JP2020139137A - Foaming agent, and method for producing rigid foamed synthetic resin and system liquid using the same - Google Patents

Abstract

To provide a foaming agent that can improve workability in foaming, and can be used as one component of a system liquid for producing a rigid foamed synthetic resin, to satisfactorily maintain the storage stability of the system liquid and the reactivity of the system liquid after storage, and a method for producing a rigid foamed synthetic resin, a system liquid, a kit for a rigid foamed synthetic resin, and a rigid foamed synthetic resin each of which uses the foaming agent, and an article including the foaming agent.SOLUTION: A foaming agent contains CF3CF=CHCl and CHF2CF=CHCl. A method for producing a rigid foamed synthetic resin includes reacting polyol with polyisocyanate, in the presence of the foaming agent, a foam stabilizer, and a catalyst.SELECTED DRAWING: None

Description

The present invention relates to a foaming agent, a method for producing a rigid foamed synthetic resin using the foaming agent, and a system liquid.

A compound having active hydrogen such as a polyol and a polyisocyanate are reacted in the presence of a foam stabilizer, a catalyst and a foaming agent to synthesize a hard foam such as a rigid polyurethane foam, a rigid urethane-modified polyisocyanurate foam or a rigid polyurea foam. It is widely practiced to produce resins.

As the foaming agent, 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) have been conventionally used. Has been done. However, the use of CFCs and HCFCs has come to be regulated from the viewpoint of environmental protection such as protection of the ozone layer.

Hydrogenated fluorinated carbon compounds (hydrofluorocarbons, so-called HFCs) are used as foaming agents in place of CFCs and HCFCs.
As the HFC, for example, CHF ₂ CH ₂ CF ₃ (HFC-245fa) and CF ₃ CH ₂ CF ₂ CH ₃ (HFC-365 mfc) are used. However, although these HFCs have an ozone depletion potential (ODP) of zero, they have a high global warming potential (GWP), so that a foaming agent having a lower GWP is required.

Hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) have been proposed as candidate substances for foaming agents with low GWP. For example, Patent Document 1 describes that the Z form (HCFO-1224yd (Z)) of 1-chloro-2,3,3,3-tetrafluoropropene (CF ₃ CF = CHCl) can be used as a foaming agent. ing. Further, Patent Document 2 describes that CF ₃ CH = CHCF ₃ (1,1,1,4,4,4-hexafluoro-2-butene, HFO-1336 mzz) can be used as a foaming agent.

Japanese Unexamined Patent Publication No. 2015-105340 Special Table 2010-534253 Gazette

At the construction site of the hard foamed synthetic resin, for example, the system liquid containing a raw material other than the polyisocyanate is reacted with the polyisocyanate to form the hard foamed synthetic resin at a desired place. However, since the boiling point of 1224yd (Z) is 15 ° C., which is lower than the outside air temperature except in winter, when 1224yd (Z) is used alone as the foaming agent, 1224yd (Z) is stored when this system liquid is stored. ) Volatilizes from the system liquid, the composition of the system liquid changes, the desired heat insulating performance cannot be obtained, and there is a problem that a bumping phenomenon occurs when the system liquid is transported or during construction. Since 1336 mzz has a boiling point of 33 ° C., which is higher than room temperature, there is a problem that it is difficult to foam.

The present invention has been made in view of the above problems, can improve workability at the time of foaming, and can stably store the system liquid as a component of a system liquid for producing a rigid foamed synthetic resin. A foaming agent capable of maintaining good properties and reactivity of the system liquid after storage, a method for producing a hard foamed synthetic resin using the foaming agent, a system liquid, a kit for hard foamed synthetic resin, a hard foamed synthetic resin, and the like. The subject is to provide the goods to be provided.

The present inventors have found that the above problems can be solved by using a specific foaming agent. That is, it has been found that the above problems can be solved by using a foaming agent containing CF ₃ CF = CHCl and CHF ₂ CF = CHCl (1-chloro-2,3,3-trifluoropropene, HCFO-1233yd). ..

The present invention is the following [1] to [14].
[1] A foaming agent containing CF ₃ CF = CHCl and CHF ₂ CF = CHCl.
[2] The foaming agent according to [1], wherein the ratio of the total mass of CF ₃ CF = CHCl and CHF ₂ CF = CHCl to the total mass of the foaming agent is 50 to 100% by mass.
[3] The foaming agent according to [1] or [2], wherein the mass ratio of the content of CF ₃ CF = CHCl to the content of CHF ₂ CF = CHCl is 1/99 to 99/1. Foaming agent.
[4] A system liquid containing a polyol, a foaming agent according to any one of [1] to [3], a foam stabilizer, and a catalyst.
[5] The system liquid according to [4], wherein the amount of the foaming agent with respect to 100 parts by mass of the polyol is 10 to 100 parts by mass.
[6] The system solution according to [4] or [5], which contains a polyether polyol as the polyol.
[7] The system solution according to [6], wherein the content ratio of the polyether polyol to the total amount of the polyol is 10 to 100% by mass.
[8] The polyether polyol is a Mannich polyol composed of a ring-opening adduct of an alkylene oxide to a Mannich condensate which is a reaction product of phenols, aldehydes, and alkanolamines, [6] or [7]. ] The system liquid described in.
[9] A method for producing a rigid foamed synthetic resin, which comprises 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 hard foamed synthetic resin 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].
[11] A hard foamed synthetic resin comprising a polyol, a polyisocyanate, and a cured foam of a foaming composition containing the foaming agent according to any one of [1] to [3], a foam regulating agent, and a catalyst.
[12] The hard foamed synthetic resin according to [10] or [11], wherein the density of the hard foamed synthetic resin is 5 to 300 kg / m ³ .
[13] An article comprising the hard foamed synthetic resin according to any one of [10] to [12].
[14] A kit for a rigid foamed synthetic resin, which comprises a first agent comprising the system solution according to any one of [4] to [8] and a second agent containing a polyisocyanate.

