JP2013018845A - Method of manufacturing polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide foam that is excellent in mechanical property even if a molding density of a polyurethane foam is decreased by a foaming agent that contains water and/or a low-boiling-point hydrocarbon.SOLUTION: The method of manufacturing a polyurethane foam comprises reacting an active hydrogen component (P) and an organic polyisocyanate (B) under the presence of a foaming agent (C), wherein (P) includes a strength improver (A) shown by General formula (I), and (C) includes water and/or a low boiling point hydrocarbon. In the General formula (I), R1 denotes a residue that excludes one active hydrogen from an active hydrogen-containing compound; two or more R1 each may be different or identical; Y denotes a residue that excludes a carboxyl group from an at least trivalent aromatic polycarboxylic acid (f); an aromatic ring is composed of a carbon atom; though a substituent of the aromatic ring may be a hydrogen atom or other substituents, at least one substituent is a hydrogen atom; a is an integer that satisfies 0≤a≤ (number of aromatic ring substituents-2); b is an integer that satisfies 0≤b≤ (number of aromatic ring substituents-2); a+b is an integer that satisfies 2≤a+b≤ (number of aromatic ring substituents-2); Z denotes a residue that excludes active hydrogen of m pieces from an active hydrogen-containing compound of at least m valencies; and m denotes an integer of 1-10.

Description

  The present invention relates to a method for producing a polyurethane foam.

In recent years, environmental considerations and cost reduction demands are strong, and there is a demand for lower density polyurethane foam.
At present, the amount of water used as a foaming agent tends to increase to meet the demand for lower density. Increasing the amount of water used (Non-patent Document 1, etc.) can increase the amount of carbon dioxide generated during foam production and is effective in reducing the density of polyurethane foam. When it falls, mechanical strength, such as compression hardness, will fall. As a specific technique for improving the hardness of the polyurethane foam, a method as in Patent Document 1 is known, but in such a method, workability is improved when density is reduced using low-boiling hydrocarbons. Therefore, depending on the production method, such as when the hydroxyl value of the raw material polyol is lowered to lower the viscosity of the reaction mixture, the compression hardness may be extremely reduced (particularly in the case of free foaming foam).

JP 2010-126546 A

Keiji Iwata, "Polyurethane Resin Handbook", Nikkan Kogyo, May 20, 1987, 1st Edition, 32 pages

  It is an object of the present invention to provide a polyurethane foam that can obtain a foam having excellent mechanical properties such as compression hardness even when the molding density of the polyurethane foam is reduced by a foaming agent containing water and / or a low-boiling hydrocarbon. It is to provide a manufacturing method.

  As a result of intensive studies to solve these problems, the present inventors have found that the strength of having a specific structure even when the molding density of polyurethane foam is reduced with a foaming agent containing water and / or low-boiling hydrocarbons. It has been found that a polyurethane foam having high mechanical properties (compression hardness, tensile strength, tear strength) can be obtained by using an improver, and the present invention has been achieved.

  That is, the polyurethane foam production method of the present invention is a method for producing a polyurethane foam by reacting an active hydrogen component (P) with an organic polyisocyanate (B) in the presence of a foaming agent (C). It contains a strength improver (A) represented by the following general formula (I), and (C) contains water and / or a low-boiling hydrocarbon.

[In general formula (I), R1 represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound. A plurality of R1 may be the same or different. ; Y represents the residue remove | excluding the carboxyl group from trivalent or more aromatic polycarboxylic acid (f). The aromatic ring is composed of carbon atoms. The substituent of the aromatic ring may be a hydrogen atom or another substituent, but at least one substituent is a hydrogen atom. A is an integer satisfying 0 ≦ a ≦ (the number of aromatic ring substituents−2). B is an integer satisfying 0 ≦ b ≦ (the number of aromatic ring substituents−2). A + b is an integer satisfying 2 ≦ a + b ≦ (the number of aromatic ring substituents−2). Z represents a residue obtained by removing m active hydrogens from an active hydrogen-containing compound having a valence of at least m; M represents an integer of 1 to 10; ]

  The present invention can obtain a polyurethane foam having high mechanical properties (compression hardness) in a method for producing a polyurethane foam in which the foaming agent contains water and / or a low-boiling hydrocarbon.

  In the present invention, the active hydrogen component (P) contains a strength improver (A) represented by the following general formula (I).

  In general formula (I), R1 represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound. Examples of the active hydrogen-containing compound include a hydroxyl group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, a thiol group-containing compound, and a phosphate compound; a compound having two or more active hydrogen-containing functional groups in the molecule. These active hydrogen-containing compounds can be used either alone or in combination. That is, the plurality of R1s may be the same or different.

Examples of the hydroxyl group-containing compound include monohydric alcohols, divalent to octavalent polyhydric alcohols, phenols and polyhydric phenols. Specifically, monohydric alcohols such as methanol, ethanol, butanol, octanol, benzyl alcohol, naphthylethanol; ethylene glycol, propylene glycol, 1,3 and 1,4-butanediol, 1,6-hexanediol, 1, Dihydric alcohols such as 10-decanediol, diethylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) benzene; glycerin and trimethylolpropane Trihydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl 4- to 8-valent alcohols such as lucoside and derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1, 3, 6 , 8-tetrahydroxynaphthalene, anthrol, phenols such as 1,4,5,8-tetrahydroxyanthracene and 1-hydroxypyrene; polybutadiene polyol; castor oil-based polyol; (co) heavy of hydroxyalkyl (meth) acrylate Examples thereof include polyfunctional (eg, 2-100 functional group) polyols such as coalesced and polyvinyl alcohol, condensates of phenol and formaldehyde (novolak), and polyphenols described in US Pat. No. 3,265,641.
(Meth) acrylate means methacrylate and / or acrylate, and the same applies hereinafter.

  Examples of the amino group-containing compound include amines, polyamines and amino alcohols. Specifically, ammonia; monoamines such as C1-C20 alkylamine (butylamine and the like) and aniline; aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; heterocyclics such as piperazine and N-aminoethylpiperazine Polyamines; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; aromatic polyamines such as phenylenediamine, tolylenediamine and diphenylmethanediamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and dicarboxylic acids Polyamide polyamine obtained by condensation with excess polyamine; polyether polyamine; hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide ( Etc. Haq acid dihydrazide and dihydrazide terephthalate), guanidine (butyl guanidine and 1-cyanoguanidine, etc.); dicyandiamide; and the like.

