples of the alkylene oxide to be subjected to the ring-opening addition reaction in the production of the polyoxyalkylene-based polyol include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide and the like, and these alkylene oxides. The oxide may 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 a polyoxyalkylene-based polyol. The polymer polyol is a kind of polyether polyol because it contains a polyoxyalkylene-based polyol.

The Mannich polyol can be produced by subjecting a condensation reaction of phenols, aldehydes, alkanolamines and the like, and if necessary, a ring-opening addition reaction of an alkylene oxide such as ethylene oxide or propylene oxide. Mannich polyol is a kind of polyether polyol because it has a plurality of ether bonds in the molecule.

Examples of suitable polyether polyols are (di) ethylene glycol-based polyether polyols, (di) propylene glycol-based polyether polyols, and (di) glycerin-based polyethers obtained by addition reaction of ethylene oxide and / or propylene oxide. Polyformates, trimethylolpropane-based polyether polyols, pentaerythritol-based polyether polyols, sucrose-based polyether polyols, dextrose-based polyether polyols, sorbitol-based polyether polyols, mono (di, tri) ethanolamine-based polyether polyols, ethylenediamine Examples thereof include polyoxyalkylene-based polyols such as based polyether polyols, tolylene diamine-based polyether polyols, and bisphenol A-based polyether polyols, polymer polyols in which polymer fine particles are dispersed in polyoxyalkylene-based polyols, and Mannig polyols.

The polyester polyol can be produced by adjusting the production conditions of the polyester, and examples thereof include polyester polyols having hydroxyl groups at least at both ends of the main chain, and more specifically, a linear polyester polyol or a small amount. Examples thereof include polyester polyols branched into. Polyester polyols can be prepared by known methods using aliphatic, alicyclic or aromatic dicarboxylic acids, diols and optionally polyvalent carboxylic acids and / or trifunctional or higher polyols. can.

Examples of the polylactone polyol are homopolymers or copolymers of lactones, such as polylactones having hydroxyl groups at least at both ends of the main chain. Specifically, using a compound having two or more active hydrogen-containing groups as described in the above polyoxyalkylene-based polyol as a starting material, ε-caprolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ -It can be produced by subjecting a lactone such as valerolactone to a ring-opening addition reaction. The polylactone polyol is a kind of polyester polyol because it has a plurality of ester bonds in the molecule.

The polycarbonate polyol can be produced by adjusting the production conditions of polycarbonate, and examples thereof include polycarbonate having hydroxyl groups at at least both ends of the main chain. Examples of the polybutadiene polyol include polybutadiene having hydroxyl groups at least at both ends of the main chain.

The composition of the present invention preferably contains a polyether polyol as the polyol. The amount of the polyether polyol is preferably 25 parts by mass or more, more preferably 25 to 40 parts by mass, and further preferably 30 to 35 parts by mass with respect to 100 parts by mass of the composition of the present invention. When a polyether polyol, particularly a polyether polyol having a relatively hydrophilic property and a high hydroxyl value, is used in the above-specified amount, the effect of the compound represented by the formula 1 described later is likely to be exhibited.

In the composition of the present invention, the hydroxyl value of the polyol is preferably 200 to 500 mgKOH / g, more preferably 300 to 400 mgKOH / g.

As used herein, the hydroxyl value is the sodium hydroxide required to completely acetylate a free hydroxyl group in 1 g of a sample with a carboxylic acid anhydride (eg, phthalic anhydride or acetic anhydride) and then neutralize it. The mg number of (see JIS K 1557 2007).

In the composition of the present invention, the molecular weight of the polyol is preferably 400 to 800 g / mol, more preferably 500 to 600 g / mol.

As used herein, the molecular weight of the polyol is a polystyrene-equivalent number average molecular weight measured by gel permeation chromatography.

In the composition of the present invention, the number of functional groups (fn) of the polyol is preferably 2.5 to 4.5, more preferably 3.0 to 4.0.