According to the present invention, workability during foaming can be improved, and when it is contained in a system liquid for producing a rigid foamed synthetic resin, the storage stability of the system liquid and the system liquid after storage are included. It is possible to provide a foaming agent capable of maintaining good reactivity of the above, a method for producing a rigid foamed synthetic resin using the same, a system liquid, a kit for a rigid foamed synthetic resin, a rigid foamed synthetic resin, and an article including the same. .. More specifically, for example, by reacting a polyol and a polyisocyanate in the presence of a foaming agent containing 1224 yd and 1233 yd, a foam stabilizer, and a catalyst, physical properties such as compressive strength and thermal conductivity can be obtained. An excellent rigid foam synthetic resin can be produced. Further, the system liquid for producing the rigid foamed synthetic resin has little composition fluctuation, good storage stability, and good reactivity after storage. In addition, workability during construction is not impaired.

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, there are Z-form and E-form which are geometric isomers 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 without particular notice, the Z-form or E-form, or Z-form and E-form Indicates any proportion of the mixture. 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.

A "foaming agent" is a compound having at least one of the following actions 1 and 2.
(Action 1) In a composition containing the compound, the compound foams the composition by utilizing a gas generated by vaporization of the compound.
(Action 2) The compound causes the composition to be foamed by utilizing the gas generated by the reaction between the compound and the polyisocyanate in the composition containing the compound and the polyisocyanate.

The "system liquid" is a composition for reacting with polyisocyanate to obtain a hard foamed synthetic resin, and is a composition containing a raw material other than polyisocyanate, for example, a polyol, a foaming agent, a foam stabilizer, and a catalyst. That is.

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 "hard foam synthetic resin" is a resin 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. Examples of the hard foamed synthetic resin include hard polyurethane foam, hard urethane-modified polyisocyanurate foam, and hard polyurea foam.

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.

Each configuration in the present invention will be described below.
<foaming agent>
The foaming agent according to the present invention contains at least 1224 yd and 1233 yd. Since the boiling point of the foaming agent is appropriately adjusted by containing 1224 yd and 1233 yd, it is difficult to volatilize when it is contained in a system liquid or the like. As a result, the composition of the system liquid is unlikely to change, and a hard foamed synthetic resin having desired heat insulating performance can be easily obtained. In addition, the system liquid is less likely to cause a bumping phenomenon during transportation or construction, and workability during construction is likely to be improved. Further, when the system liquid contains a polyester polyol, the foaming agent according to the present invention tends to have improved compatibility with the polyester polyol, as compared with the foaming agent containing 1224 yd and not containing 1233 yd.

The 1224yd may be 1224yd (Z), 1224yd (E), or a combination thereof. The 1233 yd may be 1233 yd (E), 1233 yd (Z), or a combination thereof. Thus, more specifically, the foaming agent is a foaming agent containing 1224yd (Z) and 1233yd (E); a foaming agent containing 1224yd (Z) and 1233yd (Z); 1224yd (Z) and 1233yd ( A foaming agent containing E) and 1233yd (Z); a foaming agent containing 1224yd (E) and 1233yd (E); a foaming agent containing 1224yd (E) and 1233yd (Z); 1224yd (E) and 1233yd ( A foaming agent containing E) and 1233 yd (Z); a foaming agent containing 1224 yd (Z), 1224 yd (E) and 1233 yd (E); including 1224 yd (Z), 1224 yd (E) and 1233 yd (Z). Foaming agents; include foaming agents comprising 1224yd (Z), 1224yd (E), 1233yd (E) and 1233yd (Z).

The ratio of the total mass of 1224yd and 1233yd to the total mass of the foaming agent is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 90 to 100% by mass. When it is within the above range, the density of the obtained rigid foamed synthetic resin is appropriate, the heat insulating performance is likely to be good, and the storage stability of the system liquid is likely to be good.

In the foaming agent, the mass ratio of the content of 1224 yd to the content of 1233 yd is preferably 1/99 to 99/1, more preferably 10/99 to 90/1, still more preferably 10/90 to 90/10. 25/75 to 75/25 is even more preferable, and 30/70 to 70/30 is particularly preferable. When it is within the above range, the density of the obtained rigid foamed synthetic resin becomes appropriate, and the heat insulating performance tends to be good.

