JP2004346297A - Method for producing hard polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce a polyurethane foam having good moldability. <P>SOLUTION: The hard polyurethane foam is produced by reacting an active hydrogen component (A) with an organic polyisocyanate (B) in the presence of a foaming agent. The component (A) comprises a compound (a) containing an unsaturated double bond or bonds and an active hydrogen-containing group or groups, a polyol (b) and a primary and/or a secondary amine (c). The amount of (c) in (A) is 1-5 mass%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a polyurethane foam. More particularly, it relates to a method for producing a rigid polyurethane foam.

Rigid polyurethane foams are widely used because of their excellent heat insulating performance, dimensional stability, workability, and the like.
A method for producing a polyurethane foam having excellent mechanical properties by reacting a compound having an active hydrogen-containing group and an addition-polymerizable functional group, or an active hydrogen component comprising the compound with another active hydrogen-containing compound, and a polyisocyanate ( Patent document 1) is known.
International Publication WO98 / 44016

  However, when the production method described in the above publication is used, the mechanical properties are good, but the moldability may be insufficient depending on the production conditions.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, by using a compound having an unsaturated double bond and an active hydrogen-containing group in combination with a specific active hydrogen-containing compound, The inventors have found that the above problems can be solved, and have reached the present invention.

That is, the present invention includes the following (I) and (II).
(I) A method for producing a rigid polyurethane foam by reacting an active hydrogen component (A) with an organic polyisocyanate (B) in the presence of a foaming agent, wherein (A) contains an unsaturated double bond and active hydrogen It contains a compound (a) having a group, a polyol (b), and a primary and / or secondary amine (c), and the amount of (c) in (A) is 0.1 to 5% by mass. A method for producing a rigid polyurethane foam, comprising:
(II) A heat insulating material made of a rigid polyurethane foam obtained by the above production method.

  According to the method for producing a rigid polyurethane foam of the present invention, a polyurethane foam having good moldability can be obtained. Further, a foam having a good cell state, excellent dimensional stability, and high mechanical strength can be obtained. Furthermore, when the active hydrogen component used in the present invention is used, the viscosity is lower than that of the conventional active hydrogen component, so that the workability during foam molding is excellent.

In the production method of the present invention, (a) contained in the active hydrogen component (A) as an essential component is a compound having at least one unsaturated double bond and at least one active hydrogen-containing group.
The unsaturated double bond is usually an addition polymerizable group, and may be a terminal olefin type or an internal olefin type. Examples thereof include a (meth) acryloyl group, a croton group, an allyl group, a propenyl group, a 1-butenyl group, One or more selected from 2-butenyl groups and the like are included. Among these, a (meth) acryloyl group, an allyl group and a propenyl group are preferred, and a (meth) acryloyl group and an allyl group are more preferred. Here, the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group, and the same description method will be used hereinafter.
The number of unsaturated double bonds in (a) is usually 1 or more, preferably 1 to 10, and more preferably 1 to 5.

Examples of the active hydrogen-containing group (a) include one or more selected from a hydroxyl group, a mercapto group, a carboxyl group, a primary amino group, and a secondary amino group. Preferred are a hydroxyl group, a mercapto group and a carboxyl group, more preferred are a hydroxyl group and a mercapto group, and particularly preferred are a hydroxyl group.
The number of active hydrogen-containing groups in (a) is usually 1 or more, preferably 1 to 8, more preferably 1 to 5.

Specific examples of the above (a) include the following (a1) to (a3), and two or more kinds may be used in combination.
(A1) a polyol [derived from a polyhydric alcohol, a polyhydric phenol, an alkylene oxide (hereinafter abbreviated as AO) adduct of a polyhydric alcohol or a polyhydric phenol, an AO adduct of an amine, a polyhydric alcohol and a polycarboxylic acid or a lactone. Unsaturated carboxylic acid partial ester or partially unsaturated alkyl ether [particularly (meth) acrylate or allyl ether]
(A2) Unsaturated carboxylic acid partially amidated or partially unsaturated alkylated amine [particularly partially (meth) acrylamidated or allylic compound]
(A3) Unsaturated carboxylic acid partial thioester or partially unsaturated alkylthioether of polythiol [particularly (meth) acryl thioester or allylic compound]

  Examples of the polyhydric alcohol used in the production of (a1) include dihydric alcohols having 2 to 18 (preferably 2 to 12) carbon atoms [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4- and 1 , 3-butanediol, 1,6-hexanediol, neopentyl glycol, etc.], a C3-18 (preferably 3-12) tri- to pentavalent alcohol [alkane polyol and its intramolecular or intermolecular dehydrates] For example, glycerin, trimethylolpropane, pentaerythritol, sorbitan, diglycerin; saccharides and derivatives thereof, for example, α-methylglucoside, xylitol, glucose, fructose; etc.], and 5 to 18 carbon atoms (preferably 5 to 12 A) 6 to 10 or more Cole [6 to 10 valent alkane polyols and intramolecular or intermolecular dehydrates of 3 to 5 valent alkane polyols such as dipentaerythritol; saccharides and derivatives thereof such as sorbitol, mannyl, sucrose; And combinations of two or more of these.

