JP3190589B2 - Metal salt crosslinked foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a heat insulating material, a structural material,
The present invention relates to a novel foam useful as a protective material, a sound insulating material, and the like.

[0002]

2. Description of the Related Art Conventionally, as foams, polyurethane foams, polyurea foams, polystyrene foams, polyolefin foams, polycyclopentadiene foams and the like are known. Further, as a product having improved productivity of a polyolefin-based foam, an ion-crosslinked polyethylene foam (Japanese Patent Publication No. 2-11621) in which a carboxylic acid-containing copolymer is reacted with a metal carbonate has been proposed.

[0003]

However, existing foams not only use raw materials having a high environmental load, but also generate intoxication gas and soot due to incomplete combustion during combustion, and incinerators due to excessive combustion heat generation. It is difficult to avoid damage, generation of static electricity, etc.
In such a point, there was a problem that the burden on the environment was high. Further, the ion-crosslinked polyethylene foam has an expansion ratio of only about 2 to 5 times, and a low-density foam cannot be obtained.
Also, when the carboxylic acid-containing copolymer is used in combination with another foaming agent to increase the foaming ratio, the strength at the time of foaming is insufficient, causing collapse of foam cells and the like, and a low-density foam cannot be obtained. . In addition, since the density of the foam does not decrease, the temperature-time area and the smoke generation coefficient in the flame retardancy test (JIS A-1321) become remarkably large, and there is a problem that the flame retardant does not pass the first to third grade.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on low-density foams having a low environmental load and found that a metal bonded to an organic polymer greatly contributes to imparting flame retardancy. Reached the present invention.

That is, the present invention comprises a foamed metal salt crosslinked product of a modified organic polymer having a functional group capable of crosslinking with a metal salt having a foaming ratio of 10 to 100 times, wherein the modified organic polymer is 40% by weight or less. And at least one modified polymer selected from the group consisting of polyalkyl (meth) acrylates which may have another unsaturated monomer unit, polyurethane, epoxy resin, phenol resin, urea resin and melamine resin. A foam of carbon dioxide gas of a crosslinked metal salt of a modified organic polymer containing a functional group capable of crosslinking with a metal salt, wherein the modified organic polymer contains 40% by weight or less of another unsaturated monomer unit. Selected from the group consisting of polyalkyl (meth) acrylates which may have, polyurethane, epoxy resin, phenolic resin, urea resin and melamine resin A foam is at least one modified polymer that.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a radical polymerizable polymer,
Polyaddition polymers such as polyurethane and epoxy resin,
An addition condensation type polymer such as a phenol resin is exemplified. Modification of these organic polymers is intended to contain a functional group capable of cross-linking a metal salt, and a carboxylic acid group,
Examples of the organic polymer include a compound containing a sulfonic acid group or a phosphoric acid group as a constituent unit of the organic polymer.

When a radical polymerizable polymer such as polyalkyl (meth) acrylate is used as an organic polymer, a method of (co) polymerizing a metal salt of a carboxyl group-containing unsaturated monomer and another unsaturated monomer, etc. Can be taken. Examples of the alkyl group of the polyalkyl (meth) acrylate include an alkyl group having 1 to 20 carbon atoms.

The carboxyl group-containing unsaturated monomer includes acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and the like. Among these, acrylic acid and methacrylic acid are preferred from the viewpoint of cost.

The carboxyl group-containing unsaturated monomer metal salts include salts of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, cinnamic acid and the like. Salts include alkali metals (eg, sodium, potassium,
Rubidium), alkaline earth metals (eg, magnesium, calcium, barium), typical metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, zinc) and the like.
Of these, salts of acrylic acid and methacrylic acid are preferred from the viewpoint of cost.

As the other unsaturated monomers, known ones can be used. For example, (meth) acrylamide, vinylpyrrolidone, hydroxyethyl (meth) acrylate,
(Meth) acrylic acid alkylene oxide adduct, (meth) acryloyl polyoxyethylene methyl ether,
Water-soluble monovinyl monomers such as 2- (meth) acryloylamino-2-methylpropanesulfonic acid (salt) and vinylsulfonic acid (salt), styrene, alpha methylstyrene, methyl (meth) acrylate, acrylonitrile,
Oil-soluble monovinyl monomers such as vinyl acetate can be used.