In the present specification, the number of functional groups (fn) per molecule of a polyol is calculated by the following formula from the hydroxyl value (OHV) and the number average molecular weight (Mn) of the polyol.
fn = Mn (g / mol) × OHV (mgKOH / g) / 56100

The viscosity of the polyol contained in the composition of the present invention is preferably 500 mPas (25 ° C.) or higher, more preferably 600 to 3000 mPas (25 ° C.), and even more preferably 700 to 2000 mPas (25 ° C.). If the viscosity of the polyol contained in the composition of the present invention is less than 500 mPas (25 ° C.), the composition may scatter during construction and cause foam defects. The viscosity of the polyol can be easily increased by using, for example, an aromatic amine-based polyether polyol.

In the present specification, the measurement of viscosity is measured according to JIS K 7117-1: 1999, and a Brookfield rotational viscometer type B is used.

When the composition of the present invention contains a plurality of polyols, the viscosity of the polyol is the viscosity of the entire polyol, and can be obtained, for example, from the viscosity and mass fraction of each polyol as follows.
[Viscosity of polyol]
When the polyol contained in the composition of the present invention consists of n types, the viscosities of each polyol are V ¹ , V ² , ..., V ⁿ , respectively, and the mass fraction of each polyol in the entire polyol is W ¹ , W. ² , ..., ^Wn can be obtained from the following equation.
Viscosity of polyol = exp (W ¹ x ln (V ¹ ) + W ² x ln (V ² ) + ... + W ⁿ x ln (V ⁿ ))

The polyisocyanate is a compound having a plurality of isocyanate groups, and examples thereof include aliphatic, alicyclic, aromatic or aromatic aliphatic polyisocyanates, and modified products of these polyisocyanates are also included. Examples of the modified polyisocyanate include polyisocyanates having a structure such as uretdione, isocyanurate, urethane, urea, allophanate, biuret, carbodiimide, iminooxadiazinedione, oxadiazinetrione, and oxazolidone. Further, as the polyisocyanate, an isocyanate group-containing prepolymer obtained by reacting a polyol with a polyisocyanate may be used. The polyisocyanate may be used alone or in combination of two or more.

Among the polyisocyanates, examples of the aromatic polyisocyanate include phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, and polymethylene polyphenyl polyisocyanate. Will be. Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate. Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate and the like.

The polyisocyanate preferably has an isocyanate group content of 20 to 40% by mass, more preferably 25 to 35% by mass. In the present specification, the isocyanate group content is determined according to JIS K 1603-1: 2007.

In the composition of the present invention, the amount of polyisocyanate can be indicated, for example, by an isocyanate index. In the composition of the present invention, the isocyanate index is preferably set low from the viewpoint of the heat insulating property of the polyurethane foam, and specifically, the isocyanate index is preferably 150 or less, more preferably 90 to 150. It is more preferably 90 to 130, and particularly preferably 100 to 125.

In the present specification, the isocyanate index is a value obtained by multiplying the ratio of the isocyanate group of polyisocyanate to the total amount of active hydrogen that reacts with the isocyanate group of a foaming agent or the like in addition to the polyol.

Foaming agents are generally classified into physical foaming agents and chemical foaming agents. The foaming agent may be used alone or in combination of two or more. Further, a physical foaming agent and a chemical foaming agent may be used in combination. The amount of the foaming agent is preferably 0.5 to 15 parts by mass, more preferably 3 to 12 parts by mass with respect to 100 parts by mass of the composition of the present invention.

Specific examples of the physical foaming agent include fluorocarbons such as hydrochlorofluorocarbon (HCFC) and hydrofluorocarbon (HFC), hydrocarbons such as hydrofluoroolefin (HFO), heptane, hexane, pentane, and cyclopentane, carbon dioxide, and the like. Can be mentioned. On the other hand, examples of the chemical foaming agent include water and carboxylic acids such as formic acid and acetic acid.