  Examples of the polyhydric phenol used in the production of (a1) include dihydric phenols [monocyclic dihydric phenol (hydroquinone, etc.), bisphenols (bisphenol A, bisphenol F, etc.), and tri- to pentahydric phenols [monocyclic polyphenols Phenols (pyrogallol, phloroglucin, etc.), trivalent to pentavalent, low-condensation products of formalin of phenolic compounds (number average molecular weight: 1000 or less) (intermediates of novolak resins and resols), etc .; [Hexavalent or higher phenol compound formalin low-condensate (number average molecular weight of 1000 or less) (novolak resin, resol intermediate), etc.], condensate of polyhydric phenol and alkanolamine (Mannich polyol), and these Two or more of them may be used in combination.

  Among the polyols used in the production of (a1), examples of the amine in the AO adduct of an amine include ammonia; an alkanolamine having 2 to 20 carbon atoms [mono-, di- or triethanolamine, isopropanolamine, aminoethylethanol Amines]; alkylamines having 1 to 20 carbon atoms [methylamine, ethylamine, n-butylamine, octylamine, etc.]; alkylenediamines having 2 to 6 carbon atoms [ethylenediamine, hexamethylenediamine, etc.]; 2 to 6 polyalkylene polyamines (degree of polymerization 2 to 8) [diethylene triamine, triethylene tetramine, etc.]; aromatic amines having 6 to 20 carbon atoms [aniline, phenylenediamine, tolylenediamine, xylylenediamine, methylenedianiline, Diphenyl -Terdiamine, naphthalenediamine, anthracenediamine, etc.); an alicyclic amine having 4 to 15 carbon atoms [isophoronediamine, cyclohexylenediamine, etc.]; a heterocyclic amine having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1 , 4-diaminoethylpiperazine, etc.] and a combination of two or more of these.

  Examples of AO to be added to polyhydric alcohol, polyhydric phenol or amine include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-, 1,3-, 1,4 -Or 2,3-butylene oxide, α-olefin oxide (5 to 30 or more carbon atoms), styrene oxide and the like and a combination of two or more thereof (when used in combination, random addition, block addition, Or any combination thereof). Among these AOs, those having 2 to 8 carbon atoms are preferable, and those containing PO and / or EO as a main component and optionally containing 20% or less of other AO are more preferable. The addition reaction can be performed by a conventionally known ordinary method. The number of moles of AO added per molecule is preferably 1 to 70, and more preferably 1 to 50. Above and below,% means mass% unless otherwise specified.

  Among the polyols used in the production of (a1), the polyhydric alcohols used for the polyester polyols include the same ones as described above. Examples of the polycarboxylic acids include aliphatic polycarboxylic acids having 4 to 18 carbon atoms [succinic acid , Adipic acid, sebacic acid, maleic acid, fumaric acid, etc.], aromatic polycarboxylic acids having 8 to 18 carbon atoms [phthalic acid or its isomers, trimellitic acid, etc.], and ester-forming derivatives of these polycarboxylic acids [An acid anhydride, a lower alkyl ester having 1 to 4 carbon atoms in the alkyl group, etc.] and a combination of two or more of these. Examples of the lactone include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and a combination of two or more of these.

  As the polyol used in the production of (a1), those having 2 to 8 (particularly 2 to 6) hydroxyl groups and an OH equivalent of 30 to 1200 are preferable. The upper limit of the OH equivalent is more preferably 300.

In the case of (a1) in which a partial (meth) acrylate and a partial allyl ether are used as an example, for example, the polyol exemplified above may be used in such a manner that at least one hydroxyl group remains in one molecule without being reacted. It is obtained by partial (meth) acryloylation or allylation using (meth) acrylic or allyl halide in equivalent ratio. As the (meth) acrylic halide, (meth) acryloyl chloride, (meth) acryloyl bromide, (meth) acryloyl iodide, and as the allyl halide, allyl chloride, allyl bromide, allyl iodide and the two kinds thereof Combinations of the above may be mentioned.
(A1) can also be obtained by adding the above-mentioned AO to 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid, or allyl alcohol. In this case, among the AOs, those containing PO and / or EO as a main component and optionally containing 20% or less of other AO are preferable. The addition reaction can be performed by a conventionally known ordinary method. The number of moles of AO added is preferably 1 to 70, and more preferably 1 to 50.

  (A2) is a polyamine or alkanolamine among the above-mentioned amines and the above-mentioned (meth) acrylic or allyl halide having at least one amino group or hydroxyl group (in the case of alkanolamine) in one molecule. It is obtained by reacting at an equivalent ratio that remains unreacted.

