JPWO2019088035A1 - Manufacturing method of hard foamed synthetic resin - Google Patents

Abstract

Using at least the Z form of CF3CF = CHCl and CF3CH = CHCF3 as the foaming agent, a hard foamed synthetic resin having good properties is obtained. A method for producing a rigid foamed synthetic resin in which a polyol and a polyisocyanate are reacted in the presence of a foaming agent, a foaming agent, and a catalyst. The polyol has a Mw of 100 to 3000, and the foaming agent is CF3CF =. A method for producing a rigid foamed synthetic resin, which comprises a Z-form of CHCl and CF3CH = CHCF3.

Description

The present invention relates to a method for producing a rigid foamed synthetic resin.

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 hard foam such as a rigid polyurethane foam, a rigid urethane-modified polyisocyanurate foam and 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, in Patent Documents 1 and 2, as an azeotropic mixture, CF ₃ CF = CHCl E-form (1-chloro-2,3,3,3-tetrafluoropropene E-form, HCFO-1224yd (E)) , CF ₃ CH = CHCF ₃ (1,1,1,4,4,4-hexafluoro-2-butene, HFO-1336 mzz) is disclosed and can be used as a foaming agent for thermosetting or thermoplastic resins. Is described. Further, Patent Document 3 describes that the E-form (HCFO-1233zd (E)) of 1-chloro-3,3,3-trifluoropropene can be used as a foaming agent.

International Publication No. 2012/106565 International Publication No. 2013/059550 Patent No. 5562827

At the construction site of the hard foamed synthetic resin, 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, when a mixture of 1224 yd (E) and 1336 mzz or 1233 zd (E) is used as the foaming agent, this system solution may generate suspended matter or sediment when stored, and thus floats in this way. There is a problem that the system liquid in which substances and sediments are generated is inferior in reactivity with polyisocyanate.

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 problem can be solved by using a foaming agent containing the Z form of CF ₃ CF = CHCl and CF ₃ CH = CHCF ₃ .
The present invention is the following [1] to [13].
[1] A method for producing a rigid foamed synthetic resin in which a polyol and a polyisocyanate are reacted in the presence of a foaming agent, a foam stabilizer, and a catalyst, wherein the weight average molecular weight of the polyol is 100 to 3000. A method for producing a hard foamed synthetic resin, wherein the foaming agent contains a Z-form of CF ₃ CF = CHCl and CF ₃ CH = CHCF ₃ .
[2] The production method according to [1], wherein the ratio of the total amount of CF ₃ CF = CHCl Z-form and CF ₃ CH = CHCF _{3 to} the total amount of the foaming agent is 50 to 100% by mass.
[3] The ratio of the Z-form of CF ₃ CF = CHCl to the total amount of the Z-form of CF ₃ CF = CHCl and CF ₃ CH = CHCF ₃ is 1 to 99% by mass, [1] or [2]. Manufacturing method.
[4] the blowing agent further contains E of _CF 3 CF = _CHCl, the proportion of the E isomer of _CF 3 CF = CHCl for Z of CF 3 CF = CHCl is 0.1 wt% to 10 wt The production method according to any one of [1] to [3], which is less than%.
[5] The production method according to any one of [1] to [4], wherein the amount of the foaming agent is 10 to 100 parts by mass with respect to 100 parts by mass of the polyol.

[6] The method for producing any of [1] to [5], wherein the polyol contains a polyether polyol.
[7] The production method according to [6], wherein the 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 obtained by ring-opening and adding an alkylene oxide to a Mannich condensate obtained by reacting phenols, aldehydes, and alkanolamines, [6] or [7]. Manufacturing method.
[9] The production method according to any one of [1] to [8], wherein the obtained rigid foam synthetic resin has a density of 5 to 300 kg / m ³ .
[10] A system liquid containing a polyol, a foaming agent, a foaming agent, and a catalyst, wherein the weight average molecular weight of the polyol is 100 to 3000, and the foaming agent is a Z-form of CF ₃ CF = CHCl and CF ₃ CH. A system solution comprising = CHCF ₃ .
[11] The system solution of [10], wherein the ratio of the total amount of CF ₃ CF = CHCl Z-form and CF ₃ CH = CHCF ₃ to the total amount of the foaming agent is 50 to 100% by mass.
[12] The ratio of the Z form of CF ₃ CF = CHCl to the total amount of the Z form of CF ₃ CF = CHCl and CF ₃ CH = CHCF ₃ is 1 to 99% by mass, [10] or [11]. System liquid.
[13] the blowing agent further contains E of _CF 3 CF = _CHCl, the proportion of the E isomer of _CF 3 CF = CHCl for Z of CF 3 CF = CHCl is 0.1 wt% to 10 wt The system solution according to any one of [10] to [12], which is less than%.