The composition of the present invention contains a hydrofluoroolefin as a foaming agent. Hydrofluoroolefins (HFOs) are foaming agents that are suitably used as physical foaming agents that do not fall under the category of fluorocarbons. The HFO is an olefin compound containing a fluorine atom, and includes a compound further containing a halogen atom (for example, a chlorine atom) other than fluorine. Among HFOs, those further containing a chlorine atom are also referred to as hydrochlorofluoroolefins (HCFOs). The composition of the present invention preferably contains a hydrochlorofluoroolefin. In addition, although HFO and HCFO may be distinguished, in the present specification, HCFO is included in HFO as described above.

The hydrofluoroolefin preferably has 2 to 5 carbon atoms, and preferably 3 to 7 fluorine atoms. The molecular weight of HFO is preferably 100 to 200 g / mol. Specific examples of HFO include 1,2,3,3,3-pentafluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3. , 3-Tetrafluoropropene, 3,3,3-trifluoropropene, 1,1,1,4,4,4-hexafluorobutene, 1-chloro-3,3,3-trifluoropropene, 2-chloro -3,3,3-trifluoropropene, 3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluorobutene, 2-chloro-1,1,1 Examples thereof include 1,3,4,4,4-heptafluorobutene. The HFO may be an isomer of either a cis form or a trans form. These HFOs may be used alone or in combination of two or more.

The amount of the hydrofluoroolefin is, for example, 0.5 to 15 parts by mass, preferably 3 to 12 parts by mass with respect to 100 parts by mass of the composition of the present invention.

The composition of the present invention preferably contains water as a foaming agent from the viewpoint of improving the appearance and strength of the foam. The amount of water is, for example, 0.2 to 10 parts by mass, preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the composition of the present invention.

The composition of the present invention contains at least one compound represented by the following formula 1.
RO (CH ₂ CH ₂ O) _n R (Equation 1)
[In the formula, R is a linear or branched alkyl of C1 to C3, and n is an integer of 1 or more. ]

The composition of the present invention preferably contains a polyether polyol. Due to its structure, the polyether polyol has a hydrophilic property that is easily dissolved in water. Therefore, as the reaction between the polyol and the polyisocyanate progresses, a hydrophobic structure is formed, but hydrophilicity is maintained to some extent.

On the other hand, since hydrofluoroolefin (HFO) as a foaming agent is hydrophobic, it moves to the hydrophobic side in the reaction process between the polyol and the polyisocyanate. As the heat of reaction gradually rises, HFO also volatilizes, but if there are many hydrophilic structures such as polyether polyols, it is difficult for HFO to dissolve, so HFO will volatilize at once in the early stages of the reaction. .. When HFO volatilizes all at once, the resin becomes soft at specific points due to the high solubility of HFO in the resin, and that softness causes shrinkage of the foam, which causes the surface material surface to lose its smoothness. Be done.

Since the compound represented by the above formula 1 is relatively hydrophobic, it is possible to control the dissolution of HFO in a resin obtained from a raw material containing a hydrophilic polyether polyol, for example, at a specific location. Can solve the problem of softening the resin.

In the above formula 1, R is a linear or branched alkyl of C1 to C3, and specific examples thereof include methyl, ethyl, and propyl (normal propyl, isopropyl). The two Rs in Equation 1 may be the same or different.

In the above formula 1, n is an integer of 1 or more, preferably an integer of 1 or more and 12 or less, and more preferably an integer of 5 or more and 10 or less.

The compound represented by the above formula 1 is preferably 0.2 to 6 parts by mass, preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the composition of the present invention. If the amount of the compound represented by the above formula 1 is too large, the compound tends to appear on the surface, the combustibility is lowered, and the compound becomes easy to burn.

The composition of the present invention preferably contains a catalyst. The catalysts include a catalyst that promotes the reaction between water and polyisocyanate (foaming catalyst), a catalyst that promotes the reaction between polyol and polyisocyanate (resinification catalyst), and a trimerization reaction of polyisocyanate (that is, isocyanurate ring). Examples include catalysts (triquantization catalysts) that promote the formation of

Examples of the foaming catalyst include dimorpholine-2,2-diethyl ether, N, N, N', N'', N''-pentamethyldiethylenetriamine, bis (dimethylaminoethyl) ether, and 2- (2-dimethyl). Aminoethoxy) ethanol, N, N, N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether and the like can be mentioned.