In the foaming agent, the mass ratio of the content of 1224yd (E) to the content of 1224yd (Z) may be 0/100 to 100/0, preferably 0.1 / 99.9 or more and less than 10/90, 1 / 99-9 / 91 is more preferable. When the mass ratio is in the range of 0.1 / 99.9 or more and less than 10/90, the storage stability of the system liquid tends to be good.

In the foaming agent, the mass ratio of the content of 1233yd (E) to the content of 1233yd (Z) may be 0/100 to 100/0, preferably 0/100 or more and less than 50/50, and 0/100 to 10 / 90 is more preferable. When the mass ratio is in the range of 0/100 or more and less than 50/50, the production efficiency tends to be high.

The boiling point of the foaming agent under atmospheric pressure is preferably 17 ° C. or higher and lower than 33 ° C., more preferably 18 to 32 ° C., and even more preferably 19 to 31 ° C. When it is within the above range, it is easy to prevent bumping when transporting the system liquid. The boiling point is the boiling point when a plurality of types of compounds used as a foaming agent are mixed. By adjusting the mass ratio of the content of 1224 yd to the content of 1233 yd, the boiling point of the foaming agent can be adjusted as desired.

The foaming agent preferably further contains water. When the foaming agent contains water, the foaming property tends to be better. When the foaming agent contains water, the content of water with respect to the total mass of the foaming agent is preferably 0.1% by mass or more and 50% by mass or less, preferably 0.3% by mass or more and 30% by mass or less, and 0.5% by mass. More preferably 10% by mass or less. When the water content is within the above range, the foaming agent tends to have even better foamability.

The foaming agent may further contain other foaming agents other than 1224yd, 1233yd, and water.
The other foaming agent can be appropriately selected from known foaming agents, for example, CF ₂ H ₂ , CF ₃ CF ₂ H, CF ₃ CH ₃ , CHF ₂ CF ₂ H, CF ₃ CH ₂ F, CHF ₂ CH. HCFC such as CCl 2 FCH _3;; HC such as _{cyclopentane; 3, CF 3 CHFCF 3,} CF 3 CF 2 CHFCHFCF 3, CHF 2 CH 2 CF 3, CH 3 CF 2 CH 2 CF 3, HFC etc. CF _{3 CF 2 CF 2 OCH 3, CHF} 2 CF 2 OCH such _{3 HFE;} CF ₃ CH = CClH such, 1224Yd and non 1233yd HCFO; HFO such 1336mzz; CHCl = CClH, chlorinated solvents such as _CH 2 Cl ₂ Can be mentioned.

The ratio of the mass of the other foaming agent to the total mass of the foaming agent is preferably 50% by mass or less, more preferably 10% by mass or less. When it is not more than the above upper limit value, the physical properties of the obtained rigid foamed synthetic resin are not easily impaired.

<System liquid>
The system liquid according to the present invention contains a polyol, a foaming agent according to the present invention, a foam stabilizer and a catalyst.

(Polyprethane)
The "polyol" in the present invention refers to all polyols used in the reaction with polyisocyanate, and may be one kind of polyol or may contain two or more kinds of polyols.

The average number of hydroxyl groups of the polyol is preferably 2 to 8, and 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 foamed synthetic resin 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 polyol is a value obtained by molarly averaging the number of hydroxyl groups of all the polyols contained therein.

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 foamed synthetic resin is suppressed, and the dimensional stability tends to be good. When it is at least the lower limit of the above range, the hard foamed synthetic resin is unlikely to become brittle. The Mw of the above polyol is an average value of Mw of all the polyols contained.

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, the shrinkage of the rigid foamed synthetic resin is suppressed, and the dimensional stability becomes good. When it is less than the upper limit value, the hard foamed synthetic resin is unlikely to become brittle. The average hydroxyl value of the 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 hard foamed synthetic resin has excellent physical properties. The polyether polyol preferably contains the Mannich polyol described later because it is easy to obtain good mixing with the polyisocyanate and it is easy to obtain the adhesiveness when the hard foamed synthetic resin is formed on the base material. Since the obtained rigid foamed synthetic resin 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 A polyether polyol can be produced by a conventionally known method, and is obtained by reacting a cyclic ether in the presence of a catalyst using a compound containing active hydrogen with which the cyclic ether can react as an initiator. 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, trimethylpropane, 1, Polyhydric alcohols such as 2,6-hexanetriol, pentaerythritol, diglycerin, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, galactitol, shoe cloth; bisphenol A, phenol-formaldehyde initial condensate, Mannig condensate described below. Polyvalent phenols such as: monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, alkanolamines such as N- (2-aminoethyl) ethanolamine; ethylenediamine, propylenediamine, hexamethylenediamine, piperazine, aniline, ammonia, N. -Aminomethylpiperazin, N- (2-aminoethyl) piperazine, 4-methyl-1,3-phenylenediamine, 2-methyl-1,3-phenylenediamine, 4,4'-diphenylmethanediamine, xylylenediamine, diethylenetriamine , Amines such as triethylenetetramine.

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 to be 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.

The content ratio of the above-mentioned polyether polyol to the total amount of the polyol in the present invention is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, still more preferably 50 to 100% by mass. When it is at least the lower limit of the above range, the heat insulating property and compressive strength of the obtained hard foamed synthetic resin tend to be good.