According to the present invention, a polyol having an Mw of 100 to 3000 and a polyisocyanate are reacted in the presence of a foaming agent containing 1224 yd (Z) and 1336 mzz, a defoaming agent, and a catalyst to obtain compressive strength. It is possible to produce a rigid foam synthetic resin having excellent physical properties such as thermal conductivity. Further, the system liquid for producing the rigid foamed synthetic resin has good storage stability and good reactivity after storage.

The meanings and definitions of the following terms are as follows.
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, 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.
The "foaming agent" is a compound that foams using a gas generated by vaporization of a foaming agent, and a compound that foams using a gas generated by a reaction between a foaming agent and polyisocyanate. Water works in a similar manner, but the term "foaming agent" as used herein and in the claims is used to mean water-free, unless otherwise specified. In the present invention, a foaming agent and water may be used in combination as the compound to be foamed.
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, that is, a polyol, a foaming agent, a defoaming agent, and a catalyst. That is.
"Active hydrogen" means a hydrogen atom in a reactive group capable of reacting with an isocyanate group such as a hydroxyl group, a carboxyl group, an amino group, a hydrazide group or 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.

Each configuration in the present invention will be described below.
<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.
Examples of the polyol include a polyether polyol, a polyester polyol, a polyester ether polyol, a polycarbonate 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.
Since the obtained hard foamed synthetic resin has excellent physical properties, the polyol is preferably a polyether polyol or a polyester polyol, and more preferably a polyether polyol. It is more preferable to include the Mannich polyol described later as the polyether polyol because it is easy to obtain good mixability with the polyisocyanate and it is easy to obtain the adhesiveness when the hard foamed synthetic resin is formed on the substrate. ..
The polyether polyol can be produced by a conventionally known method, and the cyclic ether is ring-opened and added in the presence of a ring-opening addition catalyst, if necessary, using a compound containing active hydrogen with which the cyclic ether can react as an initiator. The one obtained 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.
Examples of the initiator include the following polyhydric alcohols, polyhydric phenols, alkanolamines, amines and the like, in addition to the Mannich condensate described later.
Polyhydric alcohols: ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6 -Hexenediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, 1,2 , 6-Hexylene triol, pentaerythritol, diglycerin, tetramethylolcyclohexane, methylglucoside, sorbitol, mannitol, galactose, galactitol, shoe cloth, etc.
Polyvalent phenol: bisphenol A, phenol-formaldehyde initial condensate, Mannich condensate described later, etc.
Alkanolamines: monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, N- (2-aminoethyl) ethanolamine and the like.
Amines: ethylenediamine, propylenediamine, hexamethylenediamine, piperazine, aniline, ammonia, N-aminomethylpiperazine, N- (2-aminoethyl) piperazine, 4-methyl-1,3-phenylenediamine, 2-methyl-1, 3-Phenylenediamine, 4,4'-diphenylmethanediamine, xylylenediamine, diethylenetriamine, triethylenetetramine and the like.