Examples of the resinification catalyst include triethylenediamine, N, N-dimethylcyclohexylamine, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'', N''', N. '''-Hexamethyltriethylenetetramine, N-dimethylaminoethyl-N'-methylpiperazine, N, N, N', N'-tetramethylhexamethylenediamine, 1,2-dimethylimidazole, 1-isobutyl-2 -Amine catalysts such as methylimidazole, N, N-dimethylaminopropylamine, bis (dimethylaminopropyl) amine, N, N-dimethylaminoethanol, N, N, N'-trimethylaminoethylethanolamine, N- (3) -Dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N'-methylpiperazine, N, N-dimethylaminohexanol, 5-dimethylamino-3-methyl-1-pentanol Examples thereof include alkanolamine catalysts such as stannous octylate, dibutylstandium dilaurylate, lead octylate, bismuth carboxylate, and metal catalysts such as zirconium complexes. As these amine catalysts and alkanol amine catalysts, amine carbonates synthesized by adding carbonic acid or amine carboxylates synthesized by adding carboxylic acids such as formic acid and acetic acid may be used.

Examples of the trimerization catalyst include 2,4,6-tris (dialkylaminoalkyl) hexahydro-S-triazine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 2, Aromatic compounds such as 4,6-tris (dimethylaminomethyl) phenol and 2,4-bis (dimethylaminomethyl) phenol, carboxylic acid alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate and potassium octylate, Examples thereof include a quaternary ammonium salt of a carboxylic acid, and other onium salts.

The amount of the catalyst is, for example, 0.1 to 5 parts by mass, preferably 0.3 to 1.5 parts by mass with respect to 100 parts by mass of the composition of the present invention. The catalyst may be used alone or in combination of two or more.

The composition of the present invention may contain a defoaming agent. The foam stabilizer is preferably a surfactant. Examples of the surfactant include ionic surfactants such as anionic, cationic and amphoteric and nonionic surfactants, and nonionic surfactants are preferable. Moreover, as a specific example, a silicone-based surfactant and a fluorine-based surfactant are preferably mentioned. The amount of the foam stabilizer is preferably 1 to 5 parts by mass with respect to 100 parts by mass of the composition of the present invention. The foam stabilizer may be used alone or in combination of two or more.

The composition of the present invention may contain a flame retardant. The flame retardant is preferably a phosphorus-based flame retardant. Specific examples thereof preferably include tricresyl phosphate (TCP), triethyl phosphate (TEP), tris (β-chloroethyl) phosphate (TCEP), tris (β-chloropropyl) phosphate (TCPP) and the like. Further, solid (powder) flame retardants such as ammonium polyphosphate and red phosphorus are also used as needed. The amount of the flame retardant is preferably 3 to 15 parts by mass with respect to 100 parts by mass of the composition of the present invention. The flame retardant may be used alone or in combination of two or more.

In the composition of the present invention, as other components, a colorant, a filler, an antioxidant, an ultraviolet absorber, a heat stabilizer, a light stabilizer, a plasticizer, a fungicide, an antibacterial agent, a cross-linking agent, a solvent, etc. Additives such as a slimming agent, a decompressing agent, and a separation inhibitor may be appropriately added as needed. Commercially available products can be preferably used for these components.

The composition of the present invention can be prepared by mixing various components appropriately selected as needed. For example, the composition of the present invention can be prepared by mixing a polyol component containing a polyol and a polyisocyanate component composed of polyisocyanate.

The composition of the present invention is often composed of a stock solution consisting of a pair of a polyol component and a polyisocyanate component. The polyol component contains a polyol, usually including a foaming agent, a defoaming agent, a catalyst, and may contain a flame retardant or a further additive. The polyisocyanate component is composed of polyisocyanate, but may contain additives such as a foaming agent and a flame retardant. The foaming agent may be added when the polyol component and the polyisocyanate component are mixed.