As a part of the other unsaturated monomers, polyfunctional unsaturated monomers may be used. Examples of polyfunctional unsaturated monomers include divinylbenzene, di (meth) acrylate of (poly) ethylene glycol, di (meth) acrylate of (poly) propylene glycol, poly (meth) acrylate of trimethylolpropane, and poly (glycerin). Examples thereof include (meth) acrylate, poly (meth) acrylate of pentaerythritol, diallyl phthalate, and diallyl ether of (poly) ethylene glycol. Among these, poly (meth) acrylate is preferred from the viewpoint of the obtained foam quality.

The proportion of the other unsaturated monomer used may be arbitrarily selected according to the purpose. However, usually, the proportion of the unsaturated monomer is 4% based on the total weight of the unsaturated monomer in terms of foam quality and cost.
0% by weight or less. The usage ratio of the polyfunctional unsaturated monomer is usually 30% by weight or less based on the total weight of the unsaturated monomer, and preferably 20% by weight or less from the viewpoint of the quality of the obtained foam and cost.

The number average molecular weight of the modified organic polymer is usually 5,000 to 1,000,000, preferably 700
0 to 100,000.

The method and conditions for the polymerization of the modified organic polymer may be any known methods. For example, methods for initiating polymerization and catalysts are described in JP-B-63-221843 and JP-B-63-4684.
No. 45, for example.

Examples of the polymerization initiator include known radical polymerization initiators such as oil-soluble radical polymerization initiators such as azobisisobutyronitrile and benzoyl peroxide; azobiscyanovaleric acid, azobisamidinopropane salt, and ascorbic acid. Water-soluble radical polymerization initiators such as a combination of hydrogen oxide (redox) and a combination of potassium persulfate or sodium persulfate and sodium bisulfite (redox) are preferable, and a water-soluble radical polymerization initiator is preferable. In the above method, the temperature of the crosslinking polymerization is usually 0.
To 120 ° C, preferably room temperature to 90 ° C.

Examples of the metal compound include polyvalent metals such as alkaline earth metals (eg, magnesium, calcium, barium), typical metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, zinc). And salts, oxides and hydroxides of these metals. Among them, preferred are salts, oxides and hydroxides of at least one polyvalent metal selected from the group consisting of calcium, magnesium, zinc, barium, aluminum and iron.

A polyaddition polymer such as polyurethane or epoxy resin can be used as the organic polymer. When polyurethane is used, a metal salt compound obtained by reacting a hydroxyl compound having a carboxyl group with a metal compound and, if necessary, a method of reacting another hydroxyl compound with a polyisocyanate compound can be used.

Examples of the hydroxyl compound having a carboxyl group include glycolic acid, lactic acid, dimethylolpropionic acid and the like. Preferred of these are:
From the viewpoint of cost, glycolic acid and lactic acid are used.

Other hydroxyl compounds include known polyols conventionally used in the production of polyurethanes,
And polyamines. Examples of the polyol include a polyalkylene ether polyol, a polyester polyol, a polymer polyol, a polybutadiene polyol, and a mixture of two or more thereof. The number average molecular weight of the polyol is usually 500 to 20,000.
0, preferably 500 to 10,000, more preferably 1,000 to 3,000.

The polyalkylene ether polyol includes a compound having a structure in which an alkylene oxide (hereinafter abbreviated as AO) is added to an active hydrogen atom-containing polyfunctional compound, and a mixture of two or more of these compounds. Examples of the active hydrogen atom-containing polyfunctional compound include polyhydric alcohols, polyhydric phenols, amines, polycarboxylic acids, and phosphoric acids. As polyhydric alcohols, ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol,
Dihydric alcohols such as bis (hydroxymethyl) cyclohexane and bis (hydroxyethyl) benzene; glycerin, trimethylolpropane, pentaerythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose And trihydric to polyhydric alcohols such as sucrose. Examples of the polyhydric phenols include polyphenols such as pyrogallol, catechol and hydroquinone, and bisphenols such as bisphenol A, bisphenol F and bisphenol S. As the amines, ammonia, alkylamines having 1 to 20 carbon atoms (such as butylamine),
Monoamines such as aniline; aliphatic polyamines such as ethylenediamine, trimethylenediamine, hexamethylenediamine, diethylenetriamine; piperazine, N
-Aminoethylpiperazine and other JP-B-55-2
No. 1044, heterocyclic polyamines; alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine;
Aromatic polyamines such as diphenylmethanediamine, diphenyletherdiamine, and polyphenylmethanepolyamine; and alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine. Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid and adipic acid, and aromatic polycarboxylic acids such as phthalic acid, terephthalic acid and trimellitic acid. The active hydrogen atom-containing compound (a) described above may be used in combination of two or more. A to be added to the compound containing an active hydrogen atom
As O, ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- or 1,
3-butylene oxide, tetrahydrofuran (TH
F) and epichlorohydrin.

