JP2022039580A - Foaming agents and methods for manufacturing foamed plastics using them, polyurethane foams, articles, system liquids and kits for polyurethane foams. - Google Patents

Abstract

To provide a foamer that can reduce thermal conductivity of a foam to improve a heat insulation performance, a method for producing foamed plastic using the foamer, a polyurethane foam including the foamer, an article including the polyurethane foam, a system liquid including the foamer, and a kit for polyurethane foam including the foamer.SOLUTION: The present invention discloses (1) a foamer containing 1-chloro-2,3,3,3-tetrafluoropropene and trans-1,2-dichloroethylene, (2) the foamer wherein relative to a total mass of the foamer, a total content of 1-chloro-2,3,3,3-tetrafluoropropene and trans-1,2-dichloroethylene is 50-100 mass%, and (3) the foamer wherein 1-chloro-2,3,3,3-tetrafluoropropene/trans-1,2-dichloroethylene, indicating a mass ratio between a content of 1-chloro-2,3,3,3-tetrafluoropropene and a content of trans-1,2-dichloroethylene, is 90/10-20/80.SELECTED DRAWING: None

Description

The present invention relates to a foaming agent, a method for producing a foamed plastic using the foaming agent, a polyurethane foam using the foaming agent, an article containing the polyurethane foam, a system liquid containing the foaming agent, and a polyurethane containing the foaming agent. Regarding foam kits.

As foaming agents used in the production of foamed plastics, chlorinated fluorinated carbon compounds such as CCl ₃ F (chlorofluorocarbon, so-called CFC) and chlorinated fluorinated hydrocarbon compounds such as CCl ₂ FCH ₃ (hydrochlorofluorocarbon, so-called HCFC). .) Has been used conventionally. However, CFCs and HCFCs have high ozone depletion potentials (ODPs), and from the viewpoint of environmental protection such as ozone layer protection, they are subject to the Montreal Protocol regulation, and their use has been regulated.

Even for substances containing chlorine, the ODP of trans-1,2-dichloroethylene is as low as 0.00024 (Non-Patent Document 1), and it is not a regulated substance under the Montreal Protocol. It is known that this trans-1,2-dichloroethylene is used as a foaming agent (Patent Document 1).
However, it is suggested that trans-1,2-dichloroethylene has a high dissolving power in a resin and it is difficult to mold a foam (Patent Document 2).

Japanese Unexamined Patent Publication No. 2005-220345 International Publication No. 2018/101324

Weebbles and Patten, 2010. Atmosphere properties and Ozone Depletion Potentials of trans-1-chloro-3,3,3-trifluoropropylene and trans-1,2-dichloroethylene in atmosphere. Atmos. Chem. Phys. , 10, 10867-10874, 2010

Further, according to the findings of the present inventors, a foam obtained by using trans-1,2-dichloroethylene as a foaming agent may have high thermal conductivity and insufficient heat insulating performance.
INDUSTRIAL APPLICABILITY The present invention is a novel foaming agent which has good moldability of the foam and can reduce the thermal conductivity of the foam to improve the heat insulating performance, a method for producing a foamed plastic using the foaming agent, and the foaming agent. Provided are a polyurethane foam using the above, an article including the polyurethane foam, a system liquid containing the foaming agent, and a kit for polyurethane foam containing the foaming agent.

The present invention has the following aspects.
[1] A foaming agent containing 1-chloro-2,3,3,3-tetrafluoropropene and trans-1,2-dichloroethylene.
[2] The total content of the 1-chloro-2,3,3,3-tetrafluoropropene and the trans-1,2-dichloroethylene is 50 to 100% by mass with respect to the total mass of the foaming agent. There is a foaming agent of [1].
[3] 1-Chloro-2,3, which represents the mass ratio of the content of 1-chloro-2,3,3,3-tetrafluoropropene to the content of trans-1,2-dichloroethylene. The foaming agent of [1] or [2], wherein 3,3-tetrafluoropropene / trans-1,2-dichloroethylene is 90/10 to 20/80.

[4] A method for producing a foamed plastic, which comprises producing the foamed plastic using any of the foaming agents according to the above [1] to [3].
[5] The method for producing a foamed plastic according to [4], wherein the foamed plastic is a thermoplastic resin foam.
[6] The method for producing a foamed plastic according to [4], wherein the foamed plastic is a thermosetting resin foam.
[7] The foamed plastic of [6] for producing a polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a foaming agent, a foaming agent, and a catalyst according to any one of [1] to [3]. Manufacturing method.
[8] The method for producing a foamed plastic according to [7], wherein the polyurethane foam is a rigid polyurethane foam.

[9] A polyurethane foam obtained by reacting a polyol and a polyisocyanate in the presence of the foaming agent, foam stabilizer, and catalyst according to any one of [1] to [3].
[10] A polyurethane foam comprising a cured foam of an effervescent composition containing a polyol, a polyisocyanate, an effervescent agent according to any one of [1] to [3], a defoaming agent, and a catalyst.
[11] The polyurethane foam of [9] or [10], wherein the polyurethane foam is a rigid polyurethane foam.
[12] The polyurethane foam of [11], wherein the density of the rigid polyurethane foam is 5 to 300 kg / m ³ .
[13] An article comprising any of the polyurethane foams of [9] to [12].

[14] A system liquid containing a polyol, a foaming agent according to any one of [1] to [3], a defoaming agent, and a catalyst.
[15] The system liquid of [14], wherein the total mass of the foaming agent is 10 to 100 parts by mass with respect to 100 parts by mass of the polyol.
[16] The system solution of [14] or [15], wherein the polyol contains a polyether polyol.
[17] The system liquid of [16], wherein the content of the polyether polyol is 10 to 100% by mass with respect to the total mass of the polyol.
[18] A kit for polyurethane foam, which comprises a first agent composed of the system liquid according to any one of [14] to [17] and a second agent containing polyisocyanate.

According to the present invention, a foaming agent having good moldability of the foam and capable of lowering the thermal conductivity of the foam to improve heat insulating performance, a method for producing a foamed plastic using the foaming agent, and the foaming agent. The polyurethane foam used, the article containing the polyurethane foam, the system liquid containing the foaming agent, and the kit for polyurethane foam containing the foaming agent can be obtained.

The definitions and description of the following terms apply throughout the specification and claims.
For halogenated hydrocarbons, the abbreviation of the compound is written in parentheses after the compound name, but the abbreviation is used instead of the compound name as necessary. Further, as an abbreviation, only the number after the hyphen (-) and the lowercase alphabetic part (for example, "1224yd" in "HCFO-1224yd") may be used.
In 1224yd, Z-form (cis-form) and E-form (trans-form), which are geometric isomers, are present depending on the position of the substituent bonded to the carbon having a double bond. In the present specification, when a compound name or abbreviation of a compound is used for a compound having Z-form and E-form such as 1224yd, Z-form or E-form, or Z-form and E-form are used without particular mention. The mixture of any proportion is shown. When (Z) or (E) is added after the compound name or the abbreviation of the compound, it indicates that it is the Z-form or the E-form of each compound.

The "weight average molecular weight" (hereinafter referred to as "Mw") is a polystyrene-equivalent molecular weight obtained by measuring with gel permeation chromatography using a calibration curve prepared using a standard polystyrene sample having a known molecular weight.
The "hydroxyl value" is a value measured and calculated by a method based on JIS K 1557. The average hydroxyl value of the polyol is an average value of the hydroxyl values of all the contained polyols, and is a value calculated by measuring a mixture of all the contained polyols by the above method.
The numerical range represented by "-" indicates a numerical range in which the numerical values before and after "-" are the lower limit value and the upper limit value.

The "foamed plastic" is a porous body in which a large number of bubbles (cells) are dispersed in a resin matrix, and is also referred to as a resin foam. Foaming is the generation of air bubbles, and the foam is obtained by solidifying the resin in a state containing air bubbles.
The "thermoplastic resin foam" is a foam plastic in which the matrix is a thermoplastic resin.
The "thermosetting resin foam" is a foamed plastic in which the matrix is a thermosetting resin.
The "foaming agent" is a compound having the following actions. That is, the compound which is a foaming agent has an action of foaming the composition by utilizing the gas generated by vaporization of the compound in the composition containing the compound.
The "polyurethane foam" is a foamed plastic obtained by reacting a compound having active hydrogen such as a polyol with polyisocyanate in the presence of a foam stabilizer, a catalyst and a foaming agent.
The "active hydrogen" is hydrogen derived from at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a hydrazide group and a mercapto group.
The "system liquid" is a composition for obtaining a polyurethane foam. A composition containing a polyisocyanate is also referred to as a "polyisocyanate system liquid", and a composition containing a polyol, a foaming agent, a defoaming agent, and a catalyst is also referred to as a "polyol system liquid".

<Effervescent agent>
The foaming agent of the present embodiment (hereinafter, also referred to as foaming agent A) is 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) and trans-1,2-dichloroethylene (hereinafter, also referred to as "foaming agent A"). Also referred to as tDCE).
The 1224yd may be 1224yd (Z), 1224yd (E), or a combination thereof.
The foaming agent A may contain other foaming agents other than 1224yd and tDCE. As other foaming agents, known foaming agents can be appropriately used as long as the effects of the present invention are not impaired.

The ratio of the total mass of 1224yd and tDCE to the total mass of the foaming agent A is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 90 to 100% by mass.
In the foaming agent A, 1224yd / tDCE, which represents the mass ratio of the content of 1224yd and the content of tDCE, is preferably 90/10 to 20/80, more preferably 80/20 to 50/50. When the content of 1224yd is not more than the upper limit of the above range, the boiling point of the foaming agent A is not too low, and bumping of the liquid containing the foaming agent A is unlikely to occur. When it is at least the lower limit, the effect of reducing the thermal conductivity of the foam is excellent.
In the foaming agent A, the Z / E ratio representing the mass ratio of the content of 1224 yd (Z) and the content of 1224 yd (E) may be 0/100 to 100/0, exceeding 90/10, and 99.9. It is preferably /0.1 or less, and more preferably 91/9 to 99.5 / 0.5.

The boiling point of the foaming agent A at atmospheric pressure (101.3 kPa) is preferably 18 to 35 ° C, more preferably 20 to 30 ° C. If it is at least the lower limit of the above range, bumping of the liquid containing the foaming agent A is unlikely to occur at the time of blending, and if it is at least the upper limit, sufficient foaming is likely to be obtained.
The foaming agent A is a mixture of two or more compounds, and the boiling point is the boiling point of the mixture. The boiling point of the foaming agent A can be adjusted by the mass ratio of the content of 1224 yd and the content of tDCE. The higher the content of 1224yd, the lower the boiling point tends to be.

1224yd may contain other compounds due to manufacturing process or other reasons. Other compounds include hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (excluding HCFO-1224yd), hydrochloroolefins, chlorofluoroolefins (CFOs), fluoroolefins (FOs), chloroolefins, olefins, hydros. Fluorocarbon (HFC), Hydrochlorocarbon (HCC), Hydrochlorofluorocarbon (HCFC), Chlorofluorocarbon (CFC), Chlorocarbon, Fluorocarbon (FC), Hydrocarbon (HC), Hydrofluoroether (HFE), Alcohol, Ether, Examples thereof include ketones, organic acids, inert gases, and saturated hydrocarbons.
The total amount of the other compounds is preferably 5% by mass or less, preferably 1% by mass or less, and particularly preferably 0.5% by mass or less with respect to 1224yd.

