CA1108349A - Inorganic-organic combined material and preparation thereof - Google Patents
Inorganic-organic combined material and preparation thereofInfo
- Publication number
- CA1108349A CA1108349A CA317,628A CA317628A CA1108349A CA 1108349 A CA1108349 A CA 1108349A CA 317628 A CA317628 A CA 317628A CA 1108349 A CA1108349 A CA 1108349A
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- Prior art keywords
- inorganic
- combined material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/342—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more reactive oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Geophysics And Detection Of Objects (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Abstract of the disclosure:
A novel inorganic-organic combined material constituted of co-hardened inorganic and organic components is prepared by mixing a polyvalent metal salt of phosphoric acid having specific equivalent ratio and atomic ratio, a hardening agent and a thermosetting resin curable with an acid catalyst and subjecting the resultant mixture to co-hardening, optionally in the presence of a blowing agent. This inorganic-organic combined material is excellent in both nonflammability and water resistance as well as in other properties such as mechanical strength.
In particular, expanded products having cell walls made of this material are suitable for various purposes, e.g. construction materials and lagging materials.
A novel inorganic-organic combined material constituted of co-hardened inorganic and organic components is prepared by mixing a polyvalent metal salt of phosphoric acid having specific equivalent ratio and atomic ratio, a hardening agent and a thermosetting resin curable with an acid catalyst and subjecting the resultant mixture to co-hardening, optionally in the presence of a blowing agent. This inorganic-organic combined material is excellent in both nonflammability and water resistance as well as in other properties such as mechanical strength.
In particular, expanded products having cell walls made of this material are suitable for various purposes, e.g. construction materials and lagging materials.
Description
3~
This invention relates to a novel inorganic-or~anic comblned material and an expanded product CQmprisin~ cell walls constituted of said material and also to a process for producin~ said material and expanded product thereof.
Organic expanded products of prior art such as polyurethane foams, polystyrene foams or polye-thylene foams have been known to have excellent thermal insulating property as well as excellent water resistanCe and mechanical strength and therefore they have widely been used as construction materialsg various lagging materials 9 etc. Since they are organic in nature~ however, they are very inflammable to the vital de~ect which has recently been deemed as serious problem, especially at the time of flre. As organic expanded products slightly improved in fire-retardant property 3 there have been also developed such expanded products of thermosetting resins as phenol foams 3 urea foams~ etc. But these materials are not substantially changed in inflammability and have only insufficient fire-retardant property.
On the other hand, as nonflammable expanded products~ there have been developed various inorFanic expanded products such as cernent foams, gypsum foarns or glass foams. All of these are brittle and have only insufficient water resistance due to the inor~anic nature.
For improvement of these drawbacks~ there are man~ attempts to incorporate inorganic components into . ~
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OrganiC ~XI)LIIId~d prod~lcts. Thes~ components, however, are generally incompatib]e with ~ach other and, especicllly when a large amount of inorgan:;c component is incorporated, mechanical strength is noticeably lowered ~o give no excellent expanded product. It is also well known to those skilled in the art that improvement of nonElammability is smaller than is expected even when a large amount of inorganic components may be incorpo~ated.
In one particular aspect ~he present invent:ion prov:ides an inorganic-organic combined material comprising a co-hardened product containing 100 parts by weight of a hardened product of at least one polyvalent metal phosphori.c aci.d salt and 1 to 400 parts by weight of a hardened product of a thermosetting resin curable with an acid catalyst, the . equivalent ratio of the said metal to the phosp~oric acid groups in said phosphoric salt being larger than 0.65, whlle the atomic ratio of the metal atoms to the phosphorus atoms being larger than 0.67, said polyvalent metal being at least one selected from the group consisting of magnesium, calcium, strontium, barium, zinc, manganese (II), copper (II), iron (II), aluminum, iron (III), titanium (III), cobalt, and zirconium and said thermosetting resin being at least one selecLed from the group consisting of resol type phenol.
resin, melamine resin~ urea resin, furan resin, melamine- ;
urea copolymer resin, furan-phenol copolymer resin and phenol-urea copolymer resin.