AO may be used alone or in combination of two or more.
In the latter case, a mixed system of both block addition (chip type, balance type, active secondary type, etc.) and random addition [chip after random addition: 0 to 50% by weight of ethylene oxide chains arbitrarily distributed in the molecule. (Preferably 5 to 40% by weight), and 0 to 30% by weight (preferably 5 to 25% by weight) of an EO chain chipped at the molecular end]. Of these AOs, preferred are EO alone, PO alone, THF alone, PO and EO.
And the combination of PO and / or EO with THF (in the case of combined use, random, block and mixed systems of both).

Polyester polyols include low molecular weight diols and / or condensed polyester diols obtained by reacting polyalkylene ether diols having a molecular weight of 1000 or less with dicarboxylic acids, polylactone diols obtained by ring-opening polymerization of lactones, low molecular weight diols, Polycarbonate diols obtained by reacting a diol with a carbonic acid diester of a lower alcohol (such as methanol) are included. Examples of the low molecular diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-, 1,3-butanediol, neopentyl glycol, and 1,6-hexanediol; low molecular diols having a cyclic group [For example, those described in JP-B-45-1474: bis (hydroxymethyl) cyclohexane, bis (hydroxyethyl) benzene, ethylene oxide adduct of bisphenol A, etc.], and a mixture of two or more of these. Examples of the polyalkylene ether diol having a molecular weight of 1,000 or less include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, and a mixture of two or more thereof.

The dicarboxylic acids include aliphatic dicarboxylic acids (such as succinic acid, adipic acid, azelaic acid, and sebacic acid), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid, and phthalic acid), and two or more of these. Lactones include ε-caprolactone, γ-butyrolactone, γ-valerolactone, and mixtures of two or more of these.

Specific examples of these polyester polyols include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol , Polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate diol, polycaprolactone diol or triol, polyhexamethylene carbonate diol, etc. Is mentioned.

As the polymer polyol, a radical polymerizable monomer [for example, styrene, (meth) acrylonitrile, or the like] in a polyol (the polyalkylene ether polyol and / or the polyester polyol) can be used.
(Meth) acrylates, vinyl chloride, these two
And the like, and a polymer obtained by finely dispersing the polymer.

Examples of the polybutadiene polyol include 1,
Those having a 2-vinyl structure, those having a 1,2-vinyl structure and a 1,4-trans structure, and 1,4-
Those having a trans structure are exemplified. The ratio between the 1,2-vinyl structure and the 1,4-trans structure can be variously changed, and is, for example, 100: 0 to 0: 100 in molar ratio. Polybutadiene glycol (4) includes homopolymers and copolymers (styrene butadiene copolymer, acrylonitrile butadiene copolymer, etc.) and hydrogenated products thereof (hydrogenation rate: for example, 20%).
１００100%). The number average molecular weight of the polybutadiene glycol (4) is usually from 500 to 10,000.

Examples of the polyamine include ethylenediamine, diethylenetriamine, toluylenediamine, 3,5-diethyltoluylenediamine, diphenylmethanediamine and the like.

Examples of the isocyanate compound include known polyisocyanates and isocyanate group-containing monomer (co) polymers which are conventionally used in the production of polyurethane. Examples of the polyisocyanate include aromatic polyisocyanate, aliphatic polyisocyanate, alicyclic polyisocyanate, and modified products thereof (for example, carbodiimide-modified, allophanate-modified, urea-modified,
Buret-modified, isocyanurate-modified, oxazolidone-modified), isocyanate-terminated prepolymers, and mixtures of two or more of these.

The (co) polymer of the isocyanate group-containing monomer can be obtained by reacting the polyisocyanate with the hydroxyl group-containing unsaturated monomer in equimolar amounts.