Specific examples of hydrofluoroolefins include 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,1,2,3-tetrafluoropropene (HFO-1234yc), 2,3,3,3. -Tetrafluoropropene (HFO-1234yf), 1,1,2,3,3-pentafluoropropene (HFO-1225yc), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 3, 3,3-Trifluoropropene (HFO-1243zf), 3,3-difluoropropene (HFO-1252zf), 2-fluoropropene (HFO-1261yf), 1,1,1,4,4,4-hexafluoro- 2-Buten (HFO-1336mzz), 2,3,3,4,4,4-hexafluoro-1-butene (HFO-1336mcif), 1,3,3,4,4,4-hexafluoro-1- Butene (HFO-1336ze), Tetrafluorobutene (HFO-1354), 1,1,1,2,4,4,5,5-Nonafluoropentene (HFO-1429myz), 1,1,1,4 , 4,5,5,5-octafluoropent-2-ene (HFO-1438mzz), 1,3,4,5,4-pentafluoro-3-trifluoromethyl-1-butene (HFO-1438ezy), (C ₂ F ₅ ) (CF ₃ ) C = CH ₂ , (CF ₃ ) ₂ CFCH = CF ₂ , (CF ₃ ) ₂ CFCF = CHF, 1,1-difluoroethylene (HFO-1132a), 1,1, Examples thereof include 2-trifluoroethylene (HFO-1123) and 1,2,3,3,3-pentafluoro-1-propene (HFO-1225ye).

Specific examples of hydrochlorofluoroolefins (excluding HCFO-1224yd) include 2,3,3-trichloro-3-fluoropropene (HCFO-1231xf) and 2,3-dichloro-3,3-difluoropropene (excluding HCFO-1224yd). HCFO-1232xf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd), 2-chloro-3, 3,3-Trifluoropropene (HCFO-1233xf), 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 2-chloro-1,1,3,3-tetrafluoropropene (HCFO-) 1224xc), 2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe), 1,1-dichloro-2-fluoroethylene (HCFO-1121a), 1,2-dichloro-1-fluoroethylene (HCFO-1121), 1-chloro-1-fluoroethylene (HCFO-1131a), 1-chloro-2-fluoroethylene (HCFO-1131), 1-chloro-2,2-difluoroethylene (HCFO-1122), 1,1,2-Trifluoro-2-chloroethylene (HCFO-1113), 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 1-chloro-3,3,3-trifluoro -1-Propine (CF ₃ -C≡CCl) can be mentioned.

Specific examples of the hydrochloroolefin include chloroethylene and 1,2-dichloroethylene.

Specific examples of chlorofluoroolefins include 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1,1,2-trichloro-2-fluoroethylene, and 2-chloro-1. , 1,3,3,3-pentafluoro-1-propene (CFO-1215xc).

Specific examples of fluoroolefins include hexafluoropropene (FO-1216) and octafluoro-2-butene (FO-1318my).

Specific examples of the chloroolefin include tetrachlorethylene.

Specific examples of the olefin include ethylene and propylene.

Specific examples of hydrofluorocarbons include 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,2,2-pentafluoropropane (HFC-245cc), 1,1,1. 2,2,3-Pentafluoropropane (HFC-245ca), 1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,1,1,2,3,3,3-heptafluoro Propane (HFC-227ea), 1,1,1,2-tetrafluoropropane (HFC-254eb), 1,1,1,3-tetrafluoropropane (HFC-254fb), 1,1,1-trifluoropropane (HFC-263fb), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 2- Fluoropropane (HFC-281ea), 2-Chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1, 1,2-Tetrafluoroethane (HFC-134a), 1,2-difluoroethane (HFC-152), 1,1-difluoroethane (HFC-152a), difluoromethane (HFC-32), 1,1,1,2 , 2-Pentafluoroethane (HFC-125), 1,1,2-trifluoroethane (HFC-143), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,3 3-Pentafluorobutane (HFC-365mfc), Fluoroetan (HFC-161), 1,1,1,2,2,3,4,5,5-decafluoropentane (HFC-43-10mee), Examples thereof include trifluoromethane (HFC-23) and fluoromethane (HFC-41).

Specific examples of hydrochlorocarbon include chloroform, 1,1,1,2,3-pentachloropropane (HCC-240db), and 2-chloropropane.

Specific examples of hydrochlorofluorocarbons include chlorodifluoromethane (HCFC-22), chlorofluoromethane (HCFC-31), trichlorodifluoroethane (HCFC-122), and 1,1,2-trichloro-1,2-difluoroethane (HCFC). -122a), 1,1,1-trichloro-2,2-difluoroethane (HCFC-122b), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123), 2-chloro-1, 1,1,2-Tetrafluoroethane (HCFC-124), 1-chloro-1,1,2,2-tetrafluoroethane (HCFC-124a), 2-chloro-1,1,1-trifluoroethane (HCFC-124a) HCFC-133a), 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1-difluoro-2-chloroethane (HCFC-142), 1-chloro-1,2-difluoroethane (HCFC-142a) , 1-chloro-1,1-difluoroethane (HCFC-142b), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca), 1,3-dichloro-1,1 , 2,2,3-Pentafluoropropane (HCFC-225cc), 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243ab), 2,3-dichloro-1,1,1-tri Fluoropropane (HCFC-243db), 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) can be mentioned.

Specific examples of chlorofluorocarbons include trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), trichlorotrifluoroethane (CFC-113), and 1,2-dichloro. -1,1,2,2-tetrafluoroethane (CFC-114), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CFC-114a), chloropentafluoroethane (CFC-115) , Dichlorohexafluoropropane (CFC-216), 2,2,3,3-tetrachlorohexafluorobutane (CFC-316), dichlorooctafluorobutane (CFC-318).

Specific examples of chlorocarbon include dichloromethane (methylene chloride) and trichloroethane.

Specific examples of fluorocarbons include 1,1,1,2,2,2-hexafluoroethane (FC-116) and octafluoropropane (FC-218) 1,1,1,2,2,3,3-. Heptafluoropropane (FC-227ca) can be mentioned.

Specific examples of the hydrocarbon include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, isohexane and heptane.

Specific examples of the hydrofluoroether include CHF ₂ -O-CHF ₂ , CHF ₂ -O-CH ₂ F, CH ₂ F-O-CH ₂ F, CH ₂ F-O-CH ₃ , and cyclo-CF _2- . CH ₂ -CF ₂ -O, cyclo-CF ₂ -CF ₂ -CH ₂ -O, CHF ₂ -O-CF ₂ -CHF ₂ , CF ₃ -CF ₂ -O-CH ₂ F, CHF ₂ -O-CHF -CF ₃ , CHF ₂ -O-CF ₂ -CHF ₂ , CH ₂ F-O-CF ₂ -CHF ₂ , CF ₃ -O-CF ₂ -CH ₃ , CHF ₂ -CHF-O-CHF ₂ , CF ₃ -O-CHF-CH ₂ F, CF ₃ -CHF-O-CH ₂ F, CF ₃ -O-CH ₂ -CHF ₂ , CHF ₂ -O-CH ₂ -CF ₃ , CHF ₂ -CF ₂ -O- CH ₂ F, CHF ₂ -O-CF ₂ -CH ₃ , CHF ₂ -CF ₂ -O-CH ₃ , CHF ₂ -CF ₂ -O-CH ₃ , CH ₂ F-O-CHF-CH ₂ F, CHF ₂ -CHF-O-CH ₂ F, CF ₃ -O-CHF-CH ₃ , CF ₃ -CHF-O-CH ₃ , CHF ₂ -O-CH ₂ -CHF ₂ , CF ₃ -O-CH ₂ -CH ₂ F, CF ₃ -CH ₂ -O-CH ₂ F, CF ₂ H-CF ₂ -CF ₂ -O-CH ₃ , CF ₃ CF ₂ CF ₂ -O-CH ₃ , C ₄ H ₉ -O-CH ₃ is mentioned.

Specific examples of the alcohol include methanol, ethanol, propanol and isopropanol.

Specific examples of the ether include dimethyl ether, methyl ethyl ether, diethyl ether, methyl propyl ether, methyl isopropyl ether, ethyl propyl ether, ethyl isopropyl ether, dipropyl ether, diisopropyl ether, dimethoxymethane, diethoxyethane, and dipropoxymethane. Dibutoxymethane can be mentioned.

Specific examples of the ketone include ketone, methyl ethyl ketone, methyl isobutyl ketone, and perfluoroethyl isopropyl ketone.

Specific examples of the organic acid include methyl formate, ethyl formate, and formic acid.

Specific examples of the inert gas include carbon dioxide, nitrogen, argon and helium.

Specific examples of saturated hydrocarbons include methane, ethane, propane, butane, isobutane, pentane, isopentane, cyclopentane, and hexane.

<Manufacturing method of foamed plastic>
The method for producing foamed plastic of the present embodiment is a method for producing foamed plastic using the above-mentioned foaming agent A.
Examples of the foamed plastic include a thermosetting resin foam and a thermoplastic resin foam.
Specific examples of the thermosetting resin foam include polyurethane foam, polyisocyanurate foam, and phenol resin foam. The polyurethane foam (also referred to as polyurethane foam) will be described later.
Specific examples of the thermoplastic resin contained in the thermoplastic resin foam include polycarbonate resin, polystyrene resin, polyphenylene ether resin, acrylonitrile-butadiene-styrene resin, polyolefin resin, polyvinyl chloride resin, (meth) acrylic resin, and polyester resin. , Modified polyphenylene ether resin, polyacetal resin, polyetherimide resin, polyether sulfone resin, polyamide resin, polysulfone resin, polyether ether ketone resin, and polyether ketone resin.
Specific examples of the polyolefin resin include polyethylene resin and polypropylene resin. Further, the polyolefin resin may be an amorphous polyolefin resin or a crystalline polyolefin resin.
Specific examples of the polyester resin include polyethylene terephthalate resin, polybutylene terephthalate resin, total aromatic polyester resin, and polyallylate resin.
The modified polyphenylene ether resin is a polymer alloy of the polyphenylene ether resin and another thermoplastic resin (for example, polystyrene resin).
The foaming agent A is a physical foaming agent that foams by utilizing the gas generated by the vaporization of the foaming agent. In the present embodiment, a known method for producing a foamed plastic using a physical foaming agent can be appropriately used.

<Polyurethane foam and its manufacturing method>
The polyurethane foam is a resin foam obtained by mixing a polyol having two or more hydroxyl groups, a polyisocyanate having two or more isocyanate groups, and a foaming agent to simultaneously carry out a foaming reaction and a resinification reaction. ..
The method for producing a polyurethane foam of the present embodiment is a method for producing a polyurethane foam using the foaming agent A.
The method for producing a polyurethane foam of the present embodiment comprises reacting a polyol with a polyisocyanate in the presence of a foaming agent A, a foam stabilizer, and a catalyst.
Preferably, an effervescent composition comprising all components including a polyol, a polyisocyanate, a foaming agent A, a foaming agent, and a catalyst used for producing a polyurethane foam is prepared, and the polyol and poly in the effervescent composition are prepared. Polyurethane foam is produced by reacting with isocyanate.