  Examples of the carboxyl group-containing compound include aliphatic monocarboxylic acids such as acetic acid and propionic acid; aromatic monocarboxylic acids such as benzoic acid; aliphatic polycarboxylic acids such as succinic acid, fumaric acid, sebacic acid and adipic acid; phthalic acid , Isophthalic acid, terephthalic acid, trimellitic acid, naphthalene-1,4 dicarboxylic acid, naphthalene-2,3,6 tricarboxylic acid, pyromellitic acid, diphenic acid, 2,3-anthracene dicarboxylic acid, 2,3,6- Examples thereof include aromatic polycarboxylic acids such as anthracentricarboxylic acid and pyrene dicarboxylic acid; polycarboxylic acid polymers (functional group number: 2 to 100) such as (co) polymers of acrylic acid, and the like.

  Examples of the thiol group-containing compound include monofunctional phenylthiol, alkylthiol, and polythiol compounds. Examples of the polythiol include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol and 1,6-hexanedithiol.

  Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

  As the active hydrogen-containing compound, a compound having two or more active hydrogen-containing functional groups (hydroxyl group, amino group, carboxyl group, thiol group, phosphate group, etc.) in the molecule can also be used.

  Further, as the active hydrogen-containing compound, an alkylene oxide adduct of the active hydrogen-containing compound can also be used.

  Examples of the alkylene oxide (hereinafter abbreviated as AO) to be added to the active hydrogen-containing compound include AO having 2 to 6 carbon atoms such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter referred to as PO). Abbreviation), 1,3-propyloxide, 1,2 butylene oxide, 1,4-butylene oxide, and the like. Of these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoints of properties and reactivity. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

  Further, as the active hydrogen-containing compound, an active hydrogen-containing compound (polyester compound) obtained by a condensation reaction between the active hydrogen-containing compound and a polycarboxylic acid (aliphatic polycarboxylic acid or aromatic polycarboxylic acid) is used. Can do. In the condensation reaction, one type of active hydrogen-containing compound and polycarboxylic acid may be used, or two or more types may be used in combination.

The aliphatic polycarboxylic acid means a compound that satisfies the following (1) and (2).
(1) One molecule has two or more carboxyl groups.
(2) The carboxyl group is not directly bonded to the aromatic ring.

  Aliphatic polycarboxylic acids include succinic acid, adipic acid, sebacic acid, maleic acid and fumaric acid.

The aromatic polycarboxylic acid means a compound that satisfies the following (1) to (3).
(1) One molecule has one or more aromatic rings.
(2) The number of carboxyl groups in one molecule is 2 or more.
(3) The carboxyl group is directly bonded to the aromatic ring.

  Aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 2,2'-bibenzyldicarboxylic acid, trimellitic acid, hemilitic acid, trimesic acid, pyromellitic acid and naphthalene-1,4 dicarboxylic acid, naphthalene Examples include aromatic polycarboxylic acids having 8 to 18 carbon atoms such as -2,3,6 tricarboxylic acid, diphenic acid, 2,3-anthracene dicarboxylic acid, 2,3,6-anthracentricarboxylic acid and pyrene dicarboxylic acid.

  Moreover, when performing condensation reaction of polycarboxylic acid and an active hydrogen containing compound, the anhydride and lower alkyl ester of polycarboxylic acid can also be used.

  From the viewpoint of handling the strength improver (A) and improving the mechanical properties (tensile strength, compression hardness) of the polyurethane foam, the active hydrogen-containing compound R1 includes a hydroxyl group-containing compound, an amino group-containing compound, and addition of these AOs. And polyester compounds obtained by condensation reaction of active hydrogen-containing compounds and polycarboxylic acids, more preferably methanol, ethanol, butanol, ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbitol, sucrose, benzyl alcohol, Phenol, methylamine, dimethylamine, ethylamine, diethylamine, butylamine, dibutylamine, phenylamine, diphenylamine, their EO and / or PO adducts and their active hydrogen compounds and phthalic acid and / or Condensates of isophthalic acid is preferred.

  In general formula (I), Y represents the residue remove | excluding the carboxyl group from trivalent or more aromatic polycarboxylic acid (f). The aromatic ring of Y is composed of carbon atoms. The substituent of the aromatic ring may be a hydrogen atom or another substituent, but at least one substituent is a hydrogen atom. That is, the aromatic ring of Y has at least one hydrogen atom bonded to the carbon atom constituting the aromatic ring.

  Other substituents are alkyl group, vinyl group, allyl group, cycloalkyl group, halogen atom, amino group, carbonyl group, carboxyl group, hydroxyl group, hydroxyamino group, nitro group, phosphino group, thio group, thiol group Aldehyde group, ether group, aryl group, amide group, cyano group, urea group, urethane group, sulfone group, ester group and azo group. From the viewpoint of improving mechanical properties (elongation, tensile strength, compression hardness) and cost, the other substituents are preferably an alkyl group, a vinyl group, an allyl group, an amino group, an amide group, a urethane group and a urea group.

  As the arrangement of substituents on Y, from the viewpoint of improving mechanical properties, two carbonyl groups are adjacent to each other, and hydrogen is arranged as a substituent between the third carbonyl group and the first or second carbonyl group. The structure is preferred.

  Examples of trivalent or higher aromatic polycarboxylic acids (f) constituting Y include trimellitic acid, hemilitic acid, trimesic acid, pyromellitic acid, naphthalene-2,3,6 tricarboxylic acid and 2,3,6-anthracene. An aromatic polycarboxylic acid having 8 to 18 carbon atoms such as tricarboxylic acid is exemplified.

  From the viewpoint of handling the strength improver (A) and improving the mechanical properties (compression hardness, tensile strength, tear strength) of polyurethane foam, (f) used for Y is preferably a monocyclic compound, more preferably trimellit. Acid and pyromellitic acid.

  In general formula (I), a is an integer that satisfies 0 ≦ a ≦ the number of aromatic ring substituents−2. The number of aromatic ring substituents is the number of substituents bonded to the carbon atoms constituting the aromatic ring. For example, a monocyclic aromatic ring composed of 6 carbons has 6 aromatic ring substituents, and a can be 0 to 4. When the aromatic ring is a monocyclic aromatic ring, a is preferably 2 or 3 from the viewpoint of improving mechanical properties (tensile strength, tear strength, compression hardness).

  In general formula (I), b is an integer satisfying 0 ≦ b ≦ number of aromatic ring substituents−2. For example, in a monocyclic aromatic ring composed of 6 carbons, the number of aromatic ring substituents is 6, and b can be 0 to 4. When the aromatic ring is a monocyclic aromatic ring, b is preferably 0 or 1 from the viewpoint of the curing rate of the foam.

  In the general formula (I), a + b is an integer satisfying 2 ≦ (a + b) ≦ the number of aromatic ring substituents−2. For example, a monocyclic aromatic ring composed of 6 carbons has 6 aromatic ring substituents, and can take 0 to 4 as a + b. When the aromatic ring is a monocyclic aromatic ring, a + b is preferably 2 or 3 from the viewpoint of improving mechanical properties (tensile strength, tear strength, compression hardness).