Another aspect of the invention is polyurethane foam. The polyurethane foam of the present invention is obtained by foaming the above-mentioned composition for forming a polyurethane foam of the present invention. Since the composition of the present invention contains a polyol and a polyisocyanate, it is possible to proceed with the reaction and form a polyurethane foam by mixing both. The temperature at the time of forming the polyurethane foam is preferably 20 to 80 ° C.

The foaming method of the polyurethane foam is not particularly limited, and known foaming means, for example, hand mixing foaming, simple foaming, injection method, floss injection method, spray method and the like can be used. Further, the method for molding the polyurethane foam is not particularly limited, and known molding means such as molding, slab molding, laminating molding, and in-situ foam molding can be used.

The polyurethane foam of the present invention can be used for various purposes such as ships, vehicles, plants, heat insulating equipment, construction, civil engineering, furniture, interiors, etc. It can be suitably used as a heat insulating member.

The polyurethane foam of the present invention is preferably a polyurethane foam with a face material, and more preferably a polyurethane foam with a metal face material. In the present specification, the polyurethane foam with a face material is a plate-shaped composite material in which a face material such as a foil or a plate is attached to one side or both sides of the polyurethane foam, and can be used as a heat insulating material for various purposes.

Preferable examples of the object to be adhered such as a face material include metals and other inorganic materials, and in particular, aluminum and its alloys, stainless steel and its alloys, iron and its alloys, copper and its alloys and the like. Further, the surface of the object to be adhered may be coated with a coating on the surface to which the composition of the present invention is adhered, if desired. Examples of the coating include an organic polymer coating agent such as a polyester resin. The thickness of the adherend is preferably 0.2 to 0.6 mm.

The polyurethane foam of the present invention has a density of, for example, 5 to 80 kg / m ³ , preferably 25 to 70 kg / m ³ , and more preferably 40 to 65 kg / m ³ . As used herein, the density of polyurethane foam is measured according to JIS K 7222: 2005.

The polyurethane foam of the present invention preferably has a thermal conductivity of 0.0185 to 0.0280 W / m · K, preferably 0.0190 to 0.0260 W / m · K, when the center temperature of measurement is 23 ° C. It is more preferable to have. As used herein, thermal conductivity is measured in accordance with JIS A 1412-: 1999.

The polyurethane foam of the present invention can be suitably applied to various applications in which heat insulating properties are required. In particular, the polyurethane foam of the present invention is a building material or a heat insulating material used in various facilities such as condominiums and other condominiums, detached houses, schools and commercial buildings, freezer warehouses, bathtubs, factory piping, automobiles and railroad vehicles. It can be used advantageously as a.

Further, the polyurethane foam of the present invention can also be used when manufacturing on-site construction type heat insulating materials and dew condensation prevention materials by a spray method, building materials such as panels and boards on a factory line. Therefore, according to one embodiment of the present invention, the polyurethane foam is a sprayed rigid urethane foam for building heat insulation specified in JIS A 9526: 2017.

Another aspect of the present invention is a heat insulating material. The heat insulating material of the present invention is the heat insulating material made of the polyurethane foam of the present invention described above. Examples of the heat insulating material include heat insulating equipment, for example, heat insulating members of a cold storage warehouse or a freezing warehouse. Further, the heat insulating material of the present invention can be used for apartment houses such as condominiums, detached houses, various facilities such as schools and commercial buildings, freezer warehouses, bathtubs, factory pipes, automobiles and railroad vehicles.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

1. 1. Approximately Using a high-pressure foaming machine, a mixed solution (polyol component) in which a polyol and a foaming agent are mixed and a polyisocyanate are mixed at a predetermined mixing ratio, and the mixed solution is applied up and down with a metal face material at a constant temperature and pressure. Discharge to the arranged mold, obtain polyurethane foam, and measure the depth near the injection part on the lower surface after a certain period of time.