As the cyclic ether, a cyclic ether compound having a 3- to 6-membered ring having one oxygen atom in the ring is preferable. Ethylene oxide (hereinafter referred to as "EO"), propylene oxide (hereinafter referred to as "PO") and butylene oxide are more preferable, and EO, PO, and a combination of EO and PO are even more 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.
Known examples of the ring-opening addition catalyst, such as an alkali metal compound catalyst (sodium-based catalyst, potassium-based catalyst, cesium-based catalyst, etc.), which are present as necessary when the ring-opening addition of the cyclic ether is added to the initiator. A ring-opening addition catalyst can be used.
The 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 is a polyether polyol obtained by ring-opening addition of the above AO using a Mannich condensation product obtained by reacting phenols, aldehydes, and alkanolamines (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 mixing property of 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 aldehyde, 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 mole of phenols is preferably 0.5 to 3 mol, more preferably 1 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 90% by mass, and 40 to 40 to 100% by mass. 90% 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 is likely 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 when the foaming agent contains 1224 yd and 1336 mzz.

Examples of the polyester polyol include a polyester polyol obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. 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.

Examples of the polymer in which the main chain is a hydrocarbon-based polymer and a hydroxyl group is introduced into the terminal portion include hydrogenated polybutadiene polyols and polybutadiene polyols.
As the polyhydric alcohol exemplified above, the polyhydric alcohol itself can be used as the polyol in the present invention.
As the polyol, a polyol composition called a polymer polyol or a graft polyol in which fine particles of a vinyl polymer are dispersed mainly in a polyether polyol can also be used.

The polyol in the present invention preferably contains a Mannich polyol and a polyether polyol other than the Mannich polyol, and more preferably consists of a Mannich 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. 90% by mass is more preferable, and 40 to 90% by mass is further preferable. When the content ratio is within the above range, the solubility of the polyol and the foaming agent described later 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.

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 is good. When it is not more than the upper limit value, the rapid thickening behavior at the time of foaming and molding is suppressed, and the fluidity and moldability are improved. 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 100 to 3000, preferably 150 to 2000. If it is larger than the upper limit of the above range, the rigid foamed synthetic resin tends to shrink and the dimensional stability tends to deteriorate. If it is smaller than the lower limit of the above range, the hard foamed synthetic resin tends to be brittle. The Mw of the above 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, 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.

<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 (Crude 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, Crude MDI or a modified product thereof is preferable, and a modified product of Crude MDI is more preferable. The polyisocyanate may be used alone or in combination of two or more.
The amount of polyisocyanate used is 50 to 300 as 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"). 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.
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, more preferably 105 to 350, and even more preferably 110 to 300 in terms of the isocyanate index. ..

<foaming agent>
The foaming agent in the present invention contains at least 1224 yd (Z) and 1336 mzz. Further, 1224 yd (E) may be contained. By containing 1224 yd (Z) and 1336 mzz as a foaming agent, the storage stability of the system liquid and the reactivity after storage are good.
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.
The ratio of the total amount of 1224 yd (Z) and 1336 mzz to the total amount of the foaming agent is preferably 50 to 100% by mass, more preferably 70 to 90% 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.
The ratio of 1224 yd (Z) to the total amount of 1224 yd (Z) and 1336 mzz in the foaming agent is preferably 1 to 99% by mass, more preferably 10 to 99% by mass, further preferably 10 to 90% by mass, and 30. ~ 70% by mass 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.
When the foaming agent further contains 1224 yd (E), the ratio of 1224 yd (E) to 1224 yd (Z) is preferably 0.1% by mass or more and less than 10% by mass, more preferably 1 to 9% by mass. When it is within the above range, the storage stability of the system liquid tends to be good. Although the reason for this has not been clarified, it is considered that the above-mentioned HF is involved by suppressing the decomposition of 1224yd (E), which is more unstable than 1224yd (Z), and reducing the amount of HF generated during decomposition. Since the promotion of the reaction between the polyisocyanate and the raw material other than the polyisocyanate is suppressed, it is presumed that insoluble matter is less likely to be generated in the system liquid and the system liquid is less likely to thicken.
When the foaming agent contains 1224 yd (E), the ratio of the total amount of 1224 yd (E), 1224 yd (Z) and 1336 mzz to the total amount of the foaming agent is preferably 50 to 100% by mass, more preferably 80 to 100% by mass. 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 1336mzz, there are Z-form and E-form. Those containing more Z-forms than E-forms are preferable in terms of high production efficiency.
Since 1336 mzz has a symmetric molecular structure, it is estimated that the stability is higher than that of 1224 yd, and it is estimated that 1224 yd is more easily decomposed in the mixed solution of 1336 mzz and 1224 yd.
The boiling point of the foaming agent under atmospheric pressure is preferably 17 to 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.
The boiling point of the mixture can be adjusted as desired by adjusting the ratio of the contents of 1224 yd and 1336 mzz.