Specific examples of aromatic polyisocyanates include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and 4,4'-
Diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate (crude MDI), naphthylene-1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate, xylylene diisocyanate, α, α, α ′ , Α'-tetramethylxylylene diisocyanate. Specific examples of the aliphatic isocyanate include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and xylylene diisocyanate. Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and 1,4-cyclohexane diisocyanate. Specific examples of the modified polyisocyanate include carbodiimide-modified MDI, sucrose-modified TDI, castor oil-modified MDI, and the like. Of these, preferred are TDI, MDI, crude MDI
And carbodiimide-modified MDI.

Examples of the metal compound include polyvalent metals such as alkaline earth metals (eg, magnesium, calcium, barium), typical metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, zinc). And salts, oxides and hydroxides of these metals. Of these, preferred are salts, oxides and hydroxides of at least one polyvalent metal selected from the group consisting of calcium, magnesium, zinc, barium, aluminum and iron, more preferably calcium, magnesium, zinc And at least one carbonate of a polyvalent metal selected from the group consisting of barium, aluminum, and iron.

When an epoxy resin is used as an organic polymer, a compound obtained by glycidylation of a metal salt compound obtained by reacting a hydroxyl compound having a carboxyl group with a metal compound and, if necessary, another epoxy compound is reacted with an epoxy curing agent. And the like.

As the hydroxyl compound having a carboxyl group, those described above can be used. These metal salt compounds can be glycidylated by a known method. For example, there is a method in which epichlorohydrin is added to a hydroxyl group in the presence of an acid catalyst, and a glycidylation is performed by adding an alkali compound to the hydroxyl group for desalting.

Examples of the metal compound include polyvalent metals such as alkaline earth metals (eg, magnesium, calcium, barium), typical metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, zinc). And salts, oxides and hydroxides of these metals. Among them, preferred are salts, oxides and hydroxides of at least one polyvalent metal selected from the group consisting of calcium, magnesium, zinc, barium, aluminum and iron.

Other epoxy compounds include, for example, di- or polyphenol-based glycidyl ether epoxy resins such as bisphenol A, bisphenol F, phenol or cresol novolak resin, polyalkylene polyols such as polyethylene polyol and polypropylene polyol, and polyphenols such as A polyol-based polyglycidyl ether type epoxy resin such as a polyol obtained by adding a polyalkylene oxide to a di- or polyglycidyl ester type epoxy resin obtained from a polycarboxylic acid such as adipic acid, dimer acid, and hexahydrophthalic acid; epoxidized polybutadiene; Epoxidized vegetable oil, 3,
Examples thereof include aliphatic or alicyclic polyepoxide type epoxy resins such as 4 epoxy-6 methylcyclohexylmethyl carboxylate and 3,4 epoxy cyclohexylmethyl carboxylate, and a combination of two or more thereof.

Among them, preferred are a liquid bisphenol A epoxy resin having an epoxy equivalent of 150 to 340, a liquid bisphenol F epoxy resin having an epoxy equivalent of 155 to 250, and diglycidyl of polypropylene glycol having a molecular weight of 250 to 550. Ether, polypropylene-added diglycidyl ether of bisphenol A having a molecular weight of 300 to 2,000, and a mixture thereof.

Further, a monoepoxy reactive diluent may be contained together with the epoxy resin, and specific examples thereof include low-viscosity monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl. Ether, cresol glycidyl ether, butylphenyl glycidyl ether, tertiary carboxylic acid glycidyl ether, styrene oxide,
Glycidyl methacrylate and the like can be mentioned. Preferred as the monoepoxy reactive diluent (E2) is 2
-Ethylhexyl glycidyl ether, phenyl glycidyl ether, cresol glycidyl ether, butylphenyl glycidyl ether and tertiary carboxylic acid glycidyl ether.

The ratio in which the epoxy resin and the monoepoxy-based reactive diluent can be used in combination is not particularly limited, but the viscosity of the mixture at room temperature is 100 to 50,000 cp due to workability.
A ratio that can be s is preferable.

Examples of the epoxy curing agent include aliphatic polyamines and aliphatic polythiols. Examples of the aliphatic polyamines include polyalkylene polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, propylenediamine, dipropylenetriamine, hexamethylenediamine, and dihexamethylenetriamine, and xylylenediamine and Alicyclic polyamines such as isophoronediamine and 1,3 bisaminomethylcyclohexane; Examples of the aliphatic polythiol include ethanedithiol.