Z in the general formula (I) represents a residue obtained by removing m active hydrogens from an active hydrogen-containing compound having a valence of at least m. The active hydrogen-containing compound referred to here includes the active hydrogen-containing compound represented by R1 described above. The active hydrogen-containing compound represented by Z may be the same as a part of R1, but at least one of R1 and Z is preferably a different group.
In general formula (I), m represents an integer of 1 to 10.
From the viewpoint of handling the strength improver (A) and improving the mechanical properties (compression hardness, tensile strength, tear strength) of polyurethane foam, Z includes a hydroxyl group-containing compound, an amino group-containing compound, these AO adducts, and these It is preferable to use a condensate of polycarboxylic acid and m is preferably 1-8.

In the present invention, the hydroxyl value (mgKOH / g) of the strength improver (A) is preferably from 0 to 700, more preferably from 0 to 650, and further from the viewpoint of handling (viscosity) and tensile strength during molding. Preferably it is 0-600.
In the present invention, the hydroxyl value is measured in accordance with JISK-1557.
Moreover, that the hydroxyl value of (A) is 0 means that none of R1, Y, and Z has a hydroxyl group in general formula (I).

In the present invention, the aromatic ring concentration (mmol / g) of the strength improver (A) is preferably 0.1 to 10.0, more preferably 0.2 to 9.5, from the viewpoint of improving the tensile strength. More preferably, it is 0.3-9.0.
The aromatic ring concentration in (A) means the number of moles of aromatic rings in 1 g of the strength improver (A).

  The content of Y derived from (f) having 3 or more valences is 0.5 to 0.5 from the viewpoint of improving mechanical properties (compression hardness, tensile strength, tear strength) based on the number average molecular weight of the strength improver (A). It is preferably 50%, more preferably 4 to 47%, and still more preferably 6 to 45%.

  As active hydrogen component (P) used for this invention, the above-mentioned intensity | strength improving agent (A) should just be contained as an essential component. The component (P) other than (A) includes polyol (PL). When (A) has no active hydrogen, (P) preferably contains (PL). (PL) includes conventional polyols used in the production of polyurethane foam. (PL) is preferably a compound having a structure in which AO is added to an active hydrogen-containing compound.

Examples of (PL) include compounds having a structure in which AO is added to divalent to tetravalent or higher compounds among the active hydrogen-containing compounds, and two or more of them may be used in combination.
AO includes PO and EO. AO preferably contains only these, but may be an adduct in which other AO is used in combination within a range of 10% by weight or less (particularly 5% by weight or less) in AO.

The number average functional group number of the active hydrogen component (P) is 2 to 8. Even if the number of functional groups other than this range is included, the number average functional group number may be 2 to 8 (of other polyols). The same applies to the average number of functional groups). In the present invention, the number of functional groups of the polyol is considered to be the same as the number of functional groups of the starting material. In the present invention, the average functional group number means the number average functional group number.
The hydroxyl value of the active hydrogen component (P) is 10 to 1850 (mg KOH / g, and the following hydroxyl values are the same), and from the viewpoint of foam moldability, it is preferably 12 to 1500, more preferably 14 to 1000. .

  The content of (A) based on the weight of the active hydrogen component (P) is preferably 0.1 to 100% by weight, more preferably 1 to 98% by weight, from the viewpoint of moldability of the foam.

  As organic polyisocyanate (B) used by this invention, what is necessary is just a compound which has two or more isocyanate groups in a molecule | numerator, and what is normally used for manufacture of a polyurethane foam 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.

As aromatic polyisocyanate, C6-C16 aromatic diisocyanate, C6-C20 aromatic triisocyanate, and crude products of these isocyanates (excluding carbon in NCO group; the following isocyanates are also the same), etc. 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, Examples include 4′-diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, and the like.
Examples of the aliphatic polyisocyanate include aliphatic diisocyanates 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 alicyclic diisocyanates 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, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI, carbodiimide-modified MDI, sucrose-modified TDI, and castor oil-modified MDI.

  In the present invention, the reaction between the active hydrogen component (P) and the organic polyisocyanate (B) may be performed in the presence of the catalyst (D). As the catalyst (D), a usual catalyst for promoting the urethanization reaction can be used. Examples thereof include triethylenediamine, bis (N, N-dimethylamino-2-ethyl) ether, N, N, N ′, N '-Tetramethylhexamethylenediamine, tertiary amines such as PO adducts of N, N-dimethylaminopropylamine and their carboxylates, carboxylic acid metal salts such as potassium acetate, potassium octylate and stannous octoate, dibutyl And organometallic compounds such as tindilaurate.

As the foaming agent (C) in the present invention, water and / or a low boiling point hydrocarbon can be used.
In the present invention, the amount of water used in (C) is preferably 25% by weight or less, more preferably 0.1 to 24% by weight, from the viewpoint of moldability of the foam, based on the weight of the active hydrogen component (P). %.

The low boiling point hydrocarbon is a hydrocarbon having a boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, cyclopentane, and mixtures thereof. The boiling point of the low boiling point hydrocarbon is preferably 0 to 70 ° C. from the viewpoint of moldability.
From the viewpoint of moldability, the amount of the low-boiling hydrocarbon in (C) is preferably 70% by weight or less, more preferably 0 to 60% by weight, based on the weight of (P).
In addition to water and low-boiling hydrocarbons, liquefied carbon dioxide can also be used as a blowing agent. The amount of liquefied carbon dioxide used is preferably 30 parts by weight or less, more preferably 25 parts by weight or less per 100 parts by weight of (A).

  In the present invention, the foaming agent (C) is preferably water alone or a combination of water and a low-boiling hydrocarbon.

  When water and a low boiling point hydrocarbon are used in combination as the blowing agent (C), at least one R1 and Z are different groups in the strength improver (A) from the viewpoint of handling (viscosity) and foam strength. It is preferable.

In the present invention, the reaction between the active hydrogen component (P) and the organic polyisocyanate (B) may be performed in the presence of the foam stabilizer (E). As the foam stabilizer (E), all those used in the production of ordinary polyurethane foams can be used. Examples include polyether-modified dimethylsiloxane foam stabilizers (for example, “TEGOSTAB B8737LF” manufactured by Evonik Degussa Japan, Toray Industries, Inc.). “SZ-1346”, “SF-2936F”, “SZ-1327”, “SRX-274C”, “SH-193”, “L-540”, etc. ”manufactured by Dow Corning Co., Ltd.], dimethylsiloxane foam stabilizers [ Examples thereof include silicone foam stabilizers such as “SRX-253” manufactured by Toray Dow Silicone Co., Ltd.].
The amount of (E) used is preferably 0.5 to 12 parts by weight with respect to 100 parts by weight of the active hydrogen component (A) from the viewpoint of the mechanical properties of the foam.