As the polythiol used for the production of (a3), those having 2 to 4 thiol groups and having 2 to 18 carbon atoms are preferable. For example, ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-propanedithiol, 1,4-benzenedithiol, 1,2-benzenedithiol, bis (4-mercaptophenyl) sulfide, 4-t-butyl-1,2-benzenedithiol, ethylene glycol dithioglycolate, tri Methylolpropane tris (thioglycolate) thiocyanuric acid, di (2-mercaptoethyl) sulfide, di (2-mercaptoethyl) ether, and a combination of two or more of these.
(A3) is obtained by reacting the above polythiol with the above-mentioned (meth) acrylic halide or allyl halide in an equivalent ratio such that at least one thiol group remains unreacted in one molecule. .

  Among these (a), (a1) and (a2) are preferable, (a1) is more preferable, and particularly preferable is a partial allyl ether of a polyhydric alcohol or an AO adduct thereof, and a polyhydric alcohol. Alternatively, it is a partial (meth) acrylate of the AO adduct.

In the production method of the present invention, the amount of (a) used is preferably 0.1 to 70% in (A). The lower limit is preferably 0.2%, particularly preferably 1%, and the upper limit is more preferably 60%, particularly preferably 50%. When it is within the above range, both the moldability and the dimensional stability are good.

In the production method of the present invention, in addition to (a), the active hydrogen component (A) further contains a polyol (b) and a primary and / or secondary amine (c) as essential components.
(B) is a polyol having no unsaturated double bond, and is an AO adduct of an aliphatic amine (b1), an AO adduct of an aromatic amine (b2), an AO adduct of a polyhydric alcohol (b3), and a polymer Polyol (b4) and the like may be mentioned, and two or more kinds may be used in combination.
Examples of the aliphatic amine of (b1) include primary and secondary amines, and the number of primary and secondary amino groups is preferably 1 to 4, more preferably 1 to 3, and The number of active hydrogens derived is preferably 2 to 8, more preferably 2 to 4.
Specific examples of (b1) include the alkanolamines, alkylamines having 1 to 20 carbon atoms, alkylenediamines having 2 to 6 carbon atoms, and alkylene diamines having 2 to 6 carbon atoms described in the above section (a1). Polyalkylene polyamines (degree of polymerization 2 to 8). Preferred are alkanolamines and alkylenediamines.
The preferred AO to be added is one containing PO and / or EO as a main component and optionally containing 20% or less of other AO, and particularly preferred is PO or a combination of PO and EO.
The AO addition reaction can be carried out by a conventionally known ordinary method, and as a catalyst used at the time of addition, in addition to a commonly used alkali catalyst (KOH, CsOH, etc.), a catalyst described in JP-A-2000-3444881, [ Tris (pentafluorophenyl) borane, etc.], and the catalyst described in JP-A-11-120300 (magnesium perchlorate, etc.) may be used (the same applies to the following AO adducts).
The hydroxyl value of (b1) is preferably from 30 to 1800. The lower limit is more preferably 40, particularly preferably 140, and the upper limit is more preferably 1600.

Examples of the aromatic amine (b2) include the aromatic amines having 6 to 20 carbon atoms described in the above section (a1). Preferred are aniline, phenylenediamine, and tolylenediamine.
Preferred as the AO to be added are those containing PO and / or EO as a main component and optionally containing 20% or less of other AO, and particularly preferred are PO and a combination of PO and EO. The hydroxyl value is preferably from 30 to 1800. The lower limit is more preferably 40, particularly preferably 140, and the upper limit is more preferably 1600.

Examples of the polyhydric alcohol of (b3) include those exemplified as the polyhydric alcohol used in the production of (a1).
Examples of the polyhydric phenol of (b3) include those exemplified as the polyhydric phenol used in the production of (a1).
Among them, dihydric alcohols and dihydric phenols are preferable, and dihydric phenols are more preferable.
Preferred as AO to be added to these are those containing PO and / or EO as a main component and optionally containing 20% or less of other AO, and particularly preferred are PO and a combination of PO and EO. is there.
The hydroxyl value of (b3) is preferably from 30 to 1800. The lower limit is more preferably 40, particularly preferably 140, and the upper limit is more preferably 800.