The Mannich polyol consists of a ring-opening adduct of alkylene oxide (hereinafter referred to as "AO") to the Mannich condensate, which is a reaction product of phenols, aldehydes, and alkanolamines. The Mannich polyol is, for example, a polyether polyol obtained by ring-opening and adding the above AO using a Mannich condensation product obtained by reacting phenols, aldehydes, and alkanolamine with a reaction (Mannich condensation reaction) as an initiator. Since the Mannig polyol contains an amino group, the activity of the polyol tends to be high, and since it contains a hydrophilic group and a hydrophobic group and has surface activity, the miscibility between the polyol and the polyisocyanate tends to be good, and contains phenols. As a result, a carbide film is likely to be formed during combustion, so that the flame retardancy of the rigid foamed synthetic resin tends to be high.

As the phenols, at least one selected from the group consisting of phenol and phenol derivatives having a hydrogen atom at at least one ortho position with respect to the hydroxyl group of phenol is preferable.
The phenol derivative has a hydrogen atom at at least one ortho position with respect to the hydroxyl group of phenol, and at least one of the other hydrogen atoms bonded to the aromatic ring is an alkyl group having 1 to 15 carbon atoms. Substituted alkylphenols are preferred.
The substitution position of the alkyl group in the alkylphenol may be either the ortho position or the para position. The number of hydrogen atoms substituted with an alkyl group in one molecule of the alkylphenol is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1.
The number of carbon atoms of the alkyl group in the alkylphenol is more preferably 1 to 10.
As the alkylphenol, nonylphenol and cresol are preferable. Nonylphenol is more preferable in terms of improving the compatibility between the polyol and the polyisocyanate.

As the aldehydes, either one or both of formaldehyde and acetaldehyde are preferable. Of these, formaldehyde is preferable in terms of the reactivity of the Mannich condensation reaction.
Formaldehyde may be used in any form, specifically in the form of formalin aqueous solution, methanol solution, or paraformaldehyde. When used as paraformaldehyde, formaldehyde generated by heating paraformaldehyde may be used.

As the alkanolamine, at least one selected from the group consisting of monoethanolamine, diethanolamine and 1-amino-2-propanol is preferable. Of these, diethanolamine is preferable because a low-viscosity Mannich polyol can be easily obtained.

The Mannich condensation product is obtained by a Mannich condensation reaction by a known method.
In the Mannich condensation reaction, the number of moles of aldehyde per 1 mol of phenols is preferably 0.5 to 3.0 mol, more preferably 1.0 to 2.5 mol. Within the above range, good dimensional stability of the rigid foamed synthetic resin can be easily obtained.
In the Mannich condensation reaction, the number of moles of alkanolamine per 1 mol of phenols is preferably 1 to 3 mol, more preferably 1.5 to 3 mol. Within the above range, a hard foamed synthetic resin having high strength and high flame retardancy can be easily obtained.
In the Mannig condensation reaction, the number of moles of aldehyde per mol of phenols is preferably 0.5 to 3 mol, and the number of moles of alkanolamine to 1 mol of phenols is preferably 1 to 3 mol.

AO is ring-opened and added to the active hydrogen of the Mannich condensation product to obtain a Mannich polyol.
It is preferable to use EO, PO or both EO and PO as AO. The proportion of EO in the total amount of AO used in the production of the Mannich polyol may be more than 0% by mass and 100% by mass, preferably 20 to 100% by mass, more preferably 30 to 100% by mass, and 40 to 40 to 100% by mass. 100% by mass is more preferable. Within the above range, the compressive strength of the rigid foamed synthetic resin tends to increase.

The number of moles of AO added to the Mannich condensate by ring opening is preferably 1 to 30 mol, more preferably 2 to 20 mol, based on 1 mol of the phenols used in the production of the Mannich condensate. Within the above range, the hydroxyl value and viscosity of the produced polyether polyol tend to be low, and the shrinkage of the obtained rigid foamed synthetic resin is likely to be suppressed.

The average number of hydroxyl groups of the Mannich polyol is preferably 2 to 8, and more preferably 3 to 7. When the average number of hydroxyl groups of the Mannich polyol is within this range, the average number of hydroxyl groups of the polyol tends to be within the above range.
The average number of hydroxyl groups of the Mannich polyol is the same as the average number of active hydrogens contained in the Mannich condensate. By setting the raw material and the reaction ratio used for the Mannich condensation reaction in the above range, the number of active hydrogens contained in the Mannich condensation product can be adjusted, and the average number of hydroxyl groups of the Mannich polyol can be adjusted in the above range.

The hydroxyl value of the Mannich polyol is preferably 100 to 800 mgKOH / g, more preferably 200 to 700 mgKOH / g, and even more preferably 300 to 600 mgKOH / g. Within the above range, the strength of the hydrogen bond due to the hydroxyl group is appropriately adjusted, so that the viscosity of the Mannich polyol tends to decrease, the strength of the obtained rigid foamed synthetic resin tends to increase, and good dimensional stability can be obtained. Cheap.