As the foaming agent, 1224yd, 1336mzz and other foaming agents may be used in combination.
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. _{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 and the like of the HFC, HC cyclopentane _etc., CCl 2 FCH _3, etc. of HCFC, _CF 3 CF Examples thereof include HFEs such as ₂ CF ₂ OCH _3, CHF ₂ CF ₂ OCH ₃ , HCFOs other than 1224yd such as CF ₃ CH = CClH, HFOs other than 1336 mzz, and chlorine-based foaming agents such as CHCl = CClH and CH ₂ Cl _2. ..
When another foaming agent is contained as the foaming agent, the ratio of the other foaming agent is preferably 50% by mass or less, more preferably 10% by mass or less, based on the total amount of the foaming agent. 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.

<Water>
When water is used in combination with the foaming agent, the content of water is preferably 0.1 to 25 parts by mass, more preferably 0.2 to 10 parts by mass, and 0.5 parts by mass with respect to 100 parts by mass of the polyol. ~ 5 parts by mass is more preferable.
When water is used in combination with the above foaming agent, when the foaming agents are 1224 yd and 1336 mzz, the ratio of water to the total amount of 1224 yd and 1336 mzz is preferably 0.1 to 50% by mass, and 0.5 to 20%. The mass% is more preferable, and 1 to 10% by mass is further preferable.

<Foaming agent>
Defoaming agents are used to form good bubbles.
Examples of the defoaming agent include silicone-based defoaming agents and fluorine-containing compound-based defoaming agents. Commercially available products can be used for these.
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.

<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.
A tertiary amine is preferable as the urethanization catalyst.
As the trimerization reaction promoting catalyst, an organic acid metal salt excluding tin salt, lead salt and mercury salt, a quaternary ammonium salt, or both the above metal salt and a quaternary ammonium salt are preferably used.
When a trimerization reaction promoting catalyst is used, it is preferable to use a urethanization catalyst and a trimerization reaction promoting catalyst in combination, and a tertiary amine and the above metal salt are used in combination, or a tertiary amine, the above metal salt and the above quaternary ammonium salt are used together. Is more preferable in combination with.

Examples of the tertiary amine include 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'-dimethylpiperazin, dimethylcyclohexylamine, N-methylmorpholin, N-ethylmorpholin, bis (2-dimethylaminoethyl) ether, 1 Examples thereof include -methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropyl imidazole, and N-methyl-N- (N, N-dimethylaminoethyl) ethanolamine.
The tertiary amine can be used in combination with an acid as described in paragraphs [0066] to [0073] of JP-A-2017-155101, and preferred embodiments can be used in the same manner.

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.

Examples of the quaternary ammonium salt include tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetramethylammonium 2-ethylhexanate, and 2-hydroxy. Tetraalkylammonium organic acid salts such as propyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate, tertiary amines such as N, N, N', N'-tetramethylethylenediamine and carbonate diesters 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 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, the time from the start of mixing of the components used for foaming to the start of the reaction (cream time) and the time until the end of foaming (rise time) can be adjusted.

<Arbitrary ingredient>
The polyol system liquid of the present invention may further contain components other than those described above, 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 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.

<Manufacturing method of hard foamed synthetic resin>
In the method for producing a rigid foamed synthetic resin of the present invention, a polyol having an Mw of 100 to 3000 and a polyisocyanate are reacted in the presence of a foaming agent containing 1224 yd (Z) and 1336 mzz, a foam stabilizer, and a catalyst. Has a process.
Specifically, a system liquid containing the polyol, the foaming agent, a defoaming agent, and a catalyst is mixed with polyisocyanate, and the polyol and polyisocyanate in the system liquid are reacted and foamed to form a hard foam synthesis. A method of producing a resin is preferable.