Examples of the polymer polyol (b4) include those commonly used for polyurethane foams, for example, the polyether polyol obtained by adding the above-mentioned AO to the above-mentioned polycarboxylic acid, the above-mentioned polyester polyol and its AO adduct, and low-molecular-weight polyol (for example, Polymer polyols obtained by polymerizing vinyl monomers (acrylonitrile, styrene, etc.) in one or more polyols selected from the above-mentioned polyhydric alcohols), the above-mentioned alkanolamines, and the above-mentioned (b3), and mixtures thereof. . Preferred as the above-mentioned AO are those containing PO and / or EO as a main component and optionally containing 20% or less of other AO, particularly preferably PO and / or EO. Among these, the polymer polyol obtained from (b3) is preferred.
The production method (b4) can be carried out in the same manner as in the polymerization method for a conventional polymer polyol. For example, a method of polymerizing a vinyl monomer in the presence of a polymerization initiator in a polyol containing a dispersant as necessary (US Pat. No. 3,383,351, JP-B-39-24737, JP-B-47-47999 or JP-A-50-15894). The polymerization can be carried out in a batch system or a continuous system, and can be carried out under normal pressure, under pressure or under reduced pressure. If necessary, a solvent and a chain transfer agent can be used.

The volume average particle diameter of the polymer (b4) is preferably from 0.5 to 15 μm. Further, the hydroxyl value of (b4) is preferably from 20 to 1810. The lower limit is more preferably 24, particularly preferably 100, and the upper limit is more preferably 1500.
The polymer content in (b4) is preferably 5 to 40%, and more preferably 10 to 30%. The polymer content in (A) is preferably 10% or less, more preferably 0.1 to 5%.

  As (b), those containing (b1), (b2), and (b4) are preferable, and those containing (b1) to (b4) are more preferable.

In the production method of the present invention, the content of (b1) in (A) is preferably 50% or less from the viewpoint of moldability and dimensional stability. The lower limit is more preferably 5%, particularly preferably 10%, and the upper limit is more preferably 48%, particularly preferably 45%. The content of (b2) is preferably 50% or less. The lower limit is more preferably 10%, particularly preferably 15%, and the upper limit is more preferably 45%, particularly preferably 40%. The content of (b3) is preferably 50% or less. The lower limit is more preferably 5%, and the upper limit is more preferably 40%. The content of (b4) is preferably 20% or less. The lower limit is more preferably 1%, and the upper limit is more preferably 10%.
Further, the total content of (b) is preferably 25 to 99%. Preferably, the lower limit is 50% and the upper limit is 90%.

  The number of primary and / or secondary amines of the primary and / or secondary amine (c) is preferably 1 to 4, more preferably 1 to 3, and the number of active hydrogens derived from the amino group is It is preferably 2 to 8, more preferably 2 to 4. The molecular weight of (c) is preferably 400 or less, more preferably 300 or less.

(C) is preferably a primary and / or secondary amine containing no tertiary amino group. Specific examples include aromatic hydrocarbon-based poly (2-8 or more, especially divalent) amines having 6 to 24 carbon atoms, such as 2,4- and / or 2,6-tolylenediamine (TDA) , Crude TDA, 1,2-, 1,3- or 1,4-phenylenediamine, 3,5-diethyl-2,4- and / or 3,5-diethyl-2,6-tolylenediamine, 1 , 2-, 1,3- or 1,4-xylylenediamine, 2,4'- and / or 4,4'-diaminodiphenylmethane (MDA), crude MDA, naphthylene-1,5-diamine, 3, 3'-dichloro-4,4'diaminodiphenylmethane; an aromatic hydrocarbon monoamine having 6 to 24 carbon atoms, for example, aniline, methylaniline, phenylaniline; a heterocyclic mono or poly (2 to 3 carbon atoms having 2 to 24 carbon atoms) Octavalent or higher, especially divalent) amines, for example 2-, 3- or 4-aminopyridine, imidazole, piperazine, piperidine, morpholine; C2-24 aliphatic poly (2-8 or higher) And especially divalent to tetravalent) amines such as ethylenediamine and diethylenetriamine; and aliphatic monoamines having 2 to 24 carbon atoms such as propylamine, isopropylamine, ethylamine, diethylamine, allylamine, monoethanolamine and diethanolamine.
Of these, aromatic hydrocarbon diamines, aromatic hydrocarbon monoamines, and aliphatic polyamines are preferred, and aromatic hydrocarbon diamines are more preferred, and TDA and diethyl tolylene diamine are particularly preferred. Amines, and MDA.

  In the production method of the present invention, the content of (c) in (A) is 0.1 to 5%. The lower limit is preferably 0.5% and the upper limit is preferably 3%. If it is less than 0.1%, poor appearance of the foam occurs. On the other hand, if it exceeds 5%, the reactivity becomes faster and the moldability deteriorates.

  In the production method of the present invention, the number average molecular weight of (A) (based on gel permeation chromatography) is preferably from 60 to 10,000. The lower limit is more preferably 70, and the upper limit is more preferably 8,000. The hydroxyl value of (A) is preferably from 30 to 1800. The lower limit is more preferably 40 and the upper limit is more preferably 800.

  As the organic polyisocyanate (B) used in the production method of the present invention, those conventionally used for polyurethane foams can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof.