The Mw of the Mannich polyol is preferably 100 to 3,000, more preferably 150 to 2,000. Within the above range, the strength of hydrogen bonds due to hydroxyl groups is appropriately adjusted, so that the viscosity of the Mannich polyol tends to decrease, the obtained rigid foamed synthetic resin does not easily become brittle, and the adhesiveness to the substrate when molded. Is easy to develop and the compression strength is easy to improve.

The Mannich polyol may be used alone or in combination of two or more.
The content ratio of the Mannich polyol to the total amount of the polyol in the present invention 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 amount of the polyol. When it is at least the lower limit of the above range, the heat insulating property, the flame retardancy, and the compressive strength tend to be good.

-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), heavy addition of cyclic ether to polycarboxylic acid anhydride, and transesterification 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-Propylenediol, 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, shoe cloth can be exemplified.

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. Only one type of polyvalent carboxylic acid may be used, or two or more types 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, the shrinkage of the hard foamed synthetic resin is likely to be suppressed, and when it is at least the upper limit of the above range, the brittleness of the hard foamed synthetic resin is suppressed and good physical properties are obtained. Easy to get rid of.

In the present invention, 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, more preferably 10 to 65% by mass. It is preferable, and 30 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 foamed synthetic resin is likely to be suppressed.

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

-Polyhydric 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 called a polymer polyol or a graft polyol can also be used.

The polyol in the present invention preferably contains a Mannich polyol and a polyester polyol, and more preferably comprises a Mannich polyol, a polyester polyol, and a polyether polyol other than the Mannich polyol.

When the polyol in the present invention 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, preferably 20 to 100% by mass, and 30 to 100% by mass. 100% by mass is more preferable, and 40 to 100% by mass is further preferable. When the content ratio is within the above range, the solubility of the polyol and the foaming agent is appropriately adjusted, and the compressive strength of the hard foamed synthetic resin tends to increase. 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.

(Foaming agent)
The foaming agent is as described above. The amount of the foaming agent 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 foamed synthetic resin becomes appropriate, and the heat insulating performance tends to be good.

(Foam stabilizer)
Foam conditioners are used to form good bubbles.

Examples of the foam stabilizer include silicone-based foam stabilizers and fluorine-containing compound-based foam stabilizers.
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 foam stabilizer, a graft copolymer of polyoxyalkylene glycol, which is a polymer of ethylene oxide or propylene oxide, and polydimethylsiloxane can also be used, and the oxyethylene group content in the polyoxyalkylene is 70 to 100. A molar% silicone foam stabilizer 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 Co., Ltd .; B8040, B8155, B8239, B8244, B8330, B8443, B8450, B8460, B8462, B8465, B8466, B8467, manufactured by Ebonic. B8474, B8476, B8841, B8484, B8485, B8486, B8490, B8494, B8498, B8516, B8523, B8534, B8544, B8545, B8546, B8547, B8558, B8870, B8881, DC-5598; SF-5598 manufactured by Toray Dow Corning. 2937F, SF-2938F, SZ-1718, SZ-1710, SF-2936F, SF-2945F, SZ-1720, SZ-1328, SZ-1642, SZ-1671, SZ-1677, SH-193; DOW DC -193 can be mentioned.
The content of the foam stabilizer 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 trimerization reaction promoting catalyst that promotes the trimerization reaction of isocyanate groups, or both the urethanization catalyst and the trimerization reaction promoting catalyst are used.

Examples of the catalyst include amines.
Examples of amines include tertiary amines, secondary amines, and primary amines. 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-benzendiamine-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-quinucridinol (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 Lupiperazin, 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 "-pentamethyldipropylene triamine, 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 (ethyl) ether 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) butyl] ) 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.

The amine may also be an alkylated (methylated or the like) amine, and examples of such amines 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) are used in combination. Examples of amines (tertiary amines and the like) having at least one hydroxyalkyl group in the molecule 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 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 metals 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 carboxylic acid salt (zinc, bismuth, etc.).
The alkali metal carboxylic acid salt 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 metal carboxylate include aliphatic carboxylic acids (aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, etc.) and aromatic carboxylic acids (aromatic monocarboxylic acids, aromatic dicarboxylic acids, etc.). Be done.
Examples of the carboxylic acid include acetic acid, propionic acid, pentanic 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 metal carboxylate 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 a carboxylic acid (bismuth (III) carboxylate salt, a carboxylic acid metal salt of bismuth 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-ethylhexanoate, bismuth 2-ethylhexanoate, zinc 2-ethylhexanoate, lead 2-ethylhexanoate, potassium octane, and octane. Lead Acid, Stannous Octanoate, Potassium Octylate, Potassium Acetate, Potassium Octanoate, Antimon Glycolate, 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, titanyl potassium oxalate, tin diacetate, tin dioctate, tin dioleate, tin dilaurate, 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 the 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 a quaternary ammonium compound 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-ethylhexanoate, 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 (polyoxypropylenediamine), and Dabco TMR-30 (Tris-2,4). , 6- (Dimethylaminomethyl) phenyl / bis (dimethylaminomethyl) phenol), 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 (dimethylaminopropyl hexahydrotriazine, 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), Curithane52 (methyl (n-methylaminob-naolium 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), Fitsture 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-benzendiamine-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, from the viewpoint of reactivity, it is preferable to use a urethanization catalyst and a trimerization reaction promoting catalyst in combination, a tertiary amine and the organic acid metal salt in combination, or a tertiary amine and the organic acid metal salt. 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-dimethylaminopropyl imidazole, N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine. ..