As a method for reacting the polyol with the polyisocyanate, a known method can be used. 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 to foam, and a raw material containing the system liquid and a polyisocyanate is supplied between two face materials to foam. This is a method of manufacturing a laminate in which a hard foamed synthetic resin is sandwiched between these face materials, that is, 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 can be mentioned.

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 in the foaming device. Examples of articles that can be manufactured by using the injection method include refrigerating equipment such as electric refrigerators and panels for refrigerating / refrigerating vehicles.
The continuous board forming method is used, for example, in the production of heat insulating materials for building 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 polyisocyanate are mixed by a mixing head and foamed is particularly preferable.
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. Further, 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 low. 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 in order to make the thickness of the interior wall uniform, which causes problems such as increased waste. Occurs. Further, when the reactivity is low, 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 foam 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, and 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.

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 M1:
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 amount of AO added was 2.6 mol of EO and 255 mol of Mw with respect to 1 mol of nonylphenol.
Polycarbonate M2:
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, PO was ring-opened and added, and then EO was ring-opened and added. A polyether polyol having an average number of hydroxyl groups of 3.5 and a hydroxyl value of 500 mgKOH / g was obtained. The amount of AO added was 0.5 mol for PO and 4.5 mol for EO with respect to 1 mol of nonylphenol. The ratio of EO to the total amount of AO was 87.2% by mass, the ratio of PO was 12.8% by mass, and the Mw was 293.

A mixed solution of foaming agent C1: 1224 yd (Z) / 1336 mzz = 50/50 (mass ratio).
Foaming agent C2: A mixed solution of 1224 yd (Z) / 1224 yd (E) / 1336 mzz = 46/4/50 (mass ratio).
Foaming agent C3: 1233 zd (E).
Catalyst E1: 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine (reactive amine catalyst, Air Products, Inc. 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).
Defoaming agent: SH-193 (Product name of Toray Dow Corning Co., Ltd.).
Flame retardant: Tris (β-chloropropyl) phosphate (ICL-IP JAPAN product name: Phylrol PCF).
Polyisocyanate: Polymethylene polyphenylene polyisocyanate (Nippon Polyurethane Industry Co., Ltd. product name: Millionate MR-200).

(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 the column, two TSK-GEL SuperHZ 2000 and two TSK-GEL SuperHZ 1000 manufactured by Tosoh Corporation 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 the polyisocyanate were mixed to prepare a mixed solution, the mixing start time was set to 0 seconds, and the cream time, gel time and rise 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.
Rise time (rt) (seconds): Time from the mixing start time to the end of foaming.

[density]
A sample piece was obtained by cutting out the free foam foam obtained by the method described later from the core portion in the horizontal, vertical and height directions to 50 mm each. The density of the sample piece (unit: kg / m ³ ) was measured by a method according to JIS A 9511. [Compressive strength]
The compressive strength of the test piece used for measuring the density was measured according to JIS A 9511.
In the sample piece, the compressive strength in the lateral direction (unit: kPa) was measured.

[Dimensional stability]
Dimensional stability was measured by a method according to ASTM D 2126-75.
A test piece cut out from the core portion of the free-foaming foam obtained by the method described below with dimensions of width (x) 75 mm, length (y) 150 mm, and height (h) 100 mm is used as a test piece for low-temperature dimensional stability and moist heat. Each dimensional stability test was performed.
After storing the test piece in a constant temperature bath at -30 ° C (low temperature) or 70 ° C (high temperature, relative humidity 95%) for 24 hours, the dimensions of the test piece are changed by the following formula in the three directions of x, y, and h. I asked for the rate. In the dimensional change rate, a negative value means shrinkage, and a large absolute value means a large dimensional change.
Dimensional change rate (%) = (dimensions after storage-dimensions before preservation) / dimensions before preservation x 100

[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.
[Storage stability]
After storing the system liquid prepared by the method described later in a glass pressure-resistant container at 40 ° C. for 14 days, visually check the appearance of the liquid, and if sediment is generated, "x" is generated, and if suspended matter is generated, "x" is generated. “△”, “○” when there is no sediment or suspended matter.
In addition, the gel time of the system solution after storage under the above conditions was measured by the method described above. The smaller the gel time, the better the reactivity.