When all the components of the effervescent composition are mixed, the reaction starts rapidly and cures while foaming to form a cured foam. Therefore, it is preferable to store at least the polyol and the polyisocyanate separately. The effervescent composition is preferably a multi-component type, for example, a two-component type.
In the case of the two-component type, when the effervescent composition is stored, it is divided into a first agent consisting of a system liquid containing a polyol, a foaming agent A, a defoaming agent and a catalyst, and a second agent containing a polyisocyanate. It is preferable to mix the agent and the second agent to produce a polyurethane foam. Further, the first agent consisting of a system liquid containing a polyol, a foaming agent A, a foaming agent and a catalyst is divided into a second agent consisting of a system liquid containing a polyisocyanate and a foaming agent A, and the first agent and the second agent are divided into two. It may be mixed to produce a polyurethane foam.
Alternatively, all the components of the effervescent composition are divided and stored in three or more liquids, a liquid containing a polyol, a liquid containing a polyisocyanate, and a liquid containing a foaming agent A, and these are mixed to produce a polyurethane foam. You may.

The polyurethane foam of the present embodiment is obtained by reacting a polyol with a polyisocyanate in the presence of a foaming agent A, a foam stabilizer, and a catalyst. It is preferably a cured foam of the effervescent composition.

Examples of the polyurethane foam include rigid polyurethane foam, rigid urethane-modified polyisocyanurate foam, rigid polyurea foam, flexible polyurethane foam, semi-rigid polyurethane foam, and polyurethane integral skin foam.
For example, rigid polyurethane foam has a high closed cell ratio and excellent heat insulating properties. The flexible polyurethane foam has open cells, has a low closed cell ratio, and has resilience to shape deformation. The polyurethane integral skin foam has a high-density skin layer on the surface layer portion of the foam (core portion). The thickness of the skin layer is, for example, about 1 to 5 mm. The skin layer is preferably a non-foam layer containing no bubbles, a microcell layer composed of cells denser than the core portion, or a layer containing both of them.
These polyurethane foams can be produced by applying the foaming agent A to a known production method suitable for each.

<Rigid polyurethane foam and its manufacturing method>
Hereinafter, an embodiment in which the polyurethane foam is a rigid polyurethane foam will be described in detail with reference to an example.
The method for producing a rigid polyurethane foam of the present embodiment includes reacting a polyol with a polyisocyanate in the presence of a foaming agent A, a foam stabilizer, and a catalyst.
Preferably, an effervescent composition comprising all components including a polyol, a polyisocyanate, a foaming agent A, a foaming agent, and a catalyst used for producing a rigid polyurethane foam is prepared and combined with the polyol in the effervescent composition. A rigid polyurethane foam is produced by foaming while reacting with polyisocyanate to cure.
A method of producing a rigid polyurethane foam by mixing a polyol system liquid containing a polyol, a foaming agent A, a foam stabilizer and a catalyst with a polyisocyanate system liquid containing a polyisocyanate is preferable.

[Polyform system liquid]
The polyol system liquid of the present embodiment contains a polyol, a foaming agent A, a foam stabilizer and a catalyst.
(Polyol)
The polyol is not particularly limited as long as it is a polyol used for the reaction with polyisocyanate. The polyol contained in the system liquid may be one kind or two or more kinds.
The average number of hydroxyl groups of the polyol is preferably 2 to 8, more preferably 2.5 to 7.5. When it is at least the lower limit of the above range, the compressive strength of the rigid polyurethane foam is improved and shrinkage can be suppressed, so that the dimensional stability tends to be good. When it is not more than the upper limit of the above range, the viscosity of the polyol does not become too high, so that foaming, fluidity at the time of molding, and moldability tend to be good. The average number of hydroxyl groups of the above-mentioned polyol is a value obtained by molarly averaging the number of hydroxyl groups of all the contained polyols.

The Mw of the polyol is preferably 100 to 3000, more preferably 150 to 2000. When it is not more than the upper limit of the above range, the shrinkage of the rigid polyurethane foam is suppressed, and the dimensional stability tends to be good. When it is at least the lower limit of the above range, the rigid polyurethane foam is less likely to become brittle. The Mw of the above-mentioned polyol is an average value of Mw of all the polyols contained therein.

The average hydroxyl value of the polyol is preferably 100 to 800 mgKOH / g, more preferably 200 to 700 mgKOH / g, and even more preferably 300 to 600 mgKOH / g. When it is at least the lower limit of the above range, shrinkage of the rigid polyurethane foam is suppressed and dimensional stability is improved. If it is less than the upper limit, the rigid polyurethane foam is less likely to become brittle. The average hydroxyl value of the above-mentioned polyol may be calculated by weighted averaging the hydroxyl values of all the contained polyols, or may be a value measured by mixing all the contained polyols.

Examples of the polyol include a polyether polyol, a polyester polyol, a polymer having a main chain made of a hydrocarbon polymer and having a hydroxyl group introduced at the terminal portion, and a polyhydric alcohol. As the polyol, polyester ether polyol or polycarbonate polyol may be used.

A polyether polyol or a polyester polyol is preferable because the obtained rigid polyurethane foam has excellent physical characteristics. The polyether polyol contains the polyether polyol described later because it is easy to obtain good mixing with the polyisocyanate and it is easy to obtain the adhesiveness when the rigid polyurethane foam is formed between the metal face materials and the like. Is preferable. Since the obtained rigid polyurethane foam tends to have good flame retardancy, the polyester polyol preferably contains a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid.

-Polyether polyol The polyether polyol can be produced by a conventionally known method. A compound obtained by reacting the cyclic ether in the presence of a catalyst using a compound containing active hydrogen with which the cyclic ether can react is preferable.

Examples of the initiator include the compounds exemplified below or compounds obtained by adding a small amount of cyclic ether to those compounds. The compounds exemplified below may be one kind or a mixture of two or more kinds. As an initiator, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1, 6-Hexanediol, 2-Methyl-2,4-Pentanediol, 3-Methyl-1,5-Pentanediol, 1,4-Cyclohexanediol, 1,4-Cyclohexanedimethanol, Glycerin, Trimethylolpropane, 1, Polyhydric alcohols such as 2,6-hexanetriol, pentaerythritol, diglycerin, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, galactitol, sucrose; water; bisphenol A, phenol-formaldehyde initial condensate, Mannig condensate, etc. Polyvalent phenols; monoethanolamines, diethanolamines, triethanolamines, isopropanolamines, alkanolamines such as N- (2-aminoethyl) ethanolamines; ethylenediamine, propylenediamine, hexamethylenediamine, piperazine, aniline, ammonia, N- Aminomethyl piperazine, N- (2-aminoethyl) piperazine, 4-methyl-1,3-phenylenediamine, 4-methyl-1,2-phenylenediamine, 2-methyl-1,3-phenylenediamine, 4,4 '-Amines such as diphenylmethanediamine, xylylene diamine, diethylenetriamine, and triethylenetetramine can be mentioned.

As the cyclic ether, a cyclic ether compound having a 3- to 6-membered ring having one oxygen atom in the ring is preferable. The cyclic ether may be used alone or in combination of two or more. When two or more kinds are used in combination, they may be mixed and reacted, or they may be reacted sequentially. As the cyclic ether, ethylene oxide (hereinafter referred to as "EO"), propylene oxide (hereinafter referred to as "PO"), butylene oxide, or a combination of two or more thereof is more preferable, and EO, PO, or EO. The combination of PO is more preferable.

As the catalyst present when polymerizing the initiator and the cyclic ether, for example, a known catalyst such as an alkali metal compound catalyst (sodium-based catalyst, potassium-based catalyst, cesium-based catalyst, etc.) can be used, and the initiator can be used. If the initiator contains an amino group, the initiator itself acts as a catalyst, and this can also be used.

In the present embodiment, the content of the above-mentioned polyether polyol is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, still more preferably 50 to 100% by mass, based on the total mass of the polyol. When it is at least the lower limit of the above range, the heat insulating property and the compressive strength of the obtained rigid polyurethane foam tend to be good.

As the polyether polyol, for example, a polyether polyol obtained by ring-opening addition polymerization of an alkylene oxide using an aromatic amine as an initiator (hereinafter, also referred to as “aromatic amine initiator polyol”) is preferable. As the aromatic amine initiator polyol, only one kind may be used, or two or more kinds may be used in combination.

Aromatic amines, which are initiators, are amines having an aromatic ring and having 4 to 12 active hydrogen atoms. Specific examples thereof include phenylenediamine, tolylenediamine, diaminodiphenylmethane, Mannich condensate and the like.
The Mannig condensate is preferably a compound obtained by reacting phenols such as phenol and nonylphenol; aldehydes such as formaldehyde; and alkanolamines such as monoethanolamine and diethanolamine. The molecular weight of the Mannich condensate is preferably about 200 to 10,000.
Of these initiators, tolylene diamine is particularly preferred because it provides low thermal conductivity. As the tolylene diamine, o-tolylene diamine and m-tolylene diamine are preferable.

As the alkylene oxide used for producing the aromatic amine initiator polyol, it is preferable to use ethylene oxide (hereinafter, also referred to as EO) and / or propylene oxide (hereinafter, also referred to as PO). In addition, butylene oxide, isobutylene oxide, styrene oxide and the like may be used in combination. When using EO and / or PO, any of the following methods may be used. (1) A method of ring-opening addition polymerization of EO alone. (2) A method of ring-opening addition polymerization of PO alone. (3) A method of ring-opening addition polymerization of a mixture of PO and EO. (4) A method for ring-opening addition polymerization by arbitrarily combining the above methods (1) to (3).
In order to impart good physical properties to the rigid foam, it is preferable to use the combination of (1) and (2) or the method of (2). When combining (1) and (2), it is more preferable to carry out ring-opening addition polymerization in the order of (1)-(2)-(1).
The content of ethylene oxide (total EO content) in the total amount of alkylene oxide used for producing the aromatic amine initiator polyol is preferably 0 to 60% by mass, more preferably 0 to 45% by mass, and 0 to 30% by mass. Is particularly preferable. When it is not more than the upper limit of the above range, the moldability is good because it has an appropriate reactivity.
By reacting the alkylene oxide with the active hydrogen atom of the initiator, the alkylene oxide is ring-opened and added to form a polyol having an oxyalkylene group. A hydroxyalkyl group is formed by the ring-opening addition of one molecule of alkylene oxide to the active hydrogen atom, and the alkylene oxide is subsequently ring-opened and added to the hydroxyl group, and this reaction is repeated to form a chain of oxyalkylene groups. do. When the alkylene oxide is EO, the oxyethylene group is chained, and when the alkylene oxide is PO, the oxypropylene group is chained.
When ring-opening addition polymerization is carried out in the order of (1)-(2)-(1), the amount of EO to be subjected to ring-opening addition polymerization after addition in the order of EO and PO (EO content at the terminal) is aromatic. 1 to 40% by mass is preferable, 1 to 30% by mass is more preferable, and 1 to 20% by mass is particularly preferable, based on the total amount of the alkylene oxide used for producing the amine initiator polyol. When it is not more than the upper limit of the above range, the viscosity of the aromatic amine initiator polyol does not become too high, and when it is more than the lower limit, the reactivity of the aromatic amine initiator polyol is improved. In the aromatic amine initiator polyol obtained by performing ring-opening addition polymerization in the order of (1)-(2)-(1), an oxyethylene group is linked to the initiator, and then an oxypropylene group is linked. It is a polyol having an oxyethylene group chained at the end.