2. 2. Equipment and equipment High-pressure foaming machine (HK-650P, manufactured by Hennecke)
Disposable chopsticks Stopwatch (with wrap function)
Mold (made of aluminum, inner dimensions: length 2000 mm, width 900 mm, thickness 100 mm)

3. 3. Material 1) Polyol Polyol A: Polyether Polyol [SBU Polyol 0517: manufactured by Sumika Cobestrolurethane Co., Ltd.], Number of functional groups: 4.1, Hydroxyl group value 480 mgKOH / g, Viscosity 3400 mPa · s (25 ° C)
Polyol B: Polyether polyol [SBU polyol 0487: manufactured by Sumika Cobestrourethane Co., Ltd.], number of functional groups: 4, hydroxyl value 410 mgKOH / g, viscosity 1500 mPa · s (25 ° C)
Polyol C: Aromatic amine-based polyether polyol [SBU polyol Z450: manufactured by Sumika Cobestrourethane Co., Ltd.], number of functional groups: 4, hydroxyl value 340 mgKOH / g, viscosity 12000 mPa · s (25 ° C)
Polyol D: Polyether polyol [SBU polyol S429: manufactured by Sumika Cobestrourethane Co., Ltd.], number of functional groups: 3, hydroxyl value 250 mgKOH / g, viscosity 230 mPa · s (25 ° C)
2) Polyisocyanate Polyisocyanate: Polymeric MDI [Sumijour 44V20 L: manufactured by Sumika Covestro Urethane Co., Ltd.], isocyanate group content: 31.5% by mass
3) Foaming agent Foaming agent A: Water foaming agent B: HCFO-1233zd (molecular weight 130)
Foaming agent C: HFO-1224yd (molecular weight 148.5)
Foaming agent D: HFO-1336mzz (Z) (molecular weight 164)
4) Compatibility agent Compatibility agent A: Diethylene glycol dimethyl ether, molecular weight 134, viscosity 1 mPa · s (25 ° C.)
Compatibility B: Tetraethylene glycol dimethyl ether, molecular weight 222, viscosity 4 mPa · s (25 ° C)
Compatibility C: Polyoxyethylene-dimethyl ether [Uniox MM-400: manufactured by NOF CORPORATION], average molecular weight 400, viscosity 100 mPa · s (25 ° C)
Compatibility agent D: Diethylene glycol monobutyl ether, molecular weight 162, hydroxyl value 346, viscosity 6 mPa · s (25 ° C)
Compatibility E: Ethyldiglycolacetate, molecular weight 176, viscosity 2.5 mPa · s (25 ° C)
4) Other Additives Catalyst A: Dimorpholin-2,2-diethyl ether catalyst B: 1,2-dimethylimidazole 70% by mass + diethylene glycol 30% by mass
Defoaming agent: Silicone-based nonionic surfactant [TEGOSTAB B8460: manufactured by Evonik Japan Co., Ltd.]
Flame Retardant: Tris (2-Chloroisopropyl) Phosphate 5) Face Material Aluminum Face Material