In the present invention, if necessary, other auxiliary components as described below may be used and reacted in the presence thereof.
For example, colorants (dyes, pigments), flame retardants (phosphate esters, halogenated phosphate esters, etc.), anti-aging agents (triazoles, benzophenones, etc.), antioxidants (hindered phenols, hindered amines, etc.) The reaction can be carried out in the presence of a known auxiliary component such as With respect to the amount of these auxiliary components used relative to 100 parts by weight of the active hydrogen component (A), the colorant is preferably 1 part by weight or less. The flame retardant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less. The anti-aging agent is preferably 1 part by weight or less, more preferably 0.5 part by weight or less. The antioxidant is preferably 1 part by weight or less, more preferably 0.01 to 0.5 part by weight.

  In the production method of the present invention, the isocyanate index [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] (NCO index) in the production of polyurethane foam is 70 to 500 from the viewpoint of mechanical properties of the foam. More preferably, it is 75-450, Most preferably, it is 85-415.

  A specific example of a method for producing a polyurethane foam by the method of the present invention is as follows. First, a predetermined amount of the active hydrogen component (A) and the foaming agent (D) and, if necessary, the catalyst (C), the foam stabilizer (E) and other auxiliary components are mixed. Subsequently, this mixture (polyol premix) and organic polyisocyanate (B) are rapidly mixed using a polyurethane foaming machine or a stirrer. The obtained mixed solution is poured into a mold (for example, 55 to 75 ° C.) and demolded after a predetermined time to obtain a polyurethane foam.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by this.

  The materials used in the examples and comparative examples are described below. Those not described can be easily obtained as reagents.

(1) Strength improver (A)
Strength improver A-1: To a stainless steel autoclave equipped with a stirrer and a temperature controller, polypropylene glycol (Sanix Kasei Kogyo Sannix PP-2000; polypropylene glycol with a number average molecular weight of 2000, hydroxyl value 56.0) 1 Mole, 1 mol of trimellitic anhydride and 0.010 mol of an alkali catalyst (N-ethylmorpholine) were charged, and half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. After the half esterification, 82 mol of PO was controlled to be 80 ± 10 ° C. and the pressure was 0.50 MPa or less over 5 hours, followed by aging at 80 ± 10 ° C. for 1 hour. Further, 2 mol of EO was added dropwise over 1 hour, followed by aging for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 10 kPa for 1 hour to obtain a strength improver A-1. The measured values of A-1 are shown in Table 1.

  Strength improver A-2: In the same autoclave as in the production of A-1, 1 mol of glycerin PO adduct (Sanyox GP-3000NS manufactured by Sanyo Chemical Industries, Ltd .; number average molecular weight 3000, hydroxyl value 56.0), anhydrous 6 mol of phthalic acid and 0.030 mol of an alkali catalyst (N-ethylmorpholine) were charged and reacted at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere to carry out half esterification. Thereafter, 6 mol of EO was added dropwise over 5 hours while controlling the pressure to be 80 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 80 ± 10 ° C. for 1 hour. Cool to room temperature, charge 1 mol of trimellitic anhydride, and after half-esterification at 0.20 MPa and 120 ± 10 ° C. for 1 hour, 2 mol of EO is 80 ± 10 ° C. and the pressure is 0.5 MPa or less. While being controlled, the solution was dropped over 2 hours and then aged at 80 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 10 kPa for 1 hour to obtain a strength improver A-2. The measured values of A-2 are shown in Table 1.

  Strength improver A-3: In the production of A-2, glycerin PO adduct (Sanyo Chemical Industries, Ltd. Sannix GP-1500; number average molecular weight 1500, hydroxyl value instead of glycerin PO adduct (GP-3000NS) 112.0) and the strength improver A-3 was obtained in the same manner as the strength improver A-2 except that the amount of N-ethylmorpholine used was 0.010 mol. The measured values of A-3 are shown in Table 1.

  Strength improver A-4: In the production of A-1, 1 mol of glycerin PO adduct (GP-3000NS) is used instead of polypropylene glycol (PP-2000), PO is not used, and 2 mol of EO is used. A strength improver A-4 was obtained in the same manner as A-1, except that the amount was 6 mol. The measured values of A-4 are shown in Table 1.

  Strength improver A-5: An autoclave similar to the production of A-1 was charged with 1 mol of polypropylene glycol (PP-2000), 2 mol of phthalic anhydride and 0.010 mol of alkali catalyst (N-ethylmorpholine). Then, half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 2 mol of EO was added dropwise over 5 hours while controlling the pressure to be 80 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After cooling to room temperature, charging 2 mol of trimellitic anhydride and esterifying at 0.20 MPa and 120 ± 10 ° C. for 1 hour, 4 mol of EO is 80 ± 10 ° C. and the pressure is 0.5 MPa or less. The solution was dropped over 2 hours under control, and then aged at 80 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 10 kPa for 1 hour to obtain a strength improver A-5. The measured values of A-5 are shown in Table 1.

  Strength improver A-6: In the production of A-2, 1 mol of glycerin PO adduct (GP-1500) was used instead of glycerin PO adduct (GP-3000NS), and the amount of N-ethylmorpholine used was changed. The strength improver A-6 was obtained in the same manner as in Example 2 except that 0.010 mol and PO6 mol were used instead of EO6 mol. The measured values of A-6 are shown in Table 1.

  Strength improver A-7: Strength improvement in the same manner as A-2 except that the amount of phthalic anhydride used was 3 mol, EO 6 mol was 3 mol, and EO 2 mol was 6 mol in the production of A-2 Agent A-7 was obtained. The measured values of A-7 are shown in Table 1.

  Strength improver A-8: In the production of A-2, glycerin PO adduct (GP-3000NS) was converted to glycerin PO adduct (Sanix GP-4000, manufactured by Sanyo Chemical Industries, Ltd.); number average molecular weight 4000, hydroxyl value 42. 0) 1 mol and a strength improver A-8 was obtained in the same manner as A-2 except that the amount of N-ethylmorpholine used was 0.010 mol. The measured values of A-8 are shown in Table 1.

<Production of strength improvers A-9 to A-90>
Hereinafter, the production of the strength improvers A-9 to A-90 will be described. The measured values of the obtained strength improvers are shown in Tables 1 to 3.

なお、Ａ−９〜Ａ−９０の製造において使用している活性水素含有化合物のうち、上記のＡ−１〜Ａ−９に記載していない物について下記に記載する。記載していない物については、試薬として容易に入手することができる。

In addition, the thing which is not described in said A-1 to A-9 among the active hydrogen containing compounds currently used in manufacture of A-9 to A-90 is described below. Those not described can be easily obtained as reagents.