The number of hydroxyl groups of the aromatic amine initiator polyol is 4 to 12, preferably 4 to 10, and particularly preferably 4 to 8. When the number of hydroxyl groups of the aromatic amine initiator polyol is at least the lower limit of the above range, shrinkage of the rigid foam is likely to be suppressed, and when it is at least the upper limit, the viscosity is in an appropriate range and handling is easy.
The hydroxyl value of the aromatic amine initiator polyol is 100 to 800 mgKOH / g, preferably 200 to 600 mgKOH / g, and particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the aromatic amine initiator polyol is at least the lower limit of the above range, the compressive strength of the rigid foam and the like are improved, the foaming rate is also improved, and the thermal conductivity is also good. When it is not more than the upper limit of the above range, the brittleness of the hard foam is suppressed.
The content of the aromatic amine initiator polyol in the polyol composition is 30 to 70% by mass, preferably 30 to 60% by mass, and particularly preferably 30 to 50% by mass. When the content of the aromatic amine initiator polyol is at least the lower limit of the above range, the self-foaming rate is improved and good thermal conductivity is obtained. When it is not more than the upper limit of the above range, the viscosity of the polyol system liquid does not become too high and it is easy to handle.

The polyol preferably contains, in addition to the aromatic amine initiator polyol, a polyether polyol obtained by ring-opening addition polymerization of an alkylene oxide using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator. The polyol, which is started by a polyhydric alcohol having 4 to 12 active hydrogen atoms, contributes to the improvement of the compressive strength of the rigid foam and the good dimensional stability. Further, by using a polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator in addition to the aromatic amine initiator polyol, it is possible to prevent the viscosity of the polyol composition from becoming too high.
As the polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator, only one kind may be used, or two or more kinds may be used in combination.

It is preferable to use a saccharide as the initiator, which is a polyhydric alcohol having 4 to 12 active hydrogen atoms. Specific examples of the saccharide include fructose, sorbitol, sucrose and the like. Of these, sorbitol or sucrose is preferable.
Examples of the alkylene oxide used for producing the polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator include ethylene oxide, propylene oxide and butylene oxide. At least propylene oxide or butylene oxide is preferably contained, and at least propylene oxide is particularly preferable.
As the alkylene oxide used for producing the polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator, it is preferable to use propylene oxide alone or in combination with ethylene oxide and propylene oxide. When used in combination, ethylene oxide and propylene oxide may be mixed and then reacted, or may be reacted sequentially.
The ethylene oxide content (total EO content) in the total amount of alkylene oxide used for producing a polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator is 0 to 20% by mass, and 0 to 0 to 0. 10% by mass is preferable, and 0% by mass, that is, PO alone is particularly preferable. When the content of ethylene oxide is not more than the upper limit of the above range, the reactivity can be easily controlled.

The number of hydroxyl groups of the polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator is 4 to 12, preferably 4 to 10, and particularly preferably 4 to 8. When the number of hydroxyl groups of the polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator is at least the lower limit of the above range, shrinkage of the hard foam is likely to be suppressed, and when it is at least the upper limit, the viscosity is appropriate. It is within the range and easy to handle.
The hydroxyl value of the polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator is 100 to 800 mgKOH / g, preferably 200 to 600 mgKOH / g, and particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the polyol using a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator is at least the lower limit of the above range, shrinkage of the hard foam can be suppressed and dimensional stability is improved. When it is not more than the upper limit of the above range, the brittleness of the rigid polyurethane foam can be suppressed.
The content of the polyol in the polyol composition starting from a polyhydric alcohol having 4 to 12 active hydrogen atoms is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, and 5 to 45% by mass. Is particularly preferable. When the content of the polyol having a polyhydric alcohol having 4 to 12 active hydrogen atoms as an initiator is not more than the lower limit of the above range, the compressive strength of the hard foam is good and the shrinkage is well suppressed. Therefore, good dimensional stability is easily obtained. When it is not more than the upper limit of the above range, good curing characteristics (cure property) are easily ensured at the time of molding a hard foam.

The polyol preferably contains a polyether polyol obtained by ring-opening addition polymerization of an alkylene oxide using an aliphatic amine as an initiator.
Polyols using an aliphatic amine as an initiator contribute to the improvement of moldability and reactivity. Further, by using a polyol having an aliphatic amine as an initiator in addition to the aromatic amine initiator polyol, it is possible to prevent the viscosity of the polyol composition from becoming too high.
As the polyol having an aliphatic amine as an initiator, only one kind may be used, or two or more kinds may be used in combination.

The aliphatic amine as an initiator is an aliphatic amine having 2 to 4 active hydrogen atoms. Specific examples include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkylamines such as ethylenediamine, propylenediamine and 1,6-hexanediamine. Of these, ethylenediamine, monoethanolamine or diethanolamine is preferable.
Examples of the alkylene oxide used for producing the polyol using the aliphatic amine as an initiator include ethylene oxide, propylene oxide and butylene oxide. It is preferable to use propylene oxide alone or in combination with ethylene oxide and propylene oxide. When used in combination, ethylene oxide and propylene oxide may be mixed and then reacted, or may be reacted sequentially.
The ethylene oxide content (total EO content) in the total amount of the alkylene oxide used for producing the polyol using the aliphatic amine as an initiator is 0 to 50% by mass, preferably 0 to 48% by mass, preferably 0 to 45. %% by weight is more preferred, and 0% by weight, i.e. PO alone, is particularly preferred. When the content of ethylene oxide is not more than the upper limit of the above range, it is easy to control the reactivity at the time of foaming, and good moldability can be ensured.

The number of hydroxyl groups of the polyol using the aliphatic amine as an initiator is 2 to 4. When the number of hydroxyl groups of the polyol using the aliphatic amine as an initiator is not more than the upper limit of the above range, the viscosity becomes an appropriate range and it is easy to handle.
The hydroxyl value of the polyol using the aliphatic amine as an initiator is 100 to 800 mgKOH / g, preferably 200 to 600 mgKOH / g, and particularly preferably 300 to 500 mgKOH / g. When the hydroxyl value of the polyol using the aliphatic amine as an initiator is at least the lower limit of the above range, the compressive strength of the rigid polyurethane foam is improved, shrinkage is suppressed, and good dimensional stability is obtained. When it is not more than the upper limit of the above range, the viscosity does not become too high and it is easy to handle.
The content of the polyol having an aliphatic amine as an initiator in the polyol composition is preferably 10 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 10 to 25% by mass. When the content of the polyol having an aliphatic amine as an initiator is at least the lower limit of the above range, the cure property is good and the workability at the time of demolding is likely to be improved. When it is not more than the upper limit of the above range, it is easy to control the reactivity at the time of foaming.

-Polyester polyol As the polyester polyol, for example, a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid can be mentioned. In addition, there are polyester polyols obtained by polycondensation of hydroxycarboxylic acid, polymerization of cyclic ester (lactone), double addition of cyclic ether to polycarboxylic acid anhydride, and ester exchange reaction of polyethylene terephthalate.

Examples of the polyhydric alcohol used for the polycondensation include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1, 3-Propylene diol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin , Trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, diglycerin, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, galactitol, and sucrose.

As the polyvalent carboxylic acid used for the polycondensation, a dicarboxylic acid or an anhydride thereof is preferable. The dicarboxylic acid may or may not have an aromatic ring. Examples of the dicarboxylic acid having an aromatic ring include phthalic acids such as phthalic anhydride, terephthalic acid, isophthalic acid and orthophthalic acid. Examples of the dicarboxylic acid having no aromatic ring include maleic acid, fumaric acid, adipic acid and the like. Phthalic anhydride, terephthalic acid, isophthalic acid, and orthophthalic acid, which are dicarboxylic acids having an aromatic ring, are preferable in terms of improving flame retardancy. As the polyvalent carboxylic acid, only one kind may be used, or two or more kinds may be used in combination.

The average number of hydroxyl groups of the polyester polyol is preferably 2 to 3, and particularly preferably 2. When the average number of hydroxyl groups is 3 or less, the viscosity of the polyester polyol can be kept low and it is easy to handle.
The hydroxyl value of the polyester polyol is preferably 100 to 500 mgKOH / g, more preferably 150 to 350 mgKOH / g, and particularly preferably 180 to 320 mgKOH / g. When the hydroxyl value of the polyester polyol is at least the lower limit of the above range, shrinkage of the rigid polyurethane foam is likely to be suppressed, and when it is at least the upper limit of the above range, the brittleness of the rigid polyurethane foam is suppressed and good physical properties are likely to be obtained. ..

In the present embodiment, the polyester polyol is not essential, but when the polyester polyol is used, the content of the polyester polyol in 100% by mass of the polyol is preferably more than 0% by mass and 70% by mass or less, preferably 1 to 65% by mass. More preferably, 5 to 60% by mass is particularly preferable. When the content of the polyester polyol is at least the lower limit of the above range, the effect of reducing the viscosity of the system liquid can be easily obtained. When the content of the polyester polyol is not more than the upper limit of the above range, the shrinkage of the rigid polyurethane foam is likely to be suppressed.

-Polymer whose main chain is made of a hydrocarbon-based polymer and has a hydroxyl group introduced at the terminal portion Examples of the polymer having a main chain made of a hydrocarbon-based polymer and having a hydroxyl group introduced at the terminal portion include hydrogenated polybutadiene polyol and polybutadiene. Examples include polyols.

-Multivalent alcohol The polyhydric alcohol exemplified in the description of the polyester polyol can be used as the polyol in the present invention.

-Others As the above-mentioned polyol, a polyol composition in which fine particles of vinyl polymer are dispersed mainly in a polyether polyol, which is called a polymer polyol or a graft polyol, can also be used.

The polyol in the present embodiment preferably contains a polyether polyol and a polyester polyol.

When the polyol in the present embodiment contains an oxyethylene group, the content ratio of the oxyethylene group to the total amount of the oxyalkylene group may be more than 0% by mass and 100% by mass or less, and more than 0% by mass and 80% by mass or less. Is more preferable, more than 0% by mass and 60% by mass or less is more preferable, and more than 0% by mass and 50% by mass or less is further preferable. When the content ratio is within the above range, the solubility of the polyol and the foaming agent A is appropriately adjusted, and the compressive strength of the rigid polyurethane foam tends to be high. The above content ratio is calculated as the content ratio of the oxyethylene group to the total amount of the oxyalkylene group in the total amount of the contained polyol.

(Effervescent agent A)
The foaming agent A is as described above.
The foaming agent A may contain other foaming agents other than 1224yd and tDCE.
As the other foaming agent, a known physical foaming agent can be used. For example, the above-mentioned hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs, except for 1224yd), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), hydrocarbons (HCs), hydrofluoroethers (HFEs), and the like. Examples thereof include organic acids, inert gases, and saturated hydrocarbons. Further, a chlorine-based solvent such as CH ₂ Cl ₂ (however, excluding tDCE) can also be exemplified.

The amount of the foaming agent A used is preferably 10 to 100 parts by mass, more preferably 12 to 60 parts by mass, still more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the polyol. When it is within the above range, the density of the obtained rigid polyurethane foam becomes appropriate, and the heat insulating performance tends to be good.

(Foaming aid)
Further, in addition to the foaming agent A, a chemical foaming agent may be used in combination as a foaming aid. The compound used as a foaming aid is preferably a compound that foams the composition by utilizing a gas generated by the reaction between the compound and the polyisocyanate in the composition containing the compound and the polyisocyanate. For example, water is preferable.
As the chemical foaming agent other than water, an inorganic chemical foaming agent and an organic chemical foaming agent known in the production of rigid polyurethane foam can be used. Specific examples of the inorganic chemical foaming agent include sodium bicarbonate and ammonium carbonate. Specific examples of the organic chemical foaming agent include azodicarbonamide, N, N'-dinitrosopentamethylenetetramine, 4,4'-oxybis (benzenesulfonylhydrazide), and azobisisobutyronitrile.
When the foaming agent A and water are used in combination, 0.1 to 70 parts by mass of water is preferable, 0.3 to 50 parts by mass is more preferable, and 0.5 to 30 parts by mass is preferable with respect to 100 parts by mass of the foaming agent A. The unit is more preferable.