Examples of the aromatic polyisocyanate include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbon in the NCO group; the same applies to the following isocyanates), aromatic triisocyanates having 6 to 20 carbon atoms, crude products of these isocyanates, and the like. Is mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4 Examples include 4′-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate.
Examples of the aliphatic polyisocyanate include an aliphatic diisocyanate having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include an alicyclic diisocyanate having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.
Specific examples of the modified polyisocyanate include urethane modified MDI, carbodiimide modified MDI, sucrose modified TDI, castor oil modified MDI, and the like.
Of these, preferred are at least one organic polyisocyanate selected from TDI, MDI, crude TDI, crude MDI, sucrose-modified TDI, urethane-modified MDI, and carbodiimide-modified MDI.

Water, hydrogen atom-containing halogenated hydrocarbons, low-boiling hydrocarbons, liquefied carbon dioxide and the like are used as the blowing agent used in the production method of the present invention.
Specific examples of the hydrogen atom-containing halogenated hydrocarbon include those of the HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123, HCFC-141b, HCFC-22 and HCFC-142b); those of the HFC (hydrofluorocarbon) type ( For example, HFC-134a, HFC-152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, HFC-227ea) and the like. Preferred among these are HCFC-141b, HFC-245fa and HFC-365mfc and mixtures of two or more thereof. Low boiling hydrocarbons are hydrocarbons having a boiling point of usually -5 to 70 ° C, and specific examples thereof. Examples include butane, pentane, cyclopentane, and mixtures thereof. Of these, cyclopentane is preferred.
Among these foaming agents, it is preferable to use a hydrogen atom-containing halogenated hydrocarbon and / or a low-boiling hydrocarbon, and to use water and / or liquefied carbon dioxide gas (particularly water) if necessary.

In the production method of the present invention, the hydrogen atom-containing halogenated hydrocarbon is preferably used in an amount of 50 parts or less per 100 parts of (A). The lower limit is more preferably 10 parts, particularly preferably 15.5 parts, and most preferably 16 parts, and the upper limit is more preferably 48 parts, particularly preferably 45 parts. Above and below, parts mean parts by weight.
The low boiling hydrocarbon is preferably used in an amount of 40 parts or less per 100 parts of (A). The lower limit is more preferably 10 parts, particularly preferably 15.5 parts, and most preferably 16 parts, and the upper limit is more preferably 30 parts, particularly preferably 25 parts.
When a hydrogen atom-containing halogenated hydrocarbon is used in combination with water, water is used in an amount of preferably not more than 10 parts per 100 parts of (A) in addition to the above amount of hydrogen atom-containing halogenated hydrocarbon. The lower limit is more preferably 0.1 part, and the upper limit is more preferably 8 parts. When a low-boiling hydrocarbon and water are used in combination, in addition to the above-mentioned amount of low-boiling hydrocarbon, water is preferably used in an amount not exceeding 10 parts per 100 parts of (A). The lower limit is more preferably 0.1 part, and the upper limit is more preferably 8 parts.
When the hydrogen atom-containing halogenated hydrocarbon and the liquefied carbon dioxide gas are used in combination, in addition to the above amount of the hydrogen atom-containing halogenated hydrocarbon, the amount of the liquefied carbon dioxide gas preferably does not exceed 25 parts per 100 parts of (A). Is used. The lower limit is more preferably 0.1 part, and the upper limit is more preferably 20 parts. When low-boiling hydrocarbons and liquefied carbon dioxide are used in combination, in addition to the above-mentioned amount of low-boiling hydrocarbons, liquefied carbon dioxide is preferably used in an amount not exceeding 25 parts per 100 parts of (A). The lower limit is more preferably 0.1 part, and the upper limit is more preferably 20 parts.
When water is used alone, preferably not more than 15 parts per 100 parts of (A). The lower limit is more preferably 0.5 part, and the upper limit is more preferably 10 parts.
When a hydrogen atom-containing halogenated hydrocarbon and a low boiling point hydrocarbon are used in combination, the mass ratio of the hydrogen atom-containing halogenated hydrocarbon / low boiling point hydrocarbon is preferably from 1/99 to 99/1, and more preferably. 3/97 to 97/3.
The mass ratio when the hydrogen atom-containing halogenated hydrocarbon and / or low boiling point hydrocarbon is used in combination with a foaming agent other than these (water, liquefied carbon dioxide gas, particularly water) is preferably 100/0 to 65/35. And more preferably 99/1 to 70/30, particularly preferably 98/2 to 80/20.