In another particular aspect the present invention provi.des a process ~or producing an inorganic-organic combined material, which comprises mixing (a~ a water soluble acidic pllosphoric acid salt of at least one polyvalent metal wherein the `~
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equ-Lvalellt ratio of the metai :ions to the phosphate ions is in the range of ~rom 1/9 to 3/4 ancl the atomic rat:io of the metal atoms to the phosphorus atoms i9 in the range of from 1/6 to 3/2, (b) a hardening agent capable of hardening said phosphoric acid salt and (c~ a thermosetting resin curable with an acid catalyst at a mix:ing ratio of 1 to 400 parts by weight oE (c) to 100 parts by weight of (a)-l-(b), said thermosetting resin being at least one selected from the group consistLilg of resol type phenol resin, melamine res:Ln, urea res:in, f-lran resin, melamine-urea copolymer resin, Euran-phenol copolymer resin and phenol-urea copolymer resin, and then allowing the resultant mixture to harden.
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. 4 According to a preferred embodiment of the present invention, there is provided an expanded product havin~ cell walls constltuted o~ the novel inorganic-or~,anic combined material as mentioned above, having an average cell diameter of less than 3 mm and a bulk densit~ of less tha.n 0.5 3 which can readily be prepared by carryin~ out the above process in the presence of a blowing a~ent~ thereby effectin~ expansion of the mixture simultaneously with hardenin~.
In the accompanyin~ drawings:
~ ig. 1 shows a mi.croscopic photograph (magnifi-cation:xlOO) of the surface of the molded co-hardened product according to the present invention (Example 2), Fig. 2 a microscopic photograph (magnifi--cation:xlOO) of the surface of the molded organic-inorganic combined material of prior art (Comparison example l);
~ ig. 3 a microscopic photograph (magnifi-cationoxl3) of an expanded co-hardened product according to the present invention (Example 8);
Fig. 4 a microscopic photograph (m~nifi-- cation x13) of the expanded co--hardened product as sh~wn in Fig. 3 a~ter it is subjected to burning to remove the organic hardened product.
I'he specific feature of the inorganic~organic combined expanded product provided according to the preferred embodiment of the present invention resides in the cell walls which are constituted of the integrall,y combined inorganic and organic components~
as substarltially distlnguished over the organic--inorganic mixed expandecl product of prior art in whlch powclery inorganic components are dispersed on cell walls made of organic components. The difference can evidentl~
been seen lrom inflammability~ mechanical strength, water resistance, foaming or others of these products.
The novel inorganic-organic combine(l material of the present invention has a specific structure~ in which both inorganic and organic hardened components, each being formed into a three dimensional network as the result of simultaneous hardening~ exist in a homogeneous mixture~ being bound by or intertwined in one another. Such a structure can be obtained by the specific co-hardening of the both components. The starting materials (A) and (C) to be used in the - present invention are both aqueous solutions, one bein~ an aqueous solution of a water-soluble acidic phosphoric acid salt of at least one polyvalent metal and the other being an aqueous solution of a thermo-setting resin curable with an acid catalystO These solutions are completely compatible and mixed to form a completely homogeneous mixtureO By initiating hardening of the phosphoric acid salt wlth a hardening agent (B) simultaneously with hardening of the thermosetting resin with an acid catalyst~ provided by the acidic phosphoric acid salt~ there ensues co-hardening of the both components whereby the molecules of each component are crosslinked to form segments of a three-dimensionally crosslinked network.
.~..... . . ~ -' '; '~
_ r, As the result of simultaneous hardening of the homo-geneQusl~ mixecl solution~9 the resultant hardened produc~s of each component are cons~dered to be such that the,y are present in a completely homogeneous matrix in whlch both segments of the three dimensional network are uniforml,y distributed~ one being bound by the other. While details of such a structure remain to be elucidated~ it, can rairly be distinguishecl over the well-known inor~anic--organlc combined material structure of prior art9 in which one component is present as i'islandsl1 dispersed in the "sea" or matrix of the other component. This can be evidenced at least b,y the residue of the materialg when one component is removed from the material. In the accompanying drawings, Fig. 4 shows the microscopic photograph of the residue of the expanded product of the inorganic~-organic combined material of the present invention~
when the organic component is removed by burnin~ the expanded product. As is clearly shown, the lnor~anic component remained retains the original shape of the expanded productg indicating that the inorganic component as well as the organic component are present throu~hout the entire matrix of the expanded product 3 ~orming individually by skeltons which are bound by each other. Thus~ the or~anic-inorganic combined material of the present invention is a mixture of organic and inorganic components having single solid phase~ having an appearance as if' it were made of`
single component. The excellent ph,ysical properties ., , , , - , , - : . - .
such as rnechanical strength as compared with the material of the prior art are reflected in the inor~anic--or~anic comblned material of the present invention due to such a structure.