(Defoamer)
Defoaming agents are used to form good foam.
Examples of the defoaming agent include silicone-based defoaming agents and fluorine-containing compound-based defoaming agents.
As the foam stabilizer, a surfactant or the like can be used, and examples thereof include organic silicone-based surfactants such as nonionic surfactants such as organic siloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Be done.
Further, as the defoaming agent, a graft copolymer of polyoxyalkylene glycol, which is a polymer of ethylene oxide or propylene oxide, and polydimethylsiloxane can also be used, and the content of oxyethylene groups in the polyoxyalkylene is 70 to 100. A mol% silicone defoaming agent can be preferably used.

A commercially available product may be used as the foam stabilizer.
Examples of commercially available products include L5420, L5340, L6188, L6877, L6889, and L6900 manufactured by Momentive; B8040, B8155, B8239, B8244, B833, B8443, B8450, B8460, B8462, B8465, B8466, B8467, manufactured by Evonik Industries. B8474, B8476, B8841, B8844, B8485, B8486, B8490, B8494, B8498, B8516, B8523, B8534, B8544, B8545, B8546, B8547, B8558, B8870, B8781, DC-5598; Toray Dow Corning SF- 2937F, SF-2938F, SZ-1718, SZ-1710, SF-2936F, SF-2945F, SZ-1720, SZ-1328, SZ-1642, SZ-1671, SZ-1677, SH-193; DC manufactured by DOW. -193 is mentioned.
The content of the defoaming agent can be appropriately selected, but the content ratio is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyol because better bubbles are likely to be formed.

(catalyst)
As the catalyst, a urethanization catalyst that promotes the urethanization reaction, a ternation reaction accelerating catalyst that promotes the trimerization reaction of isocyanate groups, or both the urethanization catalyst and the ternation reaction promoting catalyst are used.

Examples of the catalyst include amines.
Examples of the amine include a tertiary amine, a secondary amine, and a primary amine. Further, the amine may be imidazole, alkanolamine, morpholine, ether-containing compound, higher-grade methylpolyamine, or alkoxylylated polyamine.

Examples of the amine include 1- (2'-hydroxyethyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1-( 2'-Hydroxypropyl) imidazole, 1- (2-hydroxypropyl) -2-methylimidazole, 1- (dimethylamino) -2-propanol, 1- (bis (3-dimethylamino) -propyl) amino-2- Propanol, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1-diethyl-n-propylamine, 1,2-dimethylimidazole, 1,3,5-tris (N, N-dimethylaminopropyl) Hexahydro-S-triazine, 1,3-propanediamine, 1,3-benzenediamine-2-methyl-4,6-bis (methylthio), 1,3-benzenediamine-4-methyl-2,6-bis (methylthio) Methylthio), 1,4-diazazicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undecene-7, 1,8-diazabicyclo [5.4.0] undecene- 7-Triethylenediamine, 1-isobutyl-2-methyl-1H-imidazole, 1-dimethylaminopropylimidazole, 1-methyl-4- (2-dimethylaminoethyl) piperazine, 1-methylimidazole, 2-((2-) Dimethylaminoethoxy) -ethylmethyl-amino) ethanol, 2- (2-dimethylaminoethoxy) ethanol, 2,2-dimorpholinodiethyl ether, 2,4,6-tris (dimethylaminomethyl) phenol, 2,4- Bis (dimethylaminomethyl) phenol, 2-[[2- (dimethylamino) ethyl] methylamino] ethanol, 2-[[2- [2- (dimethylamino) ethoxy] ethyl] methylamino] ethanol, 2-[ 2- (2-Dimethylaminoethoxy) ethoxy] ethanol, 2- [2- (dimethylamino) ethoxy] ethanol, 2- [N- (dimethylaminoethoxyethyl) -N-methylamino] ethanol, 3,5-dimethylthio -2,4-Propylluenediamine, 3-quinuclidinol (3-hydroxyazabicyclo [2,2,2] octane), 4,4'-(oxydiethylene) dimorpholin, 4,4'-(oxydimethylene) dimorpholin, 5-Dimethylamino-3-methyl-1-pentanol, N- (2-hydroxyethyl) -N'-methy Lupiperazine, N- (2-hydroxyethyl) imidazole, N- (2-hydroxypropyl) imidazole, N- (3-aminopropyl) imidazole), N- (3-dimethylaminopropyl) -N, N-diisopropanolamine , N, N, N', N', N "-pentamethyldiethylenetriamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N, N, N', N'-tetramethyl Ethylenediamine, N, N, N', N'-tetramethylguanidine, N, N, N', N'-tetramethylpropylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N , N', N ", N"', N "'-hexamethyltriethylenetetramine, N, N, N', N", N "-pentamethyldipropylenetriamine, N, N, N', N", N "-pentaethyldiethylenetriamine, N, N, N', N", N "-pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N", N "-pentamethyldiethylenetriamine, N, N , N'N'-tetramethylhexanediamine, N, N, N'-triethyl-N'-hydroxyethylethylenediamine, N, N, N'-trimethyl-N'-(2-hydroxyethyl) bis (2-amino Ethyl) ether, N, N, N'-trimethyl-N'-(3-aminopropyl) bis (2-aminoethyl) ether, N, N, N'-trimethyl-N'-3-aminopropyl-bis (2-aminopropyl) Aminoethyl) ether, N, N, N'-trimethyl-N'-hydroxyisopropylbis (2-aminoethyl) ether, N, N, N'-trimethyl-N'-hydroxyisopropylbisaminoethyl ether, N, N , N'-trimethyl-N'-hydroxyethylbis (aminoethyl) ether, N, N, N'-trimethylaminoethyl-ethanolamine, N, N, N'-trimethylaminopropylethanolamine, N, N, N -Tri-n-propylamine, N, N', N "-tris (3-dimethylamino-propyl) hexahydrotriazine, N, N'-diethylpiperazine, N, N'-dimethylpiperazine, N, N'- Bis (aminoethyl) piperazine, N, N'-bis [3- (diethylamino) ethyl] urea, N, N'-bis [3- (diethylamino) butyl] urea, N, N'-bis [3- (diethylamino) ) Propyl] urea, N, N'-bis [3- (di) Ethylamino) hexyl] urea, N, N'-bis [3- (diethylamino) pentyl] urea, N, N'-bis [3- (dimethylamino) ethyl] urea, N, N'-bis [3-( Dimethylamino) butyl] urea, N, N'-bis [3- (dimethylamino) propyl] urea, N, N'-bis [3- (dimethylamino) hexyl] urea, N, N'-bis [3- (Dimethylamino) Pentyl] Urea, N, N ", N" -trimethylaminoethylpiperazin, N, N-ethyldiisopropylamine, N, N-diethyl- (α-phenylethyl) amine, N, N-dicyclohexylmethylamine , N, N-dimethyl-N'-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N'-(2-hydroxyethyl) propanediamine, N, N-dimethyl-N', N'-2- Hydroxy (propyl) -1,3-propylenediamine, N, N-dimethylaminoisopropanol, N, N-dimethylaminoethanol, N, N-dimethylaminoethyl-N'-methyl-N'-ethanol, N, N- Dimethylaminoethyl-N'-methylaminoisopropanol, N, N-dimethylaminoethyl-N'-methylaminoethanol, N, N-dimethylaminoethyl-N'-methylaminoethyl-N "-methylaminoisopropanol, N, N-dimethylaminoethyl-N'-methylaminoethyl-N "-methylaminoethanol, N, N-dimethylaminoethyl-N'-methylaminoethyl-N" -methylaminoethyl-N "'-methylaminoisopropanol, N, N-dimethylaminoethyl-N'-methylaminoethyl-N "-methylaminoethyl-N"'-methylaminoethanol, N, N-dimethylaminoethyl-N'-methylethanolamine, N, N-dimethyl Aminoethoxyisopropanol, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyethoxyisopropanol, N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethylaminopropyl-N'-methylaminoisopropanol, N, N-dimethylaminopropyl-N'-methylaminoethanol, N, N-dimethylaminopropyl-N'-methylethanolamine, N, N-dimethylaminopropylamine, N, N-dimethylaminopropylurea, N, N- Dimethylaminohexanol, N, N-dimethylisopropi Luamine, N, N-dimethylcyclohexylamine (DMCHA), N, N-dimethylparatoluidine, N, N-dimethylpropanolamine, N, N-bis (2-aminoethyl) diethylenetriamine, N, N-bis (3-) Dimethylaminopropyl) -N-isopropanolamine, N. N-dimethylbenzylamine, N'-(3- (dimethylamino) propyl) -N, N-dimethyl-, N ", N" -bis (2-aminoethyl) -N- (2-aminoethyl) piperazine, N-2 (2'(2 "-aminoethyl) aminoethyl) aminoethyl piperazine, N-2 (2'-aminoethyl) aminoethyl-N'-aminoethyl piperazine, N-2 (2'-aminoethyl) Aminoethyl piperazine, N-isopropyl-N-sec-butyltrifluoroethylamine, N-ethylmorpholin, N-dimethylaminoethyl-N'-methylpiperazine, N-hydroxyethyl-2-ethyl-4-methylimidazole, N- Hydroxyethyl-2-methylimidazole, N-hydroxyethyl-4-methylimidazole, N-hydroxypropyl-2-ethyl-4-methylimidazole, N-hydroxypropyl-2-methylimidazole, N-hydroxypropyl-4-methyl Imidazole, N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine, N-methyl-N'-(2-dimethylaminoethyl) piperazine, N-methyl-N-isopropylbenzylamine, N-methyl- N-Cyclopentylbenzylamine, N-methylimidazole, N-methyldicyclohexylamine, N-methylmorpholin, t-butylisopropylamine, isopropyl-sec-butyl-trifluoroethylamine, isopropylaminoethanol, imidazole, ethylaminoethanol, ethyldiisopropyl Amine, glycerol poly (oxypropylene) triamine, di- (α-trifluoromethylethyl) amine, di- (α-phenylethyl) amine, di-sec-butylamine, dit-butylamine, diazabicycloundecene ( DBU), diazabicyclooctane (triethylenediamine), diisopropylethylamine, diethanolamine, diethylaminoethanol, diethylaminopropylamine, diethylcyclohexylamine, diethyltoluenediamine, diethylhydroxylamine, cyclohexyl-t-butylamine, dicyclohexylamine, dicyclohexylmethylamine, Dicyclopentylamine, dibutylaminoethanol, dibutylaminoethylamine, dipropylaminopropylamine, dimethylaminoethylamine, dimethylaminoethoxyethanol, dimethylaminooct Tylamine, dimethylaminocyclohexylamine, dimethylcyclohexylamine, dimethylaminotrioxyethylene, dimethylisopropylamine, dimethyloctylamine, dimethyloleylamine, dimethyldodecylamine, dimethylpiperazin, dimethylhexadecylamine, dimorpholinodiethyl ether (DMDEE), dimorpholino Dimethyl ether, tetraethylenepentamine, de-secondary butylamine, tri-n-propylamine, triethylamine, triethylenetetramine, tris (2-aminoethyl) amine, tris (dimethylaminopropyl) amine, tris-2,4,6 -(Dimethylaminomethyl) phenyl, triphenylmethylamine, tributylamine, bis (2-dimethylaminoethyl) ether, bis (N, N-dimethyl-3-aminopropyl) amine, bis (N, N-dimethylaminoethyl) ) Ether (BDMAFE), bis (diethylaminoethyl) ether, bis (dimethylamino) -2-propanol, bis (dimethylaminopropyl) -N-methylamine, bis (dimethylaminopropyl) amine, bis (dimethylaminopropyl) ether , Bis (dimethylaminomethyl) phenol, bis [2- (diethylamino) ethyl] ether, bis [2- (diethylamino) propyl] ether, bis [2- (dimethylamino) ethyl] ether, bisdimethylaminoethyl ether, hydroxy Methyltriethylenediamine, butylaminoethanol, butyldiethanolamine, hexamethyltriethylenetetraamine, heptamethyltetraethylenepentamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, polyoxypropylenediamine, N- (2-hydroxy-5-nonylphenol) ) Sodium methyl-N-methylglycinate, methyl (n-methylamino b-sodium acetate nonylphenol) 2-, methylisopropylbenzylamine, methylcyclopentylbenzylamine, methylhydroxyethylpiperazine, tertiary butylaminoethanol and the like.