Further, polyamide polyamines obtained by condensation of polymerized fatty acids and higher mono fatty acids with the above-mentioned polyamines, polyamine epoxy adducts obtained by addition reaction of monoepoxy compounds and diepoxy compounds with the above-mentioned polyamines, acrylonitrile and alkyl acrylates Amine-based curing agents for epoxy resins such as modified polyamines obtained by the addition reaction of αβ unsaturated carbonyl compounds such as the above with polyamines (“New epoxy resin”: written by Hiroshi Kakiuchi, published by Shokodo Co., Ltd.) Amine-based epoxy resin curing agent) can also be used.

Of these, preferred are polyamines which dissolve and disperse easily in water, such as triethylenetetramine, hexamethylenediamine, xylylenediamine, and polyamidepolyamines having a total amine value of 280 to 450 (for example, Polyamide L-25). -3, Polyamide L-40
51, Polyamide L-45-3, both manufactured by Sanyo Chemical Industry Co., Ltd. and Versamide 140, Versamide 125:
All are manufactured by Henkel Japan Ltd.), adducts of 1.5 to 2 mol of butyl glycidyl ether of xylylenediamine or hexamethylenediamine, adducts of 1.8 mol of acrylonitrile of xylylenediamine, and the like.

When an addition condensation polymer such as a phenol resin, a urea resin or a melamine resin is used as an organic polymer, a metal salt compound obtained by reacting a carboxyl group-containing aromatic compound with a metal compound is mixed with a phenol or urea or melamine resin. And a method in which the resol-type phenol resin or urea or melamine-formalin precondensate obtained by reacting with the above is cured by heating in the presence of a catalyst such as a strong alkali.

Examples of the aromatic compound having a carboxyl group include benzoic acid, salicylic acid, phthalic acid, isophthalic acid and terephthalic acid.

The resole type phenol resin usable in the present invention is an uncured (precondensation step) corresponding to resole (bakelite A) or resitol (bakelite B) which has been further condensed, and contains a carboxyl group. Pre-condensation of a metal salt compound obtained by reacting an aromatic compound with a metal compound, a phenol and an aldehyde with an alkali catalyst such as sodium hydroxide, barium hydroxide, a tertiary amine such as triethylenediamine or trisdimethylaminophenol. Is obtained. Examples of the phenols include mono- or di-alkylphenols such as phenol, cresol, xylenol, butylphenol, octylphenol, and nonylphenol; halogenated phenols such as chlorophenol; styrenated phenol. Aldehydes include formaldehyde, paraformaldehyde, acetaldehyde and the like. In the above production method, the molar ratio of the aromatic compound containing a carboxyl group and the phenols to the aldehydes is usually in the range of 1: 1 to 1: 3. The molar ratio of the carboxyl group-containing aromatic compound to the phenol is usually in the range of 1: 1 to 9: 1. Resol type phenol resin has a solid content of 7
5% by weight or more of unreacted phenols are reduced as much as possible. The degree of condensation is 2 to 10, and low to room temperature.
What is necessary is just a high viscosity liquid range.

Further, a resin obtained by adding a lower alcohol to a resol type phenol resin for the purpose of stabilizing storage can also be used.

Among these resole-type phenolic resins, preferred are a carboxyl group-containing aromatic compound, phenol and formalin in a ratio of 1: 1: (3.0 to 3.0).
4.0) viscosity obtained by condensation at a molar ratio of 300 to 20
000 CPS / 25 ° C., with a non-volatile content of 70 to 100%.

As a method for curing these resole-type phenol resins, a method of curing a phenol resin in the presence of an alkali catalyst such as sodium hydroxide, barium hydroxide, a tertiary amine such as triethylenediamine or trisdimethylaminophenol, or the like is used.
For example, a method of heating at 0 to 130 ° C. for 1 minute to 1 hour to cure the composition may be used.

The urea or melamine-formalin precondensate which can be used in the present invention is, for example, a metal salt compound obtained by reacting a carboxyl group-containing aromatic compound with a metal compound and urea or melamine, and formaldehyde, paraformaldehyde or the like. It is obtained by a reaction (precondensation) using an aldehyde as a raw material under an alkali catalyst such as sodium hydroxide, barium hydroxide or the like (while maintaining neutrality or alkalinity by successive addition of the catalyst during the reaction). In the above production method, the molar ratio of the aromatic compound containing a carboxyl group and urea or melamine to the aldehyde is usually in the range of 1: 1 to 1: 5.
The molar ratio of the carboxyl group-containing aromatic compound to urea or melamine is usually in the range of 1: 1 to 9: 1. As the urea or melamine-formalin initial condensation, it is preferable that the unreacted urea or melamine component having a solid content of 75% by weight or more is reduced as much as possible.
It is sufficient that the degree of condensation is from 2 to 6, and the liquid has a low to high viscosity at room temperature. Further, as the initial condensation of urea or melamine-formalin, a product obtained by adding a lower alcohol and subjecting to alkyl etherification for the purpose of storage stabilization can be used.