3. 3. Method <Preparation of polyol component>
1) Put a predetermined amount of various polyols, catalysts, etc. into a nitrogen-substituted mixing kettle and mix them.
2) Stir for 30 minutes or more, and visually confirm that the mixture has been sufficiently stirred.
3) Add the foaming agent to the mixed solution confirmed in 2) in a predetermined amount and mix well. After mixing, weigh and reduce the weight of the foaming agent, and mix again.
The compounding formulation (part by mass) of the polyol component is shown in Tables 1 and 2.
<Manufacturing of polyurethane foam>
4) Using HK-650P, which is a high-pressure foaming machine manufactured by Hennecke, the polyol component and the polyisocyanate component were adjusted to 19 to 23 ° C., and urethane injection molding was performed at a discharge pressure of 12 MPa. The mixed mass ratio of the polyol component and the polyisocyanate component is shown in Tables 1 and 2.
5) Preheat to 40 ° C., and inject the foam-forming composition into one central part of a mold (inner dimension length 2000 mm, width 900 mm, thickness 100 mm) in which aluminum facing materials are arranged vertically.
6) Inject an amount of polyurethane foam that does not clog in the length direction of the mold, cut both ends of the semicircle to sample a rectangular parallelepiped, measure the weight and volume, and measure the just density (kg / m ³ ). calculate. The density of the sample filled in the mold is called the just density.
7) The just weight of the mold (inner dimension length 2000 mm, width 900 mm, thickness 100 mm) is calculated from the just density, and 1.25 times the amount is injected to prepare a polyurethane foam molded product.
8) Twenty minutes after injecting the foam forming composition, the polyurethane foam molded product with the face material is taken out from the mold.
9) After taking out the polyurethane foam, place it under the condition of 0 ° C. within 30 minutes, and then let it elapse for about 24 hours.
10) Place a straightedge on the face material on the lower surface side injected with urethane so that it is at a right angle, and set the maximum value of the gap between the straightedge and the face material with a feeler gauge (Niigata Seiki Co., Ltd. 100ML) or a taper gauge (Niigata Seiki Co., Ltd.). 270A) is used for measurement. The obtained results are shown in Tables 1 and 2 as "maximum dent on the lower surface of the injection".
11) Further, with respect to the face material on the lower surface side, the image of the fluorescent lamp reflected on the face material was visually confirmed under a fluorescent lamp (straight tube type), and the smoothness was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2.
(Evaluation criteria)
⊚: The surface was smooth, and the image of the fluorescent lamp was seen as a straight line.
◯: The surface was smooth, and the image of the fluorescent lamp was seen as a straight line, but it seemed that there were slight irregularities.
X: The surface was not smooth, and the image of the fluorescent lamp was wavy.

<Measurement method of gel time>
In order to confirm the reactivity of the foam-forming composition, an amount that does not overflow is injected into a 2 L descup at a predetermined temperature and pressure, and when the mixed solution under injection is touched with disposable chopsticks, the mixed solution begins to pull a thread. The time until was measured as gel time (seconds). The measurement results are shown in Tables 1 and 2.

<Combustibility evaluation>
According to JIS A 9511: 2017, a test piece having a thickness of 10 mm, a length of 200 mm, and a width of 25 mm was used and evaluated according to the following criteria. The measurement was performed by cutting the manufactured polyurethane foam into test pieces of the above dimensions, and standard temperature condition class 3 (23 ° C ± 5 ° C) and standard humidity condition class 3 (50 ^+20, specified in JIS K 7100: 1999). It was allowed to stand under the condition of ^-10 % RH), and was carried out one week after the production. The evaluation results are shown in Tables 1 and 2.
(Evaluation criteria)
○ (Pass): Satisfies the criteria that the flame is extinguished within 3 seconds, there is no residue, and the combustion does not exceed the combustion limit indicator line.
× (Fail): Does not meet the above criteria for passing.

From Tables 1 and 2, it can be seen that the polyurethane foams of Examples are superior in surface quality of the molded product as compared with Comparative Examples 1 and 5-8. Further, it can be seen that the polyurethane foams of Comparative Examples 2 to 4 have poor combustibility because the amount of the compound represented by the formula 1 is too large.

Claims (7)

A composition for forming a polyurethane foam, which contains a hydrofluoroolefin as a foaming agent and contains at least one compound represented by the following formula 1 in an amount of 0.2 to 6 parts by mass with respect to 100 parts by mass of the composition. ,Composition.
RO (CH ₂ CH ₂ O) _n R (Equation 1)
[In the formula, R is a linear or branched alkyl of C1 to C3, and n is an integer of 1 or more. ] The composition according to claim 1, wherein the composition contains 25 parts by mass or more of the polyether polyol with respect to 100 parts by mass of the composition. The composition according to claim 1 or 2, wherein the isocyanate index is 150 or less. The composition according to any one of claims 1 to 3, wherein the polyol contained in the composition has a viscosity of 500 mPas (25 ° C.) or higher. A polyurethane foam obtained by foaming the composition according to any one of claims 1 to 4. The polyurethane foam according to claim 5, which is a polyurethane foam with a face material. The heat insulating material made of the polyurethane foam according to claim 5 or 6.