In the production method of the present invention, if necessary, the reaction may be carried out in the presence of another auxiliary component as described below.
For example, foam stabilizers (dimethylsiloxane-based, polyether-modified dimethylsiloxane-based, etc.), urethanization catalysts (tertiary amine-based catalysts such as triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N ', N '-Tetramethylhexamethylenediamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, diaminobicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole, 1-isobutyl-2-methylimidazole, 1,8-diazabicyclo- [5, 4,0] -undecene-7 and / or metal catalysts such as stannous octylate, dibutylstannic dilaurate, lead octylate and the like, radical polymerization initiators [azo compounds such as 2,2′- Azobisisobutyronitrile, 2 2′-azobis (2,4-dimethylvaleronitrile); organic peroxides such as dibenzoyl peroxide, t-butyl hydroperoxide; inorganic peroxides such as persulfate; etc.), coloring agents (dyes, Pigments), plasticizers (phthalates, adipates, etc.), organic fillers (synthetic short fibers, hollow microspheres made of thermoplastic or thermosetting resin, etc.), flame retardants (phosphate esters, halogenated phosphoric acid) The reaction can be performed in the presence of known auxiliary components such as an ester, an antioxidant (such as a triazole or a benzophenone), and an antioxidant (such as a hindered phenol or a hindered amine). Further, an auxiliary component using (a) as a diluent in (A) [for example, a solution of an amine-based catalyst (a)] may be used.

  (A) With respect to the use amount of these auxiliary components per 100 parts, the foam stabilizer is preferably 10 parts or less, more preferably 0.5 to 5 parts. The amount of the urethanization catalyst is preferably 10 parts or less, more preferably 0.2 to 5 parts. The amount of the radical polymerization initiator is preferably 5 parts or less, more preferably 0.01 to 1 part. The colorant is preferably at most 1 part. The amount of the plasticizer is preferably 10 parts or less, more preferably 5 parts or less. The amount of the organic filler is preferably 50 parts or less, more preferably 30 parts or less. The amount of the flame retardant is preferably 30 parts or less, more preferably 5 to 20 parts. The amount of the antioxidant is preferably 1 part or less, more preferably 0.01 to 0.5 part. The amount of the antioxidant is preferably 1 part or less, more preferably 0.01 to 0.5 part.

  The isocyanate index (NCO INDEX) [equivalent ratio of (NCO group / active hydrogen atom-containing group) × 100] in the method for producing a polyurethane foam of the present invention is preferably 80 to 150, more preferably 85 to 135, and particularly preferably. 90-130.

An example of a method for producing a polyurethane foam according to the method of the present invention is as follows.
First, a predetermined amount of the active hydrogen component (A) and, if necessary, a foaming agent, a foam stabilizer, and other auxiliary components are mixed. This mixture is then rapidly mixed with the organic polyisocyanate (B) using a polyurethane foaming machine or a stirrer. The obtained mixed solution (foaming stock solution) is poured into a mold, cured for a predetermined time, and then demolded to obtain a polyurethane foam. The mold may be either an open mold or a closed mold, and may be room temperature or heated (for example, 40 to 80 ° C.). Further, a polyurethane foam can be obtained by spray foaming or continuous foaming. When a closed mold is used, the pack ratio is preferably 100 to 500%, more preferably 105 to 350%, and particularly preferably 110 to 250%. (Pack ratio) = [(form mass) / (minimum foam mass for filling in the closed mold)] × 100. In the urethanization reaction, the one-shot method is preferred because the viscosity of the stock solution obtained by mixing the components increases in the prepolymer method.
The method of the present invention can be applied to both slab foam production and RIM (reaction injection molding) molding. Further, it can be used to obtain polyurethane by a mechanical floss method.

The rigid polyurethane foam obtained by the production method of the present invention preferably has a molecular weight between crosslinking points of 400 to 700. Further, the density is preferably 0.02 to 0.5 g / cm ³ . The lower limit is more preferably 0.025 g / cm ³ , and the upper limit is more preferably 0.1 g / cm ³ .

  Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. In the following, a ratio indicates a mass ratio.

The compositions, symbols, and the like of the raw materials used in Examples and Comparative Examples are as follows.
(1) Active hydrogen component (b1)
b11: Polyol having a hydroxyl value of 750 obtained by adding PO to ethylenediamine b12: Polyol having a hydroxyl value of 810 obtained by blocking addition of 1 mol of EO to ethylenediamine and about 3 mol of PO b13: Hydroxyl value of 360 obtained by adding PO to triethanolamine Polyol (2) active hydrogen component (b2)
b21: a polyol having a hydroxyl value of 500 obtained by block-adding 2 mol of EO and about 4 mol of PO to 1 mol of 2,4- and 2,6-tolylenediamine (2,4- / 2,6-ratio: 80/20) b22: Polyol having a hydroxyl value of 400 obtained by block addition of 2 mol of EO and about 7 mol of PO to 1 mol of 2,4- and 2,6-tolylenediamine (2,4- / 2,6- ratio: 80/20) .
(3) Active hydrogen component (b3)
b31: Polyol with a hydroxyl value of 400 in which PO is added to glycerin b32: Polyol with a hydroxyl value of 400 in which PO is added to pentaerythritol b33: Polyol with a hydroxyl value of 420 in which PO is added to sucrose b34: PO in bisphenol A (4) Active hydrogen component (b4)
b41: PO adduct of glycerin (hydroxyl value: 670), PO3 mol adduct of bisphenol A, and EO block adduct of glycerin after EO / PO random addition [EO unit content 25% (including internal EO unit 5%) Styrene / acrylonitrile (ratio: 20/80) in a mixture of 7: 2: 1 with a hydroxyl value of 28] (polyol having a hydroxyl value of 400) (polymer content: 20%).
(5) Active hydrogen component (c)
c1: 2,4- and 2,6-tolylenediamine (2,4- / 2,6-ratio: 80/20) (TDA)
c2: 3,5-diethyl-2,4- and 3,5-diethyl-2,6-tolylenediamine (ratio 2,4- / 2,6-: 80/20)
c3: 4,4'-diaminodiphenylmethane (MDA)