(Examples 1 to 6)
Examples 1, 2, 4 and 5 are examples, and examples 3 and 6 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 1 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]
Polyisocyanate was added to the container containing the system liquid, and the mixture was stirred for 5 seconds at a rotation speed of 3,000 rpm using a stirring device equipped with a disk-shaped stirring blade to prepare a mixed solution.
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, compressive strength, dimensional stability, 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 rise time) was measured by the above method. These results are shown in Table 2.
In addition, the storage stability was evaluated by the above method. The results are shown in Table 2.

In Examples 1, 2, 4, and 5 containing 1224 yd (Z) as the foaming agent, the storage stability of the system liquid was good. In addition, the gel time of the system solution after storage was short, and the reactivity was good. In Examples 3 and 6 which did not contain 1224yd (Z), the storage stability of the system solution and the reactivity of the system solution after storage were poor.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2017-212058 filed on November 01, 2017 are cited here and incorporated as disclosure of the specification of the present invention. Is.

Claims (13)

A method for producing a rigid foamed synthetic resin in which a polyol and a polyisocyanate are reacted in the presence of a foaming agent, a foam stabilizer, and a catalyst, wherein the weight average molecular weight of the polyol is 100 to 3000, and the foaming agent is , CF _{3 A} method for producing a foamed synthetic resin, which comprises a Z-form of CF = CHCl and CF ₃ CH = CHCF ₃ . The production method according to claim 1, wherein the ratio of the total amount of CF ₃ CF = CHCl Z-form and CF ₃ CH = CHCF _{3 to} the total amount of the foaming agent is 50 to 100% by mass. The production method according to claim 1 or 2, wherein the ratio of the Z-form of CF ₃ CF = CHCl to the total amount of the Z-form of CF ₃ CF = CHCl and CF ₃ CH = CHCF ₃ is 1 to 99% by mass. .. Wherein the blowing agent further contains E of _CF 3 CF = _CHCl, the proportion of the E isomer of _CF 3 CF = CHCl for Z of CF 3 CF = CHCl is less than 0.1% by weight to 10% by weight The manufacturing method according to any one of claims 1 to 3. The production method according to any one of claims 1 to 4, wherein the amount of the foaming agent is 10 to 100 parts by mass with respect to 100 parts by mass of the polyol. The production method according to any one of claims 1 to 5, wherein the polyol contains a polyether polyol. The production method according to claim 6, wherein the ratio of the polyether polyol to the total amount of the polyol is 10 to 100% by mass. The production method according to claim 6 or 7, wherein the polyether polyol is a Mannich polyol obtained by ring-opening addition of an alkylene oxide to a Mannich condensation product obtained by reacting phenols, an aldehyde, and an alkanolamine. .. The production method according to any one of claims 1 to 8, wherein the obtained rigid foamed synthetic resin has a density of 5 to 300 kg / m ³ . A system liquid containing a polyol, a foaming agent, a foam stabilizer, and a catalyst, wherein the weight average molecular weight of the polyol is 100 to 3000, and the foaming agent is a Z-form of CF ₃ CF = CHCl and CF ₃ CH = CHCF _3. A system fluid characterized by containing and. The system solution according to claim 10, wherein the ratio of the total amount of CF ₃ CF = CHCl Z-form and CF ₃ CH = CHCF ₃ to the total amount of the foaming agent is 50 to 100% by mass. The system solution according to claim 10 or 11, wherein the ratio of the Z-form of CF ₃ CF = CHCl to the total amount of the Z-form of CF ₃ CF = CHCl and CF ₃ CH = CHCF ₃ is 1 to 99% by mass. .. Wherein the blowing agent further contains E of _CF 3 CF = _CHCl, the proportion of the E isomer of _CF 3 CF = CHCl for Z of CF 3 CF = CHCl is less than 0.1% by weight to 10% by weight The system solution according to any one of claims 10 to 12.