As the organic acid metal salt other than the 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; tetramethylammonium 2-ethylhexanate, 2-. Tetraalkylammonium organic acid salts such as hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium 2-ethylhexanate; tertiary amines such as N, N, N', N'-tetramethylethylenediamine and diester carbonate Examples thereof include a quaternary ammonium compound obtained by anion-exchange reaction of a quaternary ammonium carbonate obtained by reacting with 2-ethylhexanoic acid.

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 catalysts.
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. it can.

A tertiary amine and a fatty acid compound having 7 or more carbon atoms may be used in combination. Examples of fatty acid compounds 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. , Arakidic acid, henicosylic acid, behenic acid, tricosyl acid, lignoseric acid, etc. Saturated fatty acids; α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, etc. ω-3 fatty acids; linoleic acid Ω-6 fatty acids such as, γ-linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, docosapentaenoic acid, ω-7 fatty acids such as palmitoleic acid, baccenoic acid, paulic acid, oleic acid, ellaic acid, erucic acid , Nerbonic 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 acid (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 tetraalkylguanidine and a tertiary amine may be used. It may be used in combination with a combination salt, or may be used in combination with the above organic carboxylic acid or a tertiary amine catalyst component of a combination thereof and a tetraalkylguanidine salt.

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.

(Optional ingredient)
In the present invention, components other than those described above 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, foam breaking agents, dispersants, and discoloration inhibitors. Examples of the filler include calcium carbonate and barium sulfate. Examples of the anti-aging agent include an antioxidant and an ultraviolet absorber.
The content of the 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 from the viewpoint of easily maintaining the effect of the present invention.

<Manufacturing method of hard foamed synthetic resin>
The method for producing a rigid foam synthetic resin of the present invention comprises reacting a polyol and a polyisocyanate in the presence of a foaming agent containing 1224 yd and 1233 yd, a foam stabilizer, and a catalyst. Specifically, from the viewpoint of workability, production efficiency, etc., a system liquid containing the polyol, the foaming agent, a foam stabilizer, and a catalyst is mixed with polyisocyanate, and the polyol and polyisocyanate in the system liquid are mixed. A method of producing a rigid foamed synthetic resin is preferable. The polyols, foaming agents, foam stabilizers, and catalysts are as described above.

(Polyisocyanate)
Examples of the polyisocyanate include aromatic-based, alicyclic-based, and aliphatic-based 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, and hexamethylene diisocyanate, or variants thereof. Examples of the above-mentioned modified product include a prepolymer-type modified product, an isocyanurate 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 terms of the isocyanate index from the viewpoint of more effectively advancing the nurateization reaction. ~ 350 is more preferable, and 110 to 300 is even more preferable.

(Reaction method)
A known method can be used as a method for reacting the polyol with the polyisocyanate. For example, a so-called injection method in which a raw material containing a system liquid and a polyisocyanate is injected into a frame such as a mold and foamed; a raw material containing the system liquid and a polyisocyanate is supplied between two face materials and foamed. This is a method of manufacturing a laminate in which a hard foamed synthetic resin is sandwiched between these face materials, a so-called continuous board molding method; a method of spraying a raw material containing a system liquid and a polyisocyanate. , The so-called spray method.

The injection method can be carried out 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 system liquid is injected into various molds and then foamed and cured to produce a hard foamed synthetic resin. The foaming agent 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 raw material containing the 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 raw material containing a system liquid and a polyisocyanate is agitated, foamed, and injected into a mold frame. Furthermore, a raw material 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 foamed synthetic resin 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 as a result of the thickness of the heat insulating layer being concentrated on the lower part of the wall surface, there are many parts to be cut to make the thickness of the interior wall uniform, which causes problems such as an increase in waste. 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, dew condensation prevention materials for condominiums, heat insulating materials for buildings such as detached houses; heat insulating materials for vehicles and aircraft; soundproofing materials for buildings, vehicles, and aircraft. Can be mentioned.

According to the production method of the present invention, a rigid foamed synthetic resin having a density of 5 to 300 kg / m ³ can be produced. The rigid foamed synthetic resin obtained by the above method tends to have low thermal conductivity and good compressive strength, as shown in Examples described later. The density of the hard foamed synthetic resin can be controlled by the amount of the foaming agent used. Further, the thermal conductivity can be controlled by adjusting the composition of the polyol or the foaming agent.

<Effervescent composition>
The foaming composition according to the present invention contains a polyol, a polyisocyanate, a foaming agent according to the present invention, a foam stabilizer, and a catalyst. The polyols, polyisocyanates, foaming agents, foam stabilizers and catalysts are as described above. If the components contained in the effervescent composition are simply mixed, the reaction starts quickly and the effervescent composition hardens, so that it is difficult to maintain a stable form as the composition. In order to prevent this, the effervescent composition is preferably a multi-component type, for example, a two-component type. Examples of the two-component type effervescent composition include an effervescent composition composed of a first agent containing the system solution and a second agent containing a polyisocyanate.