(6) Organic polyisocyanate (B)
MDI: Crude MDI [“MR-200” manufactured by Nippon Polyurethane Industry Co., Ltd.]
(7) Catalyst f1: "U-cat (registered trademark) 430A" amine catalyst [manufactured by San Apro Corporation]
f2: diaminobicyclooctane [“Dabco33LV” manufactured by Sankyo Air Products Co., Ltd.]
f3: N, N, N ′, N′-tetramethylhexamethylenediamine [“U-cat (registered trademark) 1000” manufactured by San Apro Corporation]
f4: Pentamethyldiethylenetriamine [“Polycat (registered trademark) -5” [manufactured by San Apro Co., Ltd.]
(8) Foam stabilizer g1: "F-388" polyether siloxane polymer [Shin-Etsu Silicone Co., Ltd.]
g2: "SH-193" polyether siloxane polymer [manufactured by Toray Dow Corning Silicone Co., Ltd.]
(9) Flame retardant h: "TMCPP" organophosphorus flame retardant (manufactured by Akzo Japan)
(10) Radical polymerization initiator i: t-butyl hydroperoxide (“Perbutyl H-69” manufactured by NOF Corporation)
(11) Foaming agent j1: HCFC-141b
j2: HFC-245fa
j3: HFC-365mfc
j4: Cyclopentane

Production Example 1 (Production example of diallyl product of polyol)
252 parts (1 mol) of a compound obtained by adding 2 mol of PO to 1 mol of pentaerythritol is reacted with 153 parts (2 mol) of allyl chloride using 80 parts (2 mol) of NaOH as a catalyst to obtain a diallyl compound of pentaerythritol (a11). Got.

Production Example 2 (Production example of PO adduct of allyl alcohol)
58 parts (1 mol) of allyl alcohol is reacted with 116 parts (2 mol) of PO using 0.56 part (0.001 mol) of potassium hydroxide as a catalyst, neutralized with phosphoric acid, and PO adduct of allyl alcohol is obtained. (A12) was obtained.

Production Example 3 (Production example of polyol monoacrylate)
Acrylic acid (72 parts (1 mol)) was reacted with sulfuric acid (0.3 parts (0.003 mol)) using diethylene glycol (106 parts (1 mol)) as a catalyst, and potassium hydroxide (0.34 part (0.006 mol)). After neutralization, 0.16 parts (0.1%) of hydroquinone was added as a stabilizer to obtain diethylene glycol monoacrylate (a13).

Production Example 4 (Production example of polyol triacrylate)
Using 216 parts (3 mol) of acrylic acid and 0.9 part (0.009 mol) of sulfuric acid as a catalyst, 368 parts (1 mol) of a polyol (hydroxyl value 610) obtained by adding 4 mol of PO to 1 mol of pentaerythritol. The reaction was neutralized with 1.01 part (0.018 mol) of potassium hydroxide, and 0.53 part (0.1%) of hydroquinone was added as a stabilizer, and pentaerythritol PO4 mol adduct triacrylate (a14) was added. ) Got.

Production Example 5 (Production example of polyol diacrylate)
Using 288 parts (2 mol) of acrylic acid and 1.2 parts (0.012 mol) of sulfuric acid as a catalyst, 180 parts (1 mol) of sorbitol were reacted, and 1.35 parts (0.024 mol) of potassium hydroxide was used. The mixture was neutralized, and 0.60 parts (0.1%) of hydroquinone was added as a stabilizer to obtain sorbitol diacrylate (a15).

Manufacture of a foam for a panel-shaped heat insulating material for a transport machine <Examples 1 to 12 and Comparative Examples 1 to 12>
Using the compounds (a11 to a15) obtained in Production Examples 1 to 5 and the above-mentioned raw materials, polyurethane foams were produced by the following foaming formulations at the raw material mixing ratios shown in Tables 1 and 2. Tables 1 and 2 show the evaluation of physical properties of the obtained foam.