(1) Ethanol-modified product / polyol (I) (ethanol EO adduct; number average molecular weight 200, hydroxyl value 280)
An autoclave similar to the production of A-1 was charged with 1 mol of ethanol and 9.0 mmol of KOH, and dehydrated at 130 ± 5 ° C. and 10 kPa for 1 hour. After completion of the dehydration, 3.5 mol of EO was added dropwise over 2 hours while controlling the temperature to be 130 ° C. ± 5 ° C. and 0.5 MPa or less, followed by aging for 2 hours after the completion of the addition. After completion of aging, the mixture was cooled to 90 ± 5 ° C., 2% by weight of water and 2% by weight of KYOWARD 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic silicate) were added and treated for 1 hour. After taking out from the autoclave, it was filtered using 1 micron filter paper and dehydrated under reduced pressure to obtain polyol (I).
Polyol (II) (ethanol EO adduct; number average molecular weight 2000, hydroxyl value 56.1)
The polyol (I) was produced in the same manner except that 90 mmol of KOH and 44.4 mol of EO were used.
Polyol (III) (ethanol, phthalic anhydride, EO copolymer; number average molecular weight 300, hydroxyl value 187)
Half-esterification was carried out by charging 1 mol of ethanol, 1 mol of phthalic anhydride and 0.01 mol of N-ethylmorpholine in an autoclave similar to the production of A-1, and reacting at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. . Thereafter, 2.4 mol of EO was added dropwise over 2 hours while controlling the pressure to be 80 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging for 3 hours. After completion of aging, N-ethylmorpholine was removed under reduced pressure at 100 ± 10 ° C. and 10 kPa for 1 hour to obtain polyol (III).
Polyol (IV) (copolymer of ethanol, phthalic anhydride, EO; number average molecular weight 1000, hydroxyl value 56.1)
In the production of polyol (III), polyol (IV) was produced in the same manner except that 4 mol of phthalic anhydride and 8.2 mol of EO were used.

(2) Alkylene glycol / PEG-200 (ethylene glycol EO adduct; number average molecular weight 200, hydroxyl value 560, “PEG-200” manufactured by Sanyo Chemical Industries, Ltd.)

(3) Modified glycerin / GP-400 (glycerin PO adduct; number average molecular weight 400, hydroxyl value 420, “SANNICS GP-400” manufactured by Sanyo Chemical Industries, Ltd.)
(4) Pentaerythritol modified product / polyol (V) (pentaerythritol EO adduct; number average molecular weight 400, hydroxyl value 561)
In the production of polyol (I), polyol (V) was produced in the same manner except that ethanol was changed to pentaerythritol, 18 mmol of KOH and 6.0 mol of EO were used.

(5) Modified sorbitol / SP-750 (sorbitol PO adduct; number average molecular weight 690, hydroxyl value 490, “Sanix SP-750” manufactured by Sanyo Chemical Industries, Ltd.)

(6) Sucrose modified product / RP-410A (sucrose PO adduct; number average molecular weight 1070, hydroxyl value 420, “Sanix RP-410A” manufactured by Sanyo Chemical Industries, Ltd.)
Polyol (VI) (sucrose, phthalic anhydride, EO copolymer; number average molecular weight 1900, hydroxyl value 236)
In an autoclave similar to the production of A-1, 1 mol of sucrose, 8 mol of phthalic anhydride, 0.03 mol of N-ethylmorpholine, and 6.5 mol of THF are charged and reacted at 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Esterification was performed. Thereafter, 8.5 mol of EO was added dropwise over 2 hours while controlling the pressure to be 80 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging for 3 hours. After completion of aging, N-ethylmorpholine and THF were removed under reduced pressure at 100 ± 10 ° C. and 10 kPa for 1 hour to obtain polyol (VI).
Polyol (VII) (sucrose, phthalic anhydride, PO, EO copolymer; number average molecular weight 4150, hydroxyl value 108)
In the production of polyol (III), RP-410A is used instead of ethanol, N-ethylmorpholine is used at 0.05 mol, THF is not used, and EO is used at 16.2 mol. Except for the above, polyol (VII) was obtained in the same manner.
Polyol (VIII) (sucrose PO adduct; number average molecular weight 3000, hydroxyl value 150)
In an autoclave similar to the production of A-1, 1 mol of RP-410A and 0.14 mol of KOH were charged and dehydrated at 110 ± 5 ° C. and 10 kPa for 1 hour. After completion of dehydration, 33.3 mol of PO was added dropwise over 4 hours while controlling to 0.5 MPa or less, and aging was carried out for 3 hours after completion of the addition. After completion of aging, the mixture was cooled to 90 ± 5 ° C., 2% by weight of water and 2% by weight of KYOWARD 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic silicate) were added and treated for 1 hour. After taking out from the autoclave, it was filtered using 1 micron filter paper and dehydrated under reduced pressure to obtain polyol (VIII).

The strength improvers A-21 to 24, 33, 35, and 37 were produced by the following manufacturing method using the raw materials and usage amounts (moles) shown in Table 4, respectively. An example will be described in A-21.
A mole of polyol (I) (Z constituent raw material), 1 mole of trimellitic anhydride (Y constituent raw material), 1 mole of triethylamine as a catalyst, and 2 moles of THF as a solvent are charged in an autoclave similar to the production of A-1. Then, half esterification was performed at 80 ± 10 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 2 moles of ethylene bromide was added as an R1 constituent raw material and reacted at 80 ± 10 ° C. for 6 hours. After the reaction, the precipitated salt was filtered off, the organic layer was washed with water, and the target product was extracted and separated with toluene. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver A-21. The measured values of each strength improver are shown in Tables 1 to 3.

The strength improvers A-30, 31, 40, 43, 47, 50, 53, and 75 to 77 were produced by the following production method using the raw materials and usage amounts (moles) shown in Table 5, respectively. An example will be described in A-30.
1 mol of polyol (I) (Z constituent raw material), 1 mol of pyromellitic anhydride (Y constituent raw material), 3.2 mol of triethylamine as a catalyst, and 2 mol of THF as a solvent are charged in an autoclave similar to the production of A-1. Then, half esterification was performed at 80 ± 10 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 1 mol of water was added and the reaction was performed for 30 minutes. Then, 3 mol of ethylene bromide was added as an R1 constituent raw material and reacted at 80 ± 10 ° C. for 6 hours. After the reaction, the precipitated salt was filtered off, the organic layer was washed with water, and the target product was extracted and separated with toluene. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver A-30. The measured values of each strength improver are shown in Tables 1 to 3.

Strength improver A-9, 10, 18-20, 25, 34, 36, 38, 39, 41, 42, 44, 45, 48, 51, 54, 55, 65-68, 78-81, 86, Using the raw materials and the amount (moles) shown in Table 6, they were produced by the following production method. An example will be described in A-9.
1 mol of PEG-200 (Z constituent raw material), 1 mol of trimellitic anhydride (Y constituent raw material), 0.02 mol of N-ethylmorpholine as a catalyst, and THF as a solvent in an autoclave similar to the production of A-1. 2 mol preparation was performed, and half esterification was performed at 80 ± 10 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 2 mol of EO as the R1 constituent raw material was added dropwise over 2 hours while controlling to 80 ± 10 ° C. and 0.5 MPa or less, and aged for 3 hours. After aging, the catalyst and the solvent were distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver A-9. The measured values of each strength improver are shown in Tables 1 to 3.