<Kit for rigid foamed synthetic resin>
The kit for a rigid foamed synthetic resin according to the present invention comprises a first agent composed of the system liquid according to the present invention and a second agent containing polyisocyanate. The system solution and polyisocyanate are as described above. By mixing the first agent and the second agent, the polyol and the polyisocyanate react in the presence of the foaming agent, the foam stabilizer, and the catalyst according to the present invention to obtain a hard foamed synthetic resin. .. The second agent may contain an additive such as a stabilizer. 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 95% by mass or more. The second agent may consist of polyisocyanate.

<Hard foamed synthetic resin>
The rigid foamed synthetic resin according to the present invention is obtained by reacting a polyol and a polyisocyanate in the presence of a foaming agent, a foam stabilizer, and a catalyst according to the present invention. The hard foamed synthetic resin comprises a cured foam of the foamable composition. The method for producing the rigid foamed synthetic resin is not particularly limited, and the rigid foamed synthetic resin can be obtained, for example, by the production method of the present invention. Further, the above-mentioned hard foamed synthetic resin may be obtained by mixing the first agent and the second agent of the kit for hard foamed synthetic resin according to the present invention. Other points regarding the rigid foamed synthetic resin are as described above.

<Article>
The article according to the present invention includes the above-mentioned rigid foamed synthetic resin. The article is not particularly limited as long as it includes the rigid foamed synthetic resin, and in addition to the articles mentioned in the description of the method for producing the rigid foamed synthetic resin, for example, a heat insulating material, a soundproofing material, and the like, such a heat insulating material. Also includes electrical appliances, vehicles, aircraft, buildings, etc. equipped with soundproofing materials.

Hereinafter, the present invention will be described in more detail with reference to 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)
Polyol m-1:
Using the reaction product obtained by reacting 1.5 mol of formaldehyde and 2.2 mol of diethanolamine with 1 mol of nonylphenol as an initiator, only EO was ring-opened and added, and the average number of hydroxyl groups was 3. 5. A polyether polyol having a hydroxyl value of 590 mg / KOH was obtained. The addition amount of AO was 2.6 mol of EO with respect to 1 mol of nonylphenol. Mw was 255.

A mixed solution of foaming agent C1: 1224yd / 1233yd = 60/40 (mass ratio).
Foaming agent C2: 1224yd / 1233yd = 65/35 (mass ratio) mixed solution.
Foaming agent C3: 1224yd / 1233yd = 70/30 (mass ratio) mixed solution.
Foaming agent C4: 1224yd.
A mixed solution of foaming agent C5: 245fa / 365mfc = 70/30 (mass ratio).

Details of the components constituting 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 (hereinafter referred to as Z / E ratio) = 99 .43 / 0.57, (AGC product name: AMOLEA 1224yd).
1233yd: 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), purity 99.93%, Z / E ratio = 90.83 / 9.16, (AGC product name: AMOLEA AS-300) ).
245fa is 1,1,3,3,3-pentafluoropropane (HFC-245fa) (Honeywell product name: Enable 245fa).
365mfc is 1,1,1,3,3-pentafluorobutane (HFC-365mfc) (Solvay product name: Solcan 365mfc).

Catalyst E1: 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine (reactive amine catalyst, Ebonic product name: Polycat 41).
Catalyst E2: Diethylene glycol solution of potassium 2-ethylhexanoate (potassium concentration 15%, Nihon Kagaku Sangyo Co., Ltd. product name: Pucat 15G).
Foam conditioner: SH-193 (Product name of Toray Dow Corning Co., Ltd.).
Flame retardant: Tris (β-chloropropyl) phosphate (Daihachi Chemical Co., Ltd. product name: TMCPP).
Polyisocyanate: Polymeric MDI (Product name of Sumika Cobestro Urethane Co., Ltd .: Sumijour 44V20).

(Measuring method)
<Measurement of vapor pressure of foaming agent>
For the foaming agent C1 composed of 1224 yd and 1233 yd, the vapor pressure of the 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 0 ° C. to 50 ° C. in 10 ° C. increments, and the vapor pressure at each temperature was measured. From the obtained results, the temperature at which the vapor pressure became 101.3 kPa was estimated. Around that temperature, the vapor pressure was actually measured in 0.1 ° C increments. The temperature at which the vapor pressure was confirmed to be 101.3 kPa was defined as the boiling point of the foaming agent C1. The boiling points of the foaming agents C2 to C5 and the other foaming agents shown in Table 1 were measured in the same manner.

The measurement results are shown in Table 1. The boiling point of the foaming agent consisting of 1224 yd and 1233 yd was 20.2 ° C. to 32.8 ° C. in the range of 25% by mass to 70% by mass of the amount of 1233 yd, which was within the range of the boiling point suitable for the foaming agent.

<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 the column, 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.

<Evaluation method of hard foamed synthetic resin>
[Reactivity]
When the system solution prepared by the method described later and polyisocyanate were mixed to prepare a mixed solution, 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 pulled out quickly.
Tuck free time (tft) (seconds): Foaming progresses from the mixing start time, 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. The time it takes for the upper surface of the foam to become non-sticky without being worn.