Production of foams for heat insulating materials for civil engineering constructions <Examples 13 to 24 and Comparative Examples 13 to 24>
Using the compounds (a11 to a15) obtained in Production Examples 1 to 5 and the above-mentioned raw materials, polyurethane foams were produced by the following foaming formulations at the raw material mixing ratios shown in Tables 3 to 5. Tables 3 to 5 show the evaluation of physical properties of the obtained foam.

<Method of foaming foam for panel-shaped heat insulating material for transport aircraft>
[1] The temperature of each of the active hydrogen component and the organic polyisocyanate is adjusted to 20 ± 2 ° C.
[2] An active hydrogen component, a foam stabilizer, water, a catalyst, and other additives are placed in a plastic beaker having a capacity of 500 ml in this order, and stirred and mixed at room temperature (20 ± 2 ° C.). An organic polyisocyanate in an amount of INDEX was added, and the mixture was stirred and foamed using a stirrer (Homodisper: manufactured by Tokushu Kika Co., Ltd., stirring condition: 5000 rpm × 7 seconds).
[3] After the stirring was stopped, the mixed solution was poured into a 400 × 400 × 50 mm aluminum mold adjusted to a temperature of 40 ° C. (pack ratio: 110%) and demolded after 10 minutes to obtain a rigid polyurethane foam. .

<Foaming prescription for insulation materials for civil engineering and construction>
[1] The temperature of each of the active hydrogen component and the organic polyisocyanate is adjusted to 20 ± 2 ° C.
[2] An active hydrogen component, a foam stabilizer, water, a catalyst, and other additives are placed in a plastic beaker having a capacity of 500 ml in this order, and stirred and mixed at room temperature (25 ± 2 ° C.). An organic polyisocyanate in an amount of INDEX was added, and the mixture was stirred and foamed using a stirrer (Homodisper: manufactured by Tokushu Kika Co., Ltd., stirring condition: 5000 rpm × 7 seconds).
[3] After stopping stirring, a 450 × 400 × 50 mm aluminum mold temperature-controlled to 60 ° C. (a 450 mm side is open on the lower surface, immediately after injection of the mixed solution, a kraft paper of 400 × 400 mm is stuck on the upper and lower surfaces in advance) The mixed liquid was poured into the upper mold of 450 × 400 mm so that the distance between the upper and lower surfaces was 50 mm, and the mold was removed after 5 minutes to obtain a rigid polyurethane foam.

The methods for evaluating foam properties in Tables 1 to 4 are as follows.
The test of the rigid polyurethane foam was carried out according to the usual test method of the rigid polyurethane foam. The dimensional stability was evaluated by cutting out a foam of 100 mm x 100 mm x 50 mm and leaving it for 1 day after molding (leaving at room temperature) and leaving it for 2 days at low temperature (-20 ° C) and moist heat (70 ° C, 95% humidity). Thereafter, the dimensions of each side were measured to determine the volume, and the rate of change in volume from one day after molding was determined. The compressive strength was measured in two directions, parallel and perpendicular to the foaming direction, based on the compressive strength test method of JIS A 9514 (1979 edition). The moldability was determined according to the following criteria based on the cell state of the obtained foam.
Formability ：: Good liquid landing point and cell condition
△: Liquid landing point, cell rough
×: There is roughening of the entire molded product cell

  The rigid polyurethane foam obtained by the production method of the present invention has high strength, good heat insulation, good flame retardancy, and particularly excellent dimensional stability, for example, a refrigerator, a freezer, a heat insulating material for buildings, etc. Widely available as.

Claims (5)

A method for producing a rigid polyurethane foam by reacting an active hydrogen component (A) with an organic polyisocyanate (B) in the presence of a foaming agent, wherein (A) has an unsaturated double bond and an active hydrogen-containing group. It contains the compound (a), the polyol (b), and the primary and / or secondary amine (c), and the amount of (c) in (A) is 0.1 to 5% by mass. Of producing rigid polyurethane foam. The method for producing a rigid polyurethane foam according to claim 1, wherein the amount of (a) in (A) is 0.1 to 70% by mass, and the amount of (b) is 25 to 99% by mass. (B) is an alkylene oxide adduct of an aliphatic amine (b1), an alkylene oxide adduct of an aromatic amine (b2), an alkylene oxide adduct of a polyhydric alcohol or polyphenol (b3), and a polymer polyol (b4) The method for producing a rigid polyurethane foam according to claim 1, comprising at least one member selected from the group consisting of: The rigid polyurethane foam according to any one of claims 1 to 3, wherein the unsaturated double bond in (a) is a (meth) acryloyl group and / or an allyl group, and the active hydrogen-containing group is a hydroxyl group and / or a mercapto group. Manufacturing method. A heat insulating material comprising a rigid polyurethane foam obtained by the production method according to claim 1.