Preferred among these urea or melamine-formalin precondensates are aromatic compounds containing a carboxyl group: (urea or melamine): formalin in a ratio of 1: 1: (3.0 to 5.0). Viscosity obtained by condensation at a molar ratio of 220 to 35000 CPS / 25
° C, 60-90% non-volatile content.

As a method for curing these urea or melamine-formalin precondensates, sodium hydroxide, barium hydroxide, a tertiary amine such as triethylenediamine or trisdimethylaminophenol or the like can be used in the presence of an alkali catalyst of 80 to 130. A method of heating to 1 ° C. for 1 minute to 1 hour to cure.

Examples of the metal compound include polyvalent metals such as alkaline earth metals (eg, magnesium, calcium, barium), typical metals (eg, aluminum, germanium, tin) and transition metals (eg, iron, cobalt, nickel, copper, zinc). And salts, oxides and hydroxides of these metals. Among them, preferred are salts, oxides and hydroxides of at least one polyvalent metal selected from the group consisting of calcium, magnesium, zinc, barium, aluminum and iron.

In the present invention, known foaming gases can be used, and examples thereof include gases such as carbon dioxide, freon gas, and butane, low-boiling solvents, and water. Among them, preferred is carbon dioxide from the viewpoint of the quality and cost of the obtained foam.

In the present invention, a metal (bi) carbonate can be used as a foaming agent, and the metal of the metal (bi) carbonate is an alkali metal (for example, sodium,
Potassium, rubidium); alkaline earth metals (eg, magnesium, calcium, barium) as polyvalent metals;
Typical metals (eg aluminum, germanium, tin)
And transition metals (eg, iron, cobalt, nickel, copper, zinc). Among these, a polyvalent metal is preferable, and it can function as a foaming agent and, at the same time, salt-crosslink a vinyl (co) polymer having a carboxyl group therein. More preferably, the polyvalent metal is at least one selected from the group consisting of calcium, magnesium, barium, zinc, aluminum and iron.
As the foaming agent, in addition to (bi) carbonate metal salts, known compounds may be used.
Examples thereof include carbonates or bicarbonates of monovalent bases such as ammonium carbonate, gases such as freon gas and butane gas, low-boiling solvents, and water.

The foam of the present invention can contain other optional components as appropriate. For example, carbon black,
Ceramic fiber, metal whisker, glass fiber,
Glauber, titanium oxide, PEG, dyes and pigments, chelates, fats, oils, surfactants, bentonite, cellulose, starch, flame retardants, water and the like. The amount of these optional components is not particularly limited, but is usually 50% by weight or less, preferably 20% by weight or less based on the quality of the obtained foam.

The expansion ratio of the foam of the present invention can be arbitrarily selected depending on the purpose.
It is 100 times, preferably 10 to 50 times, more preferably 10 to 40 times.

The foam of the present invention can be formed into a molded product, a plate, a sheet, a film, a rod, a cylinder, or the like having an arbitrary shape. These can also adopt a known processing method such as a known foam molding method such as RIM or transfer molding. Further, the foam of the present invention can be appropriately subjected to post-treatment such as surface treatment such as painting and impregnation with an aromatic agent. Applications of the foam include structural materials, protective materials, heat insulating materials, sound insulating materials, and the like.

[0057]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following, “parts” and “%” are based on weight, respectively.

The compositions, symbols, etc. of the raw materials used in the examples and comparative examples are as follows. PAAc: polyacrylic acid Freon having a number average molecular weight of about 10,000: Daiflon 141b manufactured by Daicel Chemical Co., Ltd. Polymeric MDI: "Coronate MR-200" manufactured by Nippon Polyurethane Industry Co., Ltd. PBAAc: butyl acrylate having an average molecular weight of about 10,000 Acrylic acid copolymer (acrylic acid content: 20% by weight) Polycat 41: Urethane / isocyanurate-forming catalyst manufactured by San Apro Co., Ltd. Foam stabilizer: "SZ-1627" manufactured by Nippon Unicar Co., Ltd.