Further, the amine may be an alkylated (methylated or the like) amine, and examples of such an amine include triethylenetetramine, tris (2-aminoethyl) amine, and N, N'-bis (aminoethyl) piperazine. , N-2 (2'-aminoethyl) aminoethyl piperazine, tetraethylenepentamine, N-2 (2'(2 "-aminoethyl) aminoethyl) aminoethyl piperazine, N-2 (2'-aminoethyl) Alkylation of aminoethyl-N'-aminoethyl piperazine, N ", N" -bis (2-aminoethyl) -N- (2-aminoethyl) piperazine, N, N-bis (2-aminoethyl) diethylenetriamine. It may be a compound (methylated product or the like). Such an alkylated (methylated or the like) amine and an amine having at least one hydroxyalkyl group in the molecule (tertiary amine or the like) may be used in combination. Examples of the amine having at least one hydroxyalkyl group in the molecule (such as a tertiary amine) include alkanolamines (for example, alkanolamines among the amines exemplified in the upper row).
The amine may be used in the form of an imidazole-boron composition or in the form of an aminopropyl-bis (aminoethyl) ether composition.

Further, as the catalyst, a Lewis acid complex salt of an amine as described above may be used.
Amines (particularly tertiary amines) may be used in combination with the metal catalysts described below. For example, it may be used in combination with a tertiary amine and an organotin compound, a tin (II) carboxylate salt, a bismuth (III) carboxylate salt or a combination thereof.

Amines are organic carboxylic (mono, di, tri, or poly) acids (eg, malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glutaconic acid, Primary-OH groups, secondary-OH groups, primary amines, in the presence of traumatic acid, muconic acid, phthalic acid, isophthalic acid, terephthalic acid, polyacrylic acid, etc.) or combinations thereof. It may be a tertiary amine containing an isocyanate-reactive group such as a secondary amine, amide, urea, urethane or imine.

The catalyst may be a metal catalyst which is a catalyst containing a metal.
The metal catalyst may be, for example, a transition metal catalyst containing a transition metal or an alkali (earth) metal catalyst containing an alkali (earth) metal.
Examples of the metal catalyst include organic metals and metal salts.
The metal catalyst is also preferably an organic acid metal salt excluding tin salt, lead salt and mercury salt.

Examples of the metal in the metal catalyst include bismuth, lead, tin, antimony, cadmium, cobalt, iron, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, titanium, vanadium, copper, manganese, zirconium, magnesium and calcium. , Sodium, potassium, lithium, and combinations thereof.

As the metal catalyst, for example, a carboxylate of a metal (for example, a metal exemplified as a metal in a metal catalyst) can also be used.
The metal carboxylate may be, for example, an alkali metal (lithium, sodium, potassium, etc.) carboxylate, an alkaline earth metal (calcium, magnesium, etc.) carboxylate, or a transition metal (iron, lead, etc.). It may be a carboxylate of zinc, bismuth, etc.).
The alkali metal carboxylate may be, for example, an alkali metal salt of a carboxylic acid having 2 to 12 carbon atoms.
Examples of the carboxylic acid in the carboxylic acid salt of a metal include an aliphatic carboxylic acid (aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid, etc.) and an aromatic carboxylic acid (aromatic monocarboxylic acid, aromatic dicarboxylic acid, etc.). Be done.
Examples of the carboxylic acid include acetic acid, propionic acid, pentanoic acid, neopentanoic acid, hexanoic acid, 2-ethylhexylcarboxylic acid, neohexanoic acid, octanoic acid, neooctanoic acid, heptanic acid, neoheptanic acid, nonanoic acid and neononanoic acid. Examples thereof include decanoic acid, neodecanoic acid, undecanoic acid, neoundecanoic acid, dodecanoic acid, neododecanoic acid, benzoic acid and phthalic acid.
The carboxylic acid salt of the metal may be, for example, a tin salt of a carboxylic acid (such as a tin (II) carboxylate salt) or a dialkyltin salt of a carboxylic acid. Further, a bismuth salt of carboxylic acid (bismuth (III) carboxylate salt, bismuth carboxylic acid metal salt of 2-ethylhexanoate, etc.) may be used.

The metal catalyst may be, for example, an alkali metal salt of asertiacetone or salicylaldehyde, or an organotin compound.

Examples of the metal catalyst include potassium 2-ethylhexanoate, tin (II) 2-ethylhexanate, bismuth 2-ethylhexanate, zinc 2-ethylhexanate, lead 2-ethylhexanate, potassium octane, and octane. Lead Acid, Stannous Octanoate, Potassium Octylate, Potassium Acetate, Potassium Octanoate, Antimon Glycoate, Dioctyltin Dilaurate, Dibutyltin Oxide, Dibutyltin Diacetate, Dibutyltin Diisooctyl Maleate, Dibutyltin Dichloride, Dibutyltin Dilauryl Merca Petit, dibutyltin dilaurate (DGTDL), dibutyltin dilaurate, dibutyltinbi (2-ethylhexyl mercaptoacetate), dibutyltin mercaptide, dimethyldiacetate, dimethyltindiisooctylmaleate, dimethyltindilauryl mercaptide, dimethyltindilaurate, dimethyltinbi ( 2-Ethylhexyl mercaptoacetate), titanyl oxalate, potassium titanyl oxalate, tindiacetate, tindioctate, tindioleate, tindilaurate, cobalt naphthenate, nickel naphthenate, lead naphthenate, bismuth 2-ethylhexanoate, bismuth Examples thereof include carboxylate, phenylmercury propionate, lead benzoate, ferric chloride, antimony trichloride, bismuth nitrate, potassium acetate, magnesium acetate and ferric acetylacetonate.

Also, alkaline earth carboxylate, alkaline carboxylate, as well as bismuth, zinc, cobalt, tin, cerium, lanthanum, aluminum, vanadium, manganese, copper, nickel, iron, titanium, zirconium, chromium, scandium, Metal salts such as calcium, magnesium, strontium, and barium carboxylates have good hydrofluoric acid (HF) trapping agent activity. In addition, these catalysts can stabilize catalyst performance when used in combination with amine (particularly imidazole) catalysts.
For example, a metal salt having one or more functional carboxyl groups may be used as an HF scavenger. Examples of such metal salts include magnesium formate, magnesium benzoate, magnesium octanate, calcium formate, calcium octanate, zinc octanate, cobalt octanate, stannous octanate, dibutyltin dilaurate (DBTDL). ..

The catalyst may be a quaternary ammonium salt.
Examples of the quaternary ammonium salt include tetraalkylammonium halides, tetraalkylammonium hydroxides, tetraalkylammonium organic acid salts, tetraalkylammonium organic acid salts, N, N, N', and N'-tetramethylethylenediamine. Examples thereof include quaternary ammonium compounds obtained by anion exchange reaction of a quaternary ammonium carbonate obtained by reacting a tertiary amine such as the above with a carbonic acid diester with 2-ethylhexanoic acid.
Examples of the quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium 2-ethylhexanate, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium 2-ethylhexanoate, and tetramethyl. Examples thereof include ammonium chloride, tetramethylammonium hydroxide salt, tetramethylammonium 2-ethylhexanate and tetramethylammonium 2-ethylhexanoate.

In addition, as the catalyst, for example, tertiary phosphines, onium salt compounds of phosphorus, and the like may be used.

Commercially available products may be used as the catalyst, and examples of the commercially available products include PolycatDBU (DBU), Dabco33LV (diazabicyclooctane), Jeffamine D230 (polyoxypropylene diamine), and Dabco TMR-30 (Tris-2,4). , 6- (Dimethylaminomethyl) phenyl / bis (dimethylaminomethyl) phenyl), Jeffcat ZR70 (dimethylaminoethoxyethanol / ethylene glycol), Toyocat RX5 (bis (dimethylaminoethyl) ether), Polycat201 (reactive amine), Polycat9 (bis (dimethylaminopropyl) -n), Polycat30 (tertiary amine (10-30%), gelation catalyst (30-60%) fatty amine (10-30%)), Lupragen1-methylimidazole (1) -Methylimidazole), Polycat5 (pentamethyldiethylenetriamine), Polycat41 (dimethylaminopropylhexahydrotriazine, N, N', N''), Dabco DEOA-LF (diethanolamine), Lupragen1-methylimidazole (1-methylimidazole), DABCO H1010 (50/50 blend of water + amine salt), Toyocat DM70 (70% 1,2-dimethylimidazole / 30% ethylene glycol) Toyocat TRX (trimerization catalyst), Polycat TMR-7 (trimerization catalyst) , DIPFA (diisopropylethylamine), Polycat12 (n-methyldicyclohexylamine), Cutane52 (methyl (n-methylaminob-na-lium acetate nonylphenol) 2-), Jeffamine T500 (glycerol poly (oxypropylene) triamine), K- Kat x614 zinc (zinc-catalyzed complex), Jeffcat DMDEE (2,2-dimorpholinodiethyl ether), Polycat12 (N-methyldicyclohexylamine), Fitnesscure N, N-dimethylparatoluidine (N, N-dimethylparatoluidine), Ethacure300 Curative (3,5-dimethylthio-2,4-luenediamine), Tysor TE titanium (titanium complex), Dabco MB20 (bismascarpoxylate catalyst), Borchi O xycoat1101 (iron catalyst), PUCAT25 (bismuth 2-ethylhexanoate), Ethacure100 curing agent (diethyltoluenediamine) Ethacure300 curing agent (1,3-benzenediamine-4-methyl-2,6-bis (methylthio) / 1, 3-Benzendiamine-2-methyl-4,6-bis (methylthio)) can be mentioned.

Among them, as the urethanization catalyst, a tertiary amine (for example, an amine corresponding to the tertiary amine among the amines exemplified in the upper row) is preferable from the viewpoint of reactivity.
From the viewpoint of reactivity, the organic acid metal salt excluding tin salt, lead salt and mercury salt, the quaternary ammonium salt, or both the above metal salt and the quaternary ammonium salt are preferably used as the trimerization reaction promoting catalyst. Be done.
When isocyanurate is used, it is preferable to use a urethanization catalyst and a trimerization reaction promoting catalyst in combination from the viewpoint of reactivity, and a tertiary amine and the above organic acid metal salt are used in combination, or a tertiary amine and the organic acid metal salt are used in combination. Is more preferable in combination with the above-mentioned quaternary ammonium salt.