Strength improvers A-26 to 28, 46, 49, 52, and 69 to 72 were each prepared using the raw materials and amounts used (moles) shown in Table 7 by the following production method. One example of 1-butanol (Z constituent raw material), one mole of pyromellitic anhydride (Y constituent raw material), and N-ethylmorpholine 0 as a catalyst in an autoclave similar to the production of A-1 described in A-26 as an example 0.03 mol and 2 mol of THF as a solvent were charged, and half esterification was performed at 80 ± 10 ° C. for 2 hours in a nitrogen atmosphere. Thereafter, 1 mol of water was added, and after 30 minutes of reaction, 3 mol of EO as an R1 constituent raw material was added dropwise over 2 hours while controlling to 80 ± 10 ° C. and 0.5 MPa or less, and aged for 3 hours. After aging, the catalyst and the solvent were distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver A-26. The measured values of each strength improver are shown in Tables 1 to 3.

Strength improvers A-11 to 17, 29, 32, 56 to 64, 73, 74, 89, and 90 were produced by the following production method using the raw materials and the amounts (moles) shown in Table 8. As an example, PTMG-1000 (polytetramethylene glycol; number average molecular weight 1000, hydroxyl value 112) is added to a reactor equipped with a stirrer, a temperature controller, a pressure controller, a cooler, a trap, and a liquid circulation pump. "PTMG-1000" manufactured by Mitsubishi Chemical Corporation) (Z constituent raw material) 1 mol, trimellitic anhydride (Y constituent raw material) 1 mol, N-ethylmorpholine 0.02 mol as a catalyst, toluene 5 as a solvent Mole charging was performed, and half esterification was performed at 80 ± 10 ° C. and 0.1 MPa for 2 hours in a nitrogen atmosphere. Then, 2 mol of PEG-200 was added as an R1 constituent raw material and reacted for 6 hours while controlling to 95 ± 5 ° C. and 0.06 MPa. During the reaction, volatile toluene and water were condensed with a cooler, and toluene separated by the trap was returned to the reactor again. After the reaction, the catalyst and the solvent were distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver A-11. The measured values of each strength improver are shown in Tables 1 to 3.

Strength improvers A-82 to 85 were each prepared using the raw materials and amounts used (in moles) shown in Table 9 by the following production method. One example of diethylene glycol (Z constituent raw material) and hemilitnic acid (Y constituent raw material) in a reactor equipped with a stirrer, temperature control device, pressure control device, cooler, trap, and liquid circulation pump will be described as an example. 1 mol, 0.02 mol of N-ethylmorpholine as a catalyst, and 2 mol of toluene as a solvent were charged, and half esterification was performed at 95 ± 5 ° C. and 0.06 MPa for 4 hours. During the reaction, volatile toluene and water were condensed with a cooler, and toluene separated by the trap was returned to the reactor again. Thereafter, 2 moles of ethylene glycol was added as an R1 constituent raw material and reacted at 95 ± 5 ° C. and 0.06 MPa for 6 hours. During the reaction, volatile toluene and water were condensed with a cooler, and toluene separated by the trap was returned to the reactor again. After the reaction, the catalyst and the solvent were distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver A-82. The measured values of each strength improver are shown in Table 3.

Strength improvers A-87 and 88 were produced by the following production method using the raw materials and amounts used (mole) shown in Table 10, respectively. An example will be described in A-87.
1 mol of ethylene glycol (Z constituent raw material), 1 mol of trimellitic anhydride (Y constituent raw material), 0.02 mol of N-ethylmorpholine as a catalyst, and 2 THF as a solvent in an autoclave similar to the production of A-1. A half esterification was performed for 2 hours at 80 ± 10 ° C. in a nitrogen atmosphere. Thereafter, 2 mol of EO as the R1 constituent raw material was added dropwise over 2 hours while controlling to 80 ± 10 ° C. and 0.5 MPa or less, and aged for 3 hours. After aging, the AV was adjusted to 1.0 with 10 wt% sodium hydroxide, and then dehydrated at 100 ° C. and 10 kPa to obtain a strength improver A-87. The measured values of each strength improver are shown in Tables 1 to 3.

[Examples 1 to 28, Comparative Examples 1 to 7]
The manufacturing method of the rigid polyurethane foam of an Example and a comparative example is as follows. In the formulation described in Tables 11 and 12, a polyol premix containing a predetermined amount other than the organic polyisocyanate (B) was charged into a polyol component tank of a high-pressure foaming machine, and (B) was charged into an isocyanate tank at 25 ° C. The mixture was spray-collised and mixed at 6 MPa, and sprayed onto two continuously supplied kraft papers whose temperature was adjusted to 50 ° C. Immediately, the two kraft papers were put into a circulating dryer temperature-controlled at 50 ° C., taken out after 5 minutes, and immediately cut (3000 mm × 1000 mm × 50 mm) to obtain a rigid polyurethane board foam.

[Examples 29 to 46, Comparative Examples 8 to 11]
The manufacturing method of the rigid polyurethane foam of an Example and a comparative example is as follows. In the formulation described in Tables 11 and 12, a polyol premix containing a predetermined amount other than the organic polyisocyanate (B) was charged into a polyol component tank of a high-pressure foaming machine, and (B) was charged into an isocyanate tank at 25 ° C. The mold (aluminum, length x width x height = 3000 mm x 1000 mm x 100 mm, top and bottom molds with a thickness of 0.1 mm as the face material was impact-mixed at 15 MPa and mixed by collision at 15 MPa. After injecting into the set), the mold was removed after 20 minutes to obtain a rigid polyurethane panel foam.

[Examples 47 to 69, Comparative Examples 12 to 16]
The manufacturing method of the rigid polyurethane foam of an Example and a comparative example is as follows. First, a predetermined amount of a polyol premix in which a predetermined amount other than the organic polyisocyanate (B) was blended was blended according to the blending recipe described in Tables 11 and 12. To this mixture, organic isocyanate (B) adjusted to 25 ± 5 ° C. was added so as to be a predetermined NCO INDEX, and rapidly mixed at 4000 rpm × 6 seconds with a stirrer [Homodisper: made by Special Machine Co., Ltd.]. The mixture was immediately poured into an aluminum box without a canopy of 240 × 240 × 240 mm at 25 ° C. and subjected to free foaming to obtain a rigid polyurethane foam.