Production Example 1 152 g of glycolic acid and barium hydroxide (octahydrate) 3
15.3 g is reacted in water at 25 ° C. for 1 hour, and then the reaction product is pulverized by removing the water content, and further dried at 120 ° C. for 2 hours. Then, 176 g of ethylene oxide was added thereto using 2 g of triethylamine as a catalyst, and a hydroxyl value of 240 g was added.
Of polyether diol (compound A) was obtained.

Production Example 2 1 g of boron trifluoride-diethyl ether complex was added as a catalyst to 463.3 g of the above compound A, and 277.5 g (3 mol) of epichlorohydrin was added dropwise at 60 ° C., followed by reaction for about 2 hours. Added. Then, 160 g of a 50% aqueous sodium hydroxide solution was added, and the mixture was reacted at 25 ° C. for 4 hours to perform a desalination reaction. Further remove water to make epoxy equivalent 3
Thus, 34 diglycidyl compounds (compound B) were obtained.

Production Example 3 138 g of salicylic acid and barium hydroxide (octahydrate) 15
7.6 g was reacted in water at 25 ° C. for 1 hour, then 94 g of phenol was added, and the mixture was stirred at 20-30 ° C. and cooled with 4 g of sodium hydroxide as a catalyst.
After dripping 4 g, it was made to react at 90 degreeC for 2.5 hours.
In addition, sodium hydroxide was sequentially added to maintain the pH at 8.5 to 9.5 during the reaction. Then, after adjusting the pH to 7 to 8 with paratoluenesulfonic acid, the mixture was cooled and the unreacted raw materials and a part of the condensed water were removed from the system under reduced pressure to obtain a liquid resol type having a solid content of 79% and a viscosity of 41,000 cps. A phenol resin (compound C) was obtained.

Production Example 4 138 g of salicylic acid and barium hydroxide (octahydrate) 15
7.6 g was reacted in water at 25 ° C. for 1 hour, then 60 g of urea was added, 284 g of formalin was added dropwise at 20 ° C. to 30 ° C. while stirring and cooling, and 4 g of sodium hydroxide was used as a catalyst. The reaction was carried out for 5 hours. In addition, sodium hydroxide was sequentially added to maintain the pH at 8.5 to 9.5 during the reaction. Then, after adjusting the pH to 7 to 8 with paratoluenesulfonic acid, the mixture was cooled and the unreacted raw material and a part of the condensed water were removed from the system under reduced pressure to obtain a liquid urea having a solid content of 78% and a viscosity of 50,000 cps. A formalin precondensate (compound D) was obtained.

Production Example 5 138 g of salicylic acid and 15 barium hydroxide (octahydrate)
7.6 g was reacted in water at 25 ° C. for 1 hour, then 126 g of melamine was added, and the mixture was stirred at 20-30 ° C. and cooled with 4 g of sodium hydroxide as a catalyst.
After dripping 4 g, it was made to react at 90 degreeC for 2.5 hours.
In addition, sodium hydroxide was sequentially added to maintain the pH at 8.5 to 9.5 during the reaction. Then, after adjusting the pH to 7 to 8 with paratoluenesulfonic acid, the mixture was cooled and the unreacted raw material and a part of the condensed water were removed from the system under reduced pressure to obtain a liquid melamine having a solid content of 76% and a viscosity of 42,000 cps. A formalin precondensate (Compound E) was obtained.

[0064]

Example 2 A mixture A, a mixture B and a urethanization catalyst shown in Table 1 were mixed at a predetermined ratio, and the mixture was placed in a container. After 5 seconds, polymerization and foaming occurred, and a foam was obtained within a few minutes. The quality of this foam is shown in Table 1.

Example 3 Mixture A and Mixture B shown in Table 1 were mixed at a predetermined ratio.
This was placed in a container. Put this container in a heating furnace at 100 ° C for 2 hours.
The mixture was allowed to stand for 0 minutes to foam and crosslink to obtain a foam. The quality of this foam is shown in Table 1.

Examples 4 to 6 The mixture A and the mixture B shown in Table 1 were mixed at a predetermined ratio.
This was placed in a container. Place this container in a heating furnace at 120 ° C for 1
The mixture was allowed to stand for a period of time to foam and crosslink to obtain a foam. The quality of this foam is shown in Table 1.