Among them, preferred tertiary amines include, for example, N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N', N ", N "-pentamethyldiethylenetriamine, N, N, N', N", N "-pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N", N "-pentamethyldipropylenetriamine, N , N, N', N'-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7 -Triethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholin, N-ethylmorpholin, bis (2-dimethylaminoethyl) Examples include ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine. ..

As the organic acid metal salt excluding tin salt, lead salt and mercury salt, for example, a carboxylic acid metal salt of potassium acetate, potassium 2-ethylhexanoate or bismuth 2-ethylhexanoate is preferable from the viewpoint of reactivity.

Preferred quaternary ammonium salts include, for example, tetraalkylammonium halides such as tetramethylammonium chloride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide salt; tetramethylammonium 2-ethylhexanate, 2-. Tetraalkylammonium organic acid salts such as hydroxypropyltrimethylammonium hydrochloride, 2-hydroxypropyltrimethylammonium 2-ethylhexanate; tertiary amines such as N, N, N', N'-tetramethylethylenediamine and carbonate diesters. Examples thereof include a quaternary ammonium compound obtained by subjecting a quaternary ammonium carbonate obtained by reacting with 2-ethylhexanoic acid to an anion exchange reaction.

The catalyst may be used in combination with other components to adjust the performance of the catalyst. The other components referred to here may have properties as a catalyst.
For example, the tertiary amine is preferably used in combination with an acid as described in paragraphs [0066] to [0073] of JP-A-2017-155101, and preferred embodiments may be used in the same manner. can.

A tertiary amine and a fatty acid compound having 7 or more carbon atoms may be used in combination. Examples of the fatty acid compound having 7 or more carbon atoms include enanthic acid, capric acid, pelargonic acid, capric acid, undecic acid, lauric acid, tridecic acid, myristic acid, pentadecic acid, palmitic acid, margaric acid, stearic acid and nonadesilic acid. Saturated fatty acids such as arachidic acid, henicosyl acid, behenic acid, trichosyl acid, lignoseric acid, etc .; , Μ-6 fatty acids such as γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, docosapentaenoic acid, ω-7 fatty acids such as palmitellic acid, bacsenic acid, paulic acid, oleic acid, ellagic acid, erucic acid. , Nervoic acid, etc. ω-9 fatty acids.

In addition, the organic acid as an acid component suppresses the activity of the catalyst and prevents the catalyst from being deactivated due to the interaction between the HFO and the catalyst, thereby improving the storage stability of the polyol composition for rigid polyurethane foam. Has.
Examples of such an organic acid include an aliphatic organic acid and an organic acid having an aromatic ring.
The aliphatic organic acid is not particularly limited, and may be saturated or unsaturated, and may be linear or branched. As the aliphatic organic acid, an aliphatic organic acid having a hydrocarbon group having 1 to 10 carbon atoms can be used, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, and valeric acid.
As the organic acid having an aromatic ring, an organic acid having a monocyclic (non-polycyclic) aromatic ring, an organic acid having a polycyclic aromatic ring, or the like can be used. Examples of the organic acid having a monocyclic (non-polycyclic) aromatic ring include benzoic acid, phthalic acid (orthophthalic acid, isophthalic acid, terephthalic acid), and salicylic acid. Examples of the organic acid having a polycyclic aromatic ring include naphthoic acid and anthronic acid.

The catalyst is an organic carboxylic (mono, di, tri, or poly) acid (eg, malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, glutaconic acid). , Traumatic acid, muconic acid, phthalic acid, isophthalic acid, terephthalic acid, polyacrylic acid, etc.) or a combination thereof, a tetraalkylguanidine salt, etc. may be used in combination.
In addition, the catalyst may be used in combination with the tertiary amine salt of the organic carboxylic acid or a combination thereof, and the organic carboxylic acid or a combination thereof and a tetraalkylguanidine and a tertiary amine. It may be used in combination with a combination of salts, or in combination with the above organic carboxylic acid or a tertiary amine catalytic component and a tetraalkylguanidine salt of a combination thereof.

From the viewpoint of reactivity, the total amount of the catalyst is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyol. By adjusting the content of the catalyst within the above range, the time from the start of mixing of the components used for foaming to the start of the reaction (cream time) and the time from the start of mixing to the start of curing of the resin (gel time). Alternatively, the time (tack free time) from the start of the above mixing to the progress of foaming and the completion of curing of the resin can be satisfactorily adjusted.

[Polyisocyanate]
Examples of the polyisocyanate include aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups; and modified polyisocyanates obtained by modifying these. Specific examples thereof include polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate (polymeric MDI), xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and variants thereof. Examples of the above-mentioned modified product include a prepolymer-type modified product, an isocyanate-modified product, a urea-modified product, and a carbodiimide-modified product. Of these, from the viewpoint of reactivity and the strength of the foamed synthetic resin obtained, Polymeric MDI or a modified product thereof is preferable, and a modified product of Polymeric MDI is more preferable. The polyisocyanate may be used alone or in combination of two or more.

From the viewpoint of reactivity, the amount of polyisocyanate used is a value obtained by multiplying the total number of active hydrogens of polyols and other compounds having active hydrogen by 100 times the number of isocyanate groups (hereinafter, this value is referred to as "isocyanate index"). Of the above, 50 to 300 is preferable. In particular, when a urethanization catalyst is mainly used as the catalyst, the amount of polyisocyanate used is preferably 50 to 170, more preferably 70 to 150 in the isocyanate index from the viewpoint of reactivity. When a catalyst that promotes the trimerization reaction of isocyanate groups is mainly used as the catalyst, the amount of polyisocyanate used is preferably 100 to 400 in the isocyanate index from the viewpoint of more effectively advancing the nurateization reaction, 105. -350 is more preferable, and 110-300 is even more preferable.

(Optional ingredient)
In this embodiment, components other than the above-mentioned components may be further used, if necessary.
As the above other components, known compounding agents can be used. Examples of the compounding agent include fillers, antiaging agents, flame retardants, plasticizers, colorants, antifungal agents, defoaming agents, dispersants, and discoloration inhibitors. Examples of the filler include calcium carbonate and barium sulfate. Examples of the antioxidant include an antioxidant and an ultraviolet absorber.
The content of the above other components can be appropriately selected depending on the intended purpose, but is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polyol because the effect of the present invention can be easily maintained.

[Reaction method]
As a method for reacting the polyol and the polyisocyanate in the presence of the foaming agent A, the foam stabilizer, and the catalyst, a known method can be used.
For example, a method of injecting an effervescent composition containing a polyol, a polyisocyanate, a foaming agent A, a foaming agent, and a catalyst into a frame such as a mold to foam (so-called injection method); between two face materials. A method for producing a laminate in which a rigid polyurethane foam is sandwiched between these facing materials by supplying the effervescent composition to the foam (so-called continuous board molding method); spraying the effervescent composition. There is a method of spraying (so-called spray method).

The injection method can be performed by, for example, a method using a high-pressure foaming device or a low-pressure foaming device. When a high-pressure foaming device or a low-pressure foaming device is used, the foamable composition is injected into a mold having a desired shape or a press molding machine in which a mold is set, and then foamed and cured to produce a rigid polyurethane foam. The foaming agent A may be blended in the system liquid in advance or may be blended when foaming with the foaming device. Examples of articles that can be manufactured by using the injection method include freezing equipment such as electric refrigerators and panels for freezing / refrigerating vehicles.
The continuous board forming method is used, for example, in the production of heat insulating materials for vending machines and construction applications.

The spray method is roughly divided into an air spray method and an airless spray method. Of these, the airless spray method in which the system liquid and the liquid containing polyisocyanate are mixed by a mixing head and foamed is particularly preferable in terms of workability. The spraying method also includes a manufacturing method in which a system liquid and a liquid containing polyisocyanate are stirred, foamed, and injected into a mold frame. Further, a liquid containing a system liquid and a polyisocyanate is supplied by spraying on the inside of one surface of two pairs of face materials, and the other face material is laminated in the process of foaming. Also included is a method of continuously producing a laminate in which a rigid polyurethane foam is sandwiched between face materials.

When construction is performed on a vertical surface such as a wall surface by the spray method, dripping is likely to occur if the reactivity between the system liquid and the polyisocyanate is poor. When dripping occurs, the heat insulating layer cannot be kept uniform, and the thickness of the heat insulating layer is concentrated on the lower part of the wall surface. Occurs. Further, if the reactivity is poor, the thickening in the foaming process is delayed, so that the cell growth is likely to be promoted, and the heat insulating property of the obtained foamed synthetic resin is likely to be deteriorated. Articles that can be manufactured using the spray method include, for example, heat insulating materials for buildings such as dew condensation prevention in condominiums and detached houses; heat insulating materials for vehicles and aircraft; soundproofing materials for buildings, vehicles, and aircraft. Can be mentioned.

<Kit for rigid polyurethane foam>
The kit for rigid polyurethane foam according to the present embodiment comprises a first agent composed of the polyol system liquid of the present embodiment and a polyisocyanate system liquid (second agent) containing polyisocyanate. The above optional component may be contained in the first agent, the second agent, or both.
The polyol system liquid (first agent) can be prepared by mixing the above-mentioned polyol, the above-mentioned foaming agent A, the above-mentioned defoaming agent, the above-mentioned catalyst, and an optional component as required.
The polyisocyanate system liquid (second agent) may contain an additive such as a stabilizer or a foaming agent A. The main component of the second agent is preferably polyisocyanate, and specifically, the content ratio of polyisocyanate to the total amount of the second agent is preferably 80% by mass or more. The second agent may consist of polyisocyanate.

<Rigid polyurethane foam>
According to the manufacturing method of the present embodiment, a rigid polyurethane foam having a density of 5 to 300 kg / m ³ can be manufactured. The rigid polyurethane foam obtained by the above method has a low thermal conductivity and tends to have good heat insulating properties, as shown in Examples described later.
The thermal conductivity of the rigid polyurethane foam is, for example, preferably 0.021 W / m · K or less, more preferably 0.020 W / m · K or less, still more preferably 0.0195 W / m · K or less at a measurement temperature of 23 ° C. .. The thermal conductivity in the present specification is a value obtained by a measuring method according to JIS A 9511.
The density of the rigid polyurethane foam can be controlled by the amount of the foaming agent A used. Further, the thermal conductivity can be controlled by adjusting the composition of the polyol and the composition of the foaming agent A.

<Article>
The article according to the present invention includes the above-mentioned rigid polyurethane foam. The article is not particularly limited as long as it includes the rigid polyurethane foam, and in addition to the articles mentioned in the description of the method for manufacturing the rigid polyurethane foam, such as a heat insulating material and a soundproofing material, such a heat insulating material and a soundproofing material are used. It also includes electrical appliances, vehicles, aircraft, buildings, etc. equipped with materials.

Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.
The raw materials and measuring methods used in each of the following examples are as follows.

(material)
Polycarbonate 1:
1 mol of sucrose is stirred and mixed with 4.8 mol of water, 0.5 mol of glycerin is added and PO is added to the mixed initiator, 3.3 mol of water is dehydrated, and then PO is further ring-opened and added. And polymerized. Potassium hydroxide was used as a polymerization catalyst for the alkylene oxide to obtain a polyether polyol having an EO content of 0%, an average number of hydroxyl groups of 4.2, and a hydroxyl value of 450 mg / KOH.