[Examples 70 to 79, Comparative Examples 17 to 18]
The manufacturing method of the rigid polyurethane foam of an Example and a comparative example is as follows. In the formulation shown in Table 13, a polyol premix containing a predetermined amount other than the organic polyisocyanate (B) is charged into a polyol component tank of a high-pressure foaming machine (manufactured by Polymer Engineering Co., Ltd.), and (B) is charged into an isocyanate tank. The temperature was adjusted to 25 ° C., impact mixed at 15 MPa, poured into a mold (aluminum, length × width × height = 400 mm × 400 mm × 100 mm) temperature-controlled to 40 ° C., and then demolded after 6 minutes. Thus, a flexible polyurethane panel foam was obtained.

[Examples 80 to 90, Comparative Examples 19 to 21]
The manufacturing method of the rigid polyurethane foam of an Example and a comparative example is as follows. First, a predetermined amount of a polyol premix in which a predetermined amount other than the organic polyisocyanate (B) was blended was mixed according to the blending prescription described in Table 13. To this mixture, organic isocyanate (B) adjusted to 25 ± 5 ° C. was added so as to have a predetermined NCO INDEX, and rapidly mixed at 5000 rpm for 6 seconds with a stirrer [Homodisper: made by Special Machine Co., Ltd.]. The mixture was immediately poured into an aluminum box without a canopy at 250 ° C. and 250 mm at 25 ° C. and subjected to free foaming to obtain a flexible polyurethane foam.

In Tables 11 to 13, raw materials other than the above-described strength improvers are as follows.
(1) Polyol (PL)
Polyol P-1: A polyether polyol obtained by adding 5.66 mol of PO to tris (pentafluorophenyl) borane as a catalyst in the same manner as in Example 1 of JP-A-2006-063344 to 1 mol of glycerin. Hydroxyl value = 400, primary OH ratio = 80%.
Polyol P-2: A polyether polyol obtained by adding 4.00 mol of PO without any catalyst to 1 mol of ethylenediamine. Hydroxyl value = 768, primary OH ratio = 5%.
Polyol P-3: Polyether polyol obtained by adding 4.00 mol of PO without catalyst to 1 mol of ethylenediamine, and then obtaining 4.73 mol of EO without catalyst. Hydroxyl value = 449, primary OH ratio = 50%.
Polyol P-4: A polyether polyol obtained by adding 5.66 mol of PO to 1 mol of glycerin as a catalyst and removing potassium hydroxide by a conventional method. Hydroxyl value = 400, primary OH ratio = 5%.
Polyol P-5: A polyether polyol obtained by adding 3.95 mol of PO to 1 mol of triisopropanolamine using potassium hydroxide as a catalyst, and then removing potassium hydroxide by a conventional method. Hydroxyl value = 400, primary OH ratio = 5%.
Polyol P-6: Polyether polyol obtained by adding 7.31 mol of PO to 1 mol of pentaerythritol using potassium hydroxide as a catalyst and removing potassium hydroxide by a conventional method. Hydroxyl value = 401, primary OH ratio = 5%.
Polyol P-7: Polyether polyol obtained by adding 5.31 mol of PO to 1 mol of glycerin as a catalyst and removing potassium hydroxide by a conventional method. Hydroxyl value = 421, primary OH conversion ratio = 5%.
Polyol P-8: Polyether polyol obtained by adding 9.12 moles of PO to 1 mole of glycerol using potassium hydroxide as a catalyst and removing potassium hydroxide by a conventional method. Hydroxyl value = 271, primary OH ratio = 5%.
Polyol P-9: Phthalic acid-based polyester polyol. Hydroxyl value = 322. (Product name: RDK-133, manufactured by Kawasaki Kasei Co., Ltd.)
Polyol P-10: Mannich polyester polyol. Hydroxyl value = 354. (Product name: DK-3776, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Polymer polyol P-11: In a polyether polyol in which potassium hydroxide was added to 1 mol of glycerin as a catalyst, 71.7 mol of PO was added, 15.8 mol of EO was added, and potassium hydroxide was removed by a conventional method. Polymer polyol (polymer content 30%) obtained by copolymerization of styrene and acrylonitrile (weight ratio: 30/70). Hydroxyl value 24.
Polyol P-12: A polyether polyol obtained by randomly adding 32.3 mol of PO and 114.8 mol of EO to 1 mol of glycerin as a catalyst and removing potassium hydroxide by a conventional method. Hydroxyl value = 24
Polyol P-13: Polyether polyol obtained by adding 8.71 mol of PO to 1 mol of sorbitol using potassium hydroxide as a catalyst and removing potassium hydroxide by a conventional method. Hydroxyl value 490.
Polyol P-14: Glycerin. Functional group number 3.0, hydroxyl value 1829.
Polyol P-15: Polyether polyol obtained by adding 16.5 mol of PO to 1 mol of pentaerythritol and adding 25.5 mol of EO and removing potassium hydroxide by a conventional method. . Hydroxyl value 24.
Polyol P-16: A polyether polyol obtained by adding 74.0 mol of PO to 1 mol of glycerin as a catalyst and then adding 16.2 mol of EO and removing potassium hydroxide by a conventional method. Hydroxyl value 33.
Polyol H-1: Sanniks GP-3000NS (manufactured by Sanyo Chemical Industries, Ltd .; glycerin PO adduct, hydroxyl value 56.0). The measured values of (H-1) are as follows.
Hydroxyl value (mgKOH / g) = 56.0, Y content (% by weight) = 0, aromatic ring concentration (mmol / g) = 0.0.
Polyol H-2: In the same autoclave as A-1, glycerin PO adduct (Sanyox GP-1500 manufactured by Sanyo Chemical Industries, Ltd .; number average molecular weight 1500, hydroxyl value 112.0) 1 mol, phthalic anhydride 6 mol Then, 0.010 mol of an alkali catalyst (N-ethylmorpholine) was charged and reacted at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere to carry out half esterification. Thereafter, PO6 mol was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (H-2). The measured value of (H-2) is as follows.
Hydroxyl value (mgKOH / g) = 63, Y content (% by weight) = 0, aromatic ring concentration (mmol / g) = 2.26.
Polyol H-3: 1 mol of glycerin PO adduct (Sanyox GP-1500 manufactured by Sanyo Chemical Industries, Ltd .; number average molecular weight 1500, hydroxyl value 112.0), 6 mol of phthalic anhydride in the same autoclave as A-1 Then, 0.010 mol of an alkali catalyst (N-ethylmorpholine) was charged and reacted at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere to carry out half esterification. Thereafter, 20 mol of EO was added dropwise over 5 hours while controlling the pressure to be 80 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 80 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a polyol (H-3). The measured values of (H-4) are as follows.
Hydroxyl value (mgKOH / g) = 51.2, Y content (% by weight) = 0, aromatic ring concentration (mmol / g) = 1.82.