[density]
A sample piece was obtained by cutting out from the core portion of the free foam foam obtained by the method described later to a size of 50 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 flat plate type free foam foam obtained by the method described later into a width of 200 mm, a length of 200 mm, and a height of 25 mm.
Using a thermal conductivity measuring device (Hideko Seiki Co., Ltd. product name: Autolambda HC-074), average the thermal conductivity (unit: W / m · K) of the above test piece in accordance with JIS A 9511. It was measured at a temperature of 23 ° C.

(Examples 1 to 5)
Examples 1 to 3 are examples, and examples 4 and 5 are comparative examples.
Each raw material was mixed at the blending amount (part by mass) shown in Table 1 to prepare a system solution. The compounding amount of the polyol (100 parts by mass) was 120 g. The blending amount of polyisocyanate is shown in Table 2 by mass and isocyanate index.
The liquid temperatures of the system liquid and the polyisocyanate were adjusted to 15 ° C., respectively, and a free foam foam was produced by the procedure shown below.

[Manufacturing of free foam foam]
Add the compounding amount of polyisocyanate shown in Table 2 to the container containing the system liquid, and stir for 5 seconds at a rotation speed of 3,000 rpm using a stirrer equipped with a disk-shaped stirring blade to mix. The liquid was prepared. 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 flat plate type free foam]
The mixed solution prepared in the same manner as described above was quickly put into an upper open container having a width of 400 mm, a length of 400 mm, and a height of 50 mm and foamed to obtain a flat plate type free foam.

[Evaluation]
The physical properties (density, thermal conductivity) of the obtained free-foamed 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. These results are shown in Table 3.

In Examples 1 to 3 containing 1224 yd and 1233 yd as the foaming agent, it was found that the lower the boiling point of the foaming agent, the shorter the cream time, and the better the initial foamability in the on-site construction. Further, in Examples 1 to 3, the tack free time of the system liquid was short and the reactivity was good. Therefore, the entire work can be shortened, and the work efficiency is improved. In Examples 1 to 3, the boiling point of the foaming agent is within an appropriate boiling point range as the foaming agent, and the foamability is good. Therefore, it is considered that the tack-free time of the system liquid is shortened. Further, in Examples 1 to 3, the physical properties of the free foam foam, that is, the density and thermal conductivity, show the same values as in Example 4 corresponding to the case where the conventional foaming agent is used, and the performance equivalent to that of the conventional one is obtained. It was confirmed that it could be obtained.

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 it exerts the following advantageous effects. First, the system liquid containing the foaming agent is less likely to cause a bumping phenomenon during transportation or construction, and can improve workability during foaming. Secondly, since the foaming agent is hard to volatilize from the system liquid containing the foaming agent according to the present invention and the composition of the system liquid is hard to change, the storage stability of the system liquid and the storage stability of the system liquid after storage 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 a foaming agent having a boiling point higher than room temperature.

Claims (14)

A foaming agent containing CF ₃ CF = CHCl and CHF ₂ CF = CHCl. The foaming agent according to claim 1, wherein the ratio of the total mass of CF ₃ CF = CHCl and CHF ₂ CF = CHCl to the total mass of the foaming agent is 50 to 100% by mass. The foaming agent according to claim 1 or 2, wherein the mass ratio of the content of CF ₃ CF = CHCl to the content of CHF ₂ CF = CHCl in the foaming agent is 1/99 to 99/1. A system liquid containing a polyol, a foaming agent according to any one of claims 1 to 3, a foam stabilizer and a catalyst. The system liquid according to claim 4, wherein the amount of the foaming agent with respect to 100 parts by mass of the polyol is 10 to 100 parts by mass. The system solution according to claim 4 or 5, which contains a polyether polyol as the polyol. The system solution according to claim 6, wherein the content ratio of the polyether polyol to the total amount of the polyol is 10 to 100% by mass. The system according to claim 6 or 7, wherein the polyether polyol is a Mannich polyol composed of a ring-opening adduct of an alkylene oxide on a Mannich condensation product which is a reaction product of phenols, aldehydes, and alkanolamines. liquid. A method for producing a rigid foam synthetic resin, which comprises reacting a polyol and a polyisocyanate in the presence of a foaming agent, a foam stabilizer, and a catalyst according to any one of claims 1 to 3. A hard foamed synthetic resin obtained by reacting a polyol and a polyisocyanate in the presence of the foaming agent, foam stabilizer, and catalyst according to any one of claims 1 to 3. A hard foamed synthetic resin comprising a polyol, a polyisocyanate, and a cured foam of a foaming composition containing the foaming agent, foam stabilizer, and catalyst according to any one of claims 1 to 3. The hard foamed synthetic resin according to claim 10 or 11, wherein the density of the hard foamed synthetic resin is 5 to 300 kg / m ³ . An article comprising the rigid foamed synthetic resin according to any one of claims 10 to 12. A kit for a rigid foamed synthetic resin, which comprises a first agent comprising the system liquid according to any one of claims 4 to 8 and a second agent containing a polyisocyanate.