Polycarbonate 2:
Metatoluenediamine (a mixture of 80% 2,4-diaminotoluene and 20% 2,6-diaminotoluene) initiator is stirred and mixed at 125 ° C. for 0.5 hours, EO is added, then PO is added, and further. EO was ring-opened and added for polymerization. Potassium hydroxide was used as a polymerization catalyst for the alkylene oxide to obtain a polyether polyol having an EO content of 23%, an average number of hydroxyl groups of 4.0, and a hydroxyl value of 450 mg / KOH.

Polycarbonate 3:
Polyester polyol obtained by reacting phthalic anhydride with diethylene glycol: Maximol RDK-133 (acid value: 0.56 mgKOH / g, hydroxyl value: 315 mgKOH / g, water content: 0.04%, viscosity: 2400 mP · s) manufactured by Kawasaki Kasei Chemicals Co., Ltd. ).

The details of the components used as the foaming agent are as follows.
1224yd: 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), purity 99.75%, molar ratio of Z-form to E-form (Z / E ratio) = 99.43 / 0 .57, (AGC product name: AMOLEA 1224yd).
tDCE: Trans-1,2-dichloroethylene (manufactured by UNISTAR CHEMICAL Inc .: Trans-1,2-Dichloroethylene).

Catalyst 1: N, N, N', N'', N''-pentamethyldiethylenetriamine (amine catalyst, manufactured by Tosoh Corporation, product name TOYOCAT DT).
Catalyst 2: N, N-dimethylcyclohexylamine (amine catalyst, manufactured by Evonik Industries, Inc., product name POLYCAT 8).
Defoaming agent: Polyoxyalkylene-dimethylpolysiloxane copolymer (manufactured by Toray Dow Corning, product name VORAURF RF1777 Additive).
Flame retardant: Tris (β-chloropropyl) phosphate (Daihachi Kagaku Co., Ltd. product name: TMCPP).
Polyisocyanate: Polymeric MDI (Sumitomo Cobestro Urethane Product Name: Sumijour 44V20).

(Measuring method)
<Hydroxy group value of polyol>
The hydroxyl value of the polyol was measured according to JIS K1557-1 (2007 version).

<Mw of polyol>
The polystyrene-equivalent molecular weight was measured using gel permeation chromatography (manufactured by Tosoh Corporation, model: HLC-8320GPC). As columns, two TSK-GEL SuperHZ 2000 manufactured by Tosoh Corporation and two TSK-GEL SuperHZ 1000 were connected in series and used. As the eluent, a THF solution of triethylamine (0.1 mol / L) was used under the condition of a flow rate of 0.35 ml / min. The concentration of the measurement sample was adjusted to 0.05 g / 10 ml, the injection volume was 20 μL, and the column temperature was 40 ° C.

<Measurement of vapor pressure of foaming agent (measurement of boiling point)>
The vapor pressure of the foaming agent (single compound or mixture) was measured by the method shown below, and the temperature at which the vapor pressure became atmospheric pressure was confirmed. In this measurement, 101.3 kPa was used as the value of atmospheric pressure.

80 g of a foaming agent was sealed in a 95 cc SUS sampling cylinder, a pressure gauge was attached to the upper part, and the mixture was allowed to stand in a low temperature constant temperature bath. The temperature of the constant temperature bath was set to 0 ° C., and the pressure indicated value was confirmed after leaving for 3 hours. The same measurement was performed from 10 ° C. to 50 ° C. in 10 ° C. increments, and the steam pressure at each temperature was measured. From the obtained results, the temperature at which the steam pressure became 101.3 kPa was estimated. The temperature at which the vapor pressure was estimated to be 101.3 kPa was defined as the boiling point of the foaming agent.

[Measurement example]
The boiling point of the foaming agent consisting of the first component, the second component or a mixture thereof shown in Table 1 was measured by the above method. The results are shown in Table 1.
The boiling point of the foaming agent composed of 1224yd and tDCE was in the range of 17 to 34 ° C. when the mass ratio of 1224yd / tDCE was 90/10 to 20/80, which was an appropriate boiling point for the foaming agent.

<Evaluation method of rigid polyurethane foam>
[Reactivity]
When the system liquid prepared by the method described later and the polyisocyanate were mixed to prepare a mixed liquid, the mixing start time was set to 0 seconds, and the cream time, gel time and tack-free time were measured.
Cream time (ct) (seconds): The time from the mixing start time to the start of foaming of the mixed solution of the system solution and the polyisocyanate.
Gel time (gt) (seconds): From the mixing start time, as the gelation progresses, a portion of a thin glass or metal rod up to about 2 cm from the tip is inserted from the upper part of the foaming mixture. The time it takes for the mixture to start pulling the thread when it is pulled out quickly.
Tuck free time (tft) (seconds): From the mixing start time, foaming progresses, and when the metal rod is brought into contact with the upper surface of the foam, the foam resin is attached to the metal rod. Time until the upper surface of the foam is not sticky without wearing.

[density]
A sample piece was cut out from the core portion of the free foam foam obtained by the method described later into a size of 150 mm each in the horizontal, vertical and height directions. The density of the sample piece (unit: kg / m ³ ) was measured by a method according to JIS A 9511.

[Thermal conductivity]
A sample piece was obtained by cutting out the core portion of the panel foam foam obtained by the method described later into a width of 25 mm, a length of 200 mm, and a height of 200 mm.
Using a thermal conductivity measuring device (Hideko Seiki Co., Ltd. product name: Autolambda HC-074 type), the thermal conductivity (unit: W / m · K) of the above test piece is averaged according to JIS A 9511. It was measured at a temperature of 23 ° C.

(Examples 1 to 3)
Examples 1 and 2 are examples, and example 3 is a comparative example.
Each raw material was mixed at the blending ratio (part by mass) shown in Table 2 to prepare a polyol system liquid. The compounding ratio of polyisocyanate is shown in Table 2 by mass and isocyanate index.
The liquid temperatures of the polyol system liquid and the polyisocyanate were adjusted to 15 ° C., respectively, and a free-foaming foam was produced by the procedure shown below.
The foaming agents used in Examples 1 to 3 are as follows.
Example 1: A mixture of 1224 yd / tDCE = 70/30 (mass ratio).
Example 2: A mixture of 1224 yd / tDCE = 30/70 (mass ratio).
Example 3: tDCE.

[Manufacturing of free foam foam]
Polyisocyanate is added to a container containing the above polyol system solution prepared in a mass of 1.3 times (g) as shown in Table 2 in a mass (g) of 1.3 times the amount shown in Table 2, and stirred in a disk shape. A mixture was prepared by stirring for 5 seconds at a rotation speed of 3,000 rpm using a stirring device equipped with blades. The mixed solution immediately after preparation was quickly put into a wooden box having a length, width, and height of 200 mm, each equipped with a polyethylene mold release bag, and foamed to obtain a free foam.

[Manufacturing of panel foam foam]
The upper part of 50 mm in width, 400 mm in length, and 400 mm in height was opened, a polyethylene mold release bag was attached, and the mixture prepared in the same manner as above was placed in an aluminum mold container adjusted to 40 ° C. 1.5 times as much as in Table 2. The mixture was blended by mass (g), quickly added and foamed, and demolded 5 minutes after the start of stirring. The foam protruding from the upper opening of the mold was cut, and the mass of the just pack to be filled in the mold was measured. In the same way, quickly add the mixture in an amount that is 20% by mass overfilling the just pack mass to be filled in the measured mold volume, and when it foams, close the upper open part with an aluminum lid, and 5 minutes after the start of stirring. Demolding gave a 120% overpacked panel foam.

[evaluation]
The physical characteristics (density, thermal conductivity) of the obtained panel foam foam were measured by the above evaluation method. In addition, during the production of the above foam, the reactivity (cream time, gel time and tack free time) was measured by the above method. In addition, the presence or absence of deformation in the foam after molding was observed. These results are shown in Table 3.

As shown in the results of Tables 1 to 3, in Examples 1 and 2, the boiling point of the foaming agent was within an appropriate range as a foaming agent, and the thermal conductivity of the panel foam was also within an appropriate range. .. In Example 3, the dissolving power of tDCE in the foam was strong, the foam shrank after foam molding, and the density and heat insulating performance could not be evaluated. It is necessary that 1224yd / tDCE is within the range of appropriate composition.

As described above, since the foaming agent according to the present invention has a boiling point within an appropriate range as a foaming agent, it can be inferred that the foaming agent exerts the following advantageous effects. First, the system liquid containing the foaming agent is less likely to cause bumping phenomenon during transportation or construction, and can improve workability during foaming. Secondly, since the foaming agent is less likely to volatilize and the composition of the system liquid is less likely to change from the system liquid containing the foaming agent according to the present invention, the storage stability of the system liquid and the storage stability of the system liquid after storage are difficult. Good reactivity can be maintained. As a result, the desired heat insulating performance can be easily obtained. Thirdly, since the boiling point is about the same as room temperature at the highest, the foaming agent according to the present invention has better foamability even at room temperature as compared with the foaming agent having a boiling point higher than room temperature.

Claims (18)

A foaming agent comprising 1-chloro-2,3,3,3-tetrafluoropropene and trans-1,2-dichloroethylene. Claimed that the total content of the 1-chloro-2,3,3,3-tetrafluoropropene and the trans-1,2-dichloroethylene is 50 to 100% by mass with respect to the total mass of the foaming agent. Item 1. The foaming agent according to Item 1. 1-Chloro-2,3,3,3 representing the mass ratio of the content of 1-chloro-2,3,3,3-tetrafluoropropene to the content of trans-1,2-dichloroethylene. The foaming agent according to claim 1 or 2, wherein the tetrafluoropropene / trans-1,2-dichloroethylene is 90/10 to 20/80. A method for producing a foamed plastic, which comprises producing the foamed plastic using the foaming agent according to any one of claims 1 to 3. The method for producing foamed plastic according to claim 4, wherein the foamed plastic is a thermoplastic resin foam. The method for producing a foamed plastic according to claim 4, wherein the foamed plastic is a thermosetting resin foam. The foaming according to claim 6, wherein the polyol and the polyisocyanate are reacted in the presence of the foaming agent, the foam-regulating agent, and the catalyst according to any one of claims 1 to 3 to produce a polyurethane foam. How to make plastic. The method for producing a foamed plastic according to claim 7, wherein the polyurethane foam is a rigid polyurethane foam. A polyurethane foam obtained by reacting a polyol with a polyisocyanate in the presence of a foaming agent, a defoaming agent, and a catalyst according to any one of claims 1 to 3. A polyurethane foam comprising a polyol, a polyisocyanate, and a cured foam of an effervescent composition containing the effervescent agent according to any one of claims 1 to 3, a foam stabilizer, and a catalyst. The polyurethane foam according to claim 9 or 10, wherein the polyurethane foam is a rigid polyurethane foam. The polyurethane foam according to claim 11, wherein the rigid polyurethane foam has a density of 5 to 300 kg / m ³ . An article comprising the polyurethane foam according to any one of claims 9 to 12. A system liquid containing a polyol, a foaming agent according to any one of claims 1 to 3, a defoaming agent, and a catalyst. The system liquid according to claim 14, wherein the total mass of the foaming agent is 10 to 100 parts by mass with respect to 100 parts by mass of the polyol. The system solution according to claim 14 or 15, wherein the polyol contains a polyether polyol. The system liquid according to claim 16, wherein the content of the polyether polyol is 10 to 100% by mass with respect to the total mass of the polyol. A kit for polyurethane foam comprising a first agent comprising the system liquid according to any one of claims 14 to 17 and a second agent containing polyisocyanate.