(2) Organic polyisocyanate (B)
B-1: Crude MDI: NCO% = 31 (trade name: Millionate MR-200, manufactured by Nippon Polyurethane Industry Co., Ltd.)
B-2: Crude MDI: NCO% = 30.7 (trade name: Millionate MR-400, manufactured by Nippon Polyurethane Industry Co., Ltd.)
B-3: TDI: NCO% = 48.3 (trade name: Coronate T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.)
B-4: TDI-80 (2,4- and 2,6-TDI, ratio of 2,4-isomer is 80% / crude MDI (average functional group number: 2.9) = 80/20 (weight ratio) ( Product name: CE-729, manufactured by Nippon Polyurethane Industry Co., Ltd.)

(3) Foaming agent (C)
Blowing agent c-1: cyclopentane blowing agent c-2: water blowing agent c-3: isopentane

(4) Catalyst (D)
Catalyst d-1: 33% by mass dipropylene glycol solution of triethylenediamine (trade name: Minico L-1020, manufactured by Active Materials Chemical Co., Ltd.)
Catalyst d-2: Lead octylate catalyst d-3: MS-1B (manufactured by San Apro Co., Ltd.)
Catalyst d-4: U-cat 2160 (manufactured by San Apro Co., Ltd.)
Catalyst d-5: U-cat 1000 (manufactured by Sun Apro Co., Ltd.)
Catalyst d-6: MS-181 (manufactured by Sun Apro Co., Ltd.)
Catalyst d-7: MS-171 (manufactured by San Apro Co., Ltd.)
Catalyst d-8: Dibutyltin dilaurate (trade name: Neostan U-100, manufactured by Nitto Kasei Co., Ltd.)
Catalyst d-9: Ethylene glycol solution catalyst containing 10% by weight of P-15 (manufactured by San Apro Co., Ltd.) d-10: N, N-dimethylaminoethyl-N′-methylaminoethanol (trade name: TOYOCAT RX- 5, manufactured by Tosoh Corporation)
Catalyst d-11: 33% by weight dipropylene glycol solution of triethylenediamine (trade name: DABCO-33LV, manufactured by Air Products Japan Ltd., catalyst d-12: 70% by weight dipropylene glycol of bis (dimethylaminoethyl) ether Solution (trade name: TOYOCAT ET, manufactured by Tosoh Corporation)
Catalyst d-13: Tin octylate (trade name: Neostan U-28, manufactured by Nitto Kasei Co., Ltd.)

(5) Foam stabilizer (E)
Foam stabilizer e-1: Dimethylsiloxane foam stabilizer (trade name: SH-193, manufactured by Toray Dow Corning Co., Ltd.)
Foam stabilizer e-2: Dimethylsiloxane foam stabilizer (trade name: SF-2936F, manufactured by Toray Dow Corning Co., Ltd.)
Foam stabilizer e-3: Dimethylsiloxane foam stabilizer (trade name: L-5420, manufactured by Momentive Co., Ltd.)
Foam stabilizer e-4: Brand name: TEGOSTAB B8737LF, EVONIK's foam stabilizer e-5: Trade name: L-540, Toray Dow Corning Co., Ltd. (6) Flame retardant (f)
Flame retardant f-1: Trichloropropyl phosphate (manufactured by Eighth Chemical Co., Ltd.)

<Test items and test methods>
<1>: Core density of the polyurethane foam (kg / m ³ ).
<2>: Compression hardness (kPa) of the polyurethane foam.
<1> and <2> conform to JIS A9511.
<3>: Core density of the polyurethane foam (kg / m ³ ).
<4>: Elongation rate of polyurethane foam (%)
<5>: Tensile strength of polyurethane foam (kgf / cm ² )
<6>: Hardness of polyurethane foam (25% -ILD) (N / 314 cm ² )
<7>: Tear strength of polyurethane foam (kgf / cm)
<3> to <7> conformed to JIS K6400.

In Tables 11-12, this invention Examples 1-28 and Comparative Examples 1-7 are compared, Examples 29-46 and Comparative Examples 8-11 are compared, Examples 47-69 and Comparative Examples 12-16 are compared. By doing this, it can be seen that the foam physical properties, particularly the compressive strength, are improved as compared with the urethane foam obtained by the prior art.
In Table 13, by comparing the inventive examples 70-79 and comparative examples 17-18 with the examples 80-90 and comparative examples 19-21, the foam physical properties than the urethane foam obtained by the prior art. Especially, foam hardness, tensile strength, and tear strength are improved.

  The polyurethane foam of the present invention can be used for all kinds of polyurethane foam for vehicle seats, furniture, building materials, bedding, apparel, electrical equipment, electronic equipment, packaging, and other uses (sanitary goods, cosmetics). Can be suitably used.

Claims (7)

In a method for producing a polyurethane foam by reacting an active hydrogen component (P) with an organic polyisocyanate (B) in the presence of a foaming agent (C), the strength represented by the following general formula (I): A method for producing a polyurethane foam comprising an improver (A), wherein (C) contains water and / or a low-boiling hydrocarbon.

[In the general formula (I), R1 represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound. A plurality of R1 may be the same or different. ; Y represents the residue remove | excluding the carboxyl group from trivalent or more aromatic polycarboxylic acid (f). The aromatic ring is composed of carbon atoms. The substituent of the aromatic ring may be a hydrogen atom or another substituent, but at least one substituent is a hydrogen atom. A is an integer satisfying 0 ≦ a ≦ (the number of aromatic ring substituents−2). B is an integer satisfying 0 ≦ b ≦ (the number of aromatic ring substituents−2). A + b is an integer satisfying 2 ≦ a + b ≦ (the number of aromatic ring substituents−2). Z represents a residue obtained by removing m active hydrogens from an active hydrogen-containing compound having a valence of at least m; M represents an integer of 1 to 10; ] The method for producing a polyurethane foam according to claim 1, wherein the content of the strength improver (A) based on the weight of the active hydrogen component (P) is 0.1 to 100% by weight. The method for producing a polyurethane foam according to claim 1 or 2, wherein the active hydrogen compound (P) has a hydroxyl value of 10 to 1850 mgKOH / g. The content of water as foaming agent (C) is 25% by weight or less and the content of low-boiling hydrocarbons is 70% by weight or less based on the weight of active hydrogen component (P). The method for producing a polyurethane foam according to any one of the above. The method for producing a polyurethane foam according to any one of claims 1 to 4, wherein the strength improver (A) has a hydroxyl value of 0 to 700 mgKOH / g. The method for producing a polyurethane foam according to any one of claims 1 to 5, wherein the aromatic ring concentration (mmol / g) of the strength improver (A) is 0.1 to 10.0. The method for producing a polyurethane foam according to any one of claims 1 to 6, wherein the blowing agent (C) contains a low-boiling hydrocarbon, and the boiling point of the low-boiling hydrocarbon is 0 to 70 ° C.