Comparative Example 1 Mixture A and Mixture B shown in Table 2 were adjusted to a temperature of 80 ° C., mixed at a predetermined ratio, and placed in a container. The container was left standing in a heating furnace at 100 ° C. for 20 minutes to foam and crosslink to obtain a foam. Table 2 shows the quality of the obtained foam.

Comparative Example 2 After 2 parts by weight of PBAAc pellets and 3 parts by weight of calcium carbonate powder were kneaded with a Banbury mixer, a pelletized calcium carbonate masterbatch (mixture B) was prepared. The mixture B and the mixture A (mixture of 100 parts by weight of PBAAc and 0.5 part by weight of the foam stabilizer) were mixed at a ratio shown in Table 2 by a melt-kneading extruder at an extrusion rate of 10 kg / hour and a resin pressure of 190 kg / cm ^2. The resin was extruded at a resin temperature of 180 ° C. to obtain a foam. Table 2 shows the quality of the obtained foam.

[0070]

[Table 1]

[0071]

[Table 2]

Density: (kg / m ³ ): JIS K
Compliant with 6310 Compressive strength: (kg / cm ² ): Compliant with JIS A 9514 Flame retardancy: Burning speed: (cm / min): JIS A 951
Compliant with 4 Temperature time area: (° C / min): Complies with JIS A 1321 Smoke emission coefficient: (CA): Complies with JIS A 1321 Afterflame time: (seconds): Complies with JIS A 1321 Chargeability: 25 ° C, relative The chargeability at a humidity of 50% was tested, and evaluated on a four-point scale of excellent, good, acceptable, and unacceptable. Thermal conductivity: (kcal / m · h · ° C.): JIS A9
Compliant with 514 Sound insulation: (dB): Compliant with JIS A 1416

[0073]

The foam of the present invention is excellent in chargeability, heat insulation and sound insulation, and has high compressive strength even at a low density. In addition, raw materials having a high environmental load are not used, the generation of toxic gases and soot due to incomplete combustion during combustion is small, and there is no excessive generation of combustion heat. Therefore, the foam of the present invention is useful as a heat insulating material, a structural material, a protective material, a sound insulating material, and the used foam can be co-fired with other garbage in an ordinary incinerator, and therefore has a low environmental load. For example, it is extremely advantageous for garbage power generation.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hideyuki Nishida 11-11 Hitotsubashi Nohonmachi, Higashiyama-ku, Kyoto City Sanyo Chemical Industry Co., Ltd. Examiner, Takuya Tanabe (56) References JP-A-4-258612 (JP, A JP-A 9-235400 (JP, A) JP-A 10-195226 (JP, A) JP-A 10-212370 (JP, A) JP-A 10-212371 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08J 9/00-9/42

Claims (7)

(57) [Claims] 1. A foaming ratio of a crosslinked metal salt of a modified organic polymer containing a functional group capable of crosslinking a metal salt is 10 to 100.
Polyalkyl (meth) acrylate, polyurethane, epoxy resin, phenolic resin, urea resin, wherein the modified organic polymer may comprise up to 40% by weight of other unsaturated monomer units And at least one modified polymer selected from the group consisting of melamine resins. 2. A modified organic polymer containing a functional group capable of crosslinking with a metal salt, comprising a carbon dioxide gas foam of a crosslinked metal salt of a modified organic polymer, wherein the modified organic polymer is 40% by weight or less of another unsaturated monomer. Polyalkyl (meta) optionally having units
A foam that is one or more modified polymers selected from the group consisting of acrylates, polyurethanes, epoxy resins, phenolic resins, urea resins, and melamine resins. 3. The foam according to claim 1, wherein the functional group capable of crosslinking with a metal salt is a carboxylic acid group, a sulfonic acid group or a phosphoric acid group. 4. The foam according to claim 1, wherein the metal of the metal salt bridge is a polyvalent metal. 5. The polyvalent metal is calcium, magnesium,
The foam according to claim 4, wherein the foam is at least one polyvalent metal selected from the group consisting of zinc, barium, aluminum and iron. 6. Flame retardant 1 according to JIS standard A-1321
The foam according to any one of claims 1 to 5, which has a grade 2 or grade 2 flame retardancy. 7. A heat insulating material, a structural material, a protective material or a sound insulating material comprising the foam according to claim 1.