The hardened product Or the phosph~ric acid salt in the present invention is a hardened product of a phosphoric acid salt of at least one polyvalent metals selected from the ~roup conslstin~ o~ magnesium~ calcium, strontium, barlum~ æinc9 manganese(II), copper(II) 1~ iron(II), aluminumg iron(III), titanlum(III) 3 cobaltg and zirconium or a phosphoric acid salt of said poly-valent metals in which a part of the pol~valent metals is substituted with an alkali metal such as lithium9 sodium, potassium or the like~ or quaternary ammonium salt. The equivalent ratio (hereinafter referred to as i'E-valuel') of the metals to phosphoric acid gr~ups i.n said phosphoric salt is desirably larger than o.659 while the atomic ratio (hereinafter referred to as - ~IM/P-value'')of the metal atoms to the phosphorus atoms is desirably larger than o.67. The E value and the M/P-value herein mentioned are defined by the following formulas~
~i x ~i E - -3~
~Ei M/P = N
, .
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wherein i indicates val.ence o:f the metals, Ei the number of atoms of .he rnetals in the phosphoric acid salt with valence i and Np the number of phosphorus atoms in the phosphoric acid salt~ When the E value is smaller than o.65 or the M/P-value smaller than 0.679 the phosphor~c acid salt cannot completely be hardened to give unfavorably in~erior properties as ko water resistance9 heat resistance 9 hardness and mechanical strength.
The hardenecl product o r the phosphoric acid salt can be formed by reacting a hardenin~ agent with a phosphoric acid salt havin~ E-value in the range from 1/9 to 3/4 and M/P~value in the range from 1/6 to 3/2 or an aqueous solution thereof. The hardening agent to be u.sed in the present i.nvention may include at least one selected from the group consistlng of the metals havin~ two or more valences such as magnesium~ calciumg . strontium~ barium, zinc9 manganese(II~g coppertII)g iron(II), aluminumg iron(lII)g titanium(III)g cobalt and zirconium, and hydroxidesg oxidesg silicates, titanates and carbonates of said metals. In order to allow the hardening reaction of the phosphoric acid : or an aqueous solution thereof to proceed smoothly to :. ~ive favorable hardened productg the E value is required to be in the ran~e rrom 1/9 to 3/LI and the M/P-v~lue in the range from 1/6 to 3/2. If the R-value is smaller than 1/9 or the M/P-value smaller than 1/6; the acidity .~ of said phosphoric acid salt is too highg whereby the reaction with the hardening agent is uncontrollably too vigorous. On the contrary9 if the E-value is larger , _ 9 ~
than 3~4 or ~he ~1/P~value larger than 3/2, thermoplasticity or water solubility Qf said phosphoric acid salt ls unfavourably poor to give no Kood hardened produc-t.
Further~ in this case, the acidity is too weak to have catal,ytic activit,y sufficient for hardenin~ of the thermosetting resin curahle with an acid catalyst as hereinafter descrlbed. Of course~ as mentioned above 3 the E value after hardening is required t,o be greater than o.65~ whîle the M/P^value great;er than o.67~
10 Thus~ the amount of the hardening agent can be deter- ~, mined corresponding to these requirements.
When an expanded product i,s desired to be obtainedg this hardening reaction is conducted in the presence of a blowing agent. As blowing agents, there may be employed water~ low boiling point fluoro-carbons or hydrocarbons (e.g. ~reon, pentane~ etc.)~
hydrogen peroxide3 metallic powders or carbonates.
Further~ compressed gas such as nitrogen~ argon or air ma~ also be available. Especially when carbonates or metallic powders of a metal having two or more valences are used as hardening agent, they can function as blowing a~ent simultaneously as hardening agent to a great advantage.
The thermosettin~; resins curable with an acid catal,yst to be used in the present invention may preferably be water~-soluble resins, includin~ resol type phenol resins, melamine resins, urea resins~ furan resins9melamine--urea copolymer resins~ furan-urea copolymer resins~ phenol-urea copolymer resins and `~A
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ketone res3.ns, ~s descr~bed above, the acidic phosphoric acid salt under~oes p~l charl~e with lapse ol' time in the course of the reactio~ with the hardening agent and the blowillg a~ent until it ls changed to neutral region org in some cases, to alkaline re~ion. During this procedure~
the aforesaid thermosetti.ng resin curable with an acid catalyst is hardened to give an inorganic-organic combined material having integrally--formed inorganic and organic components, I.1sua.11yg an expanded product is prepared by mixing the .four components of the phosphoric acid saltg the hardening agent, the blowing agent and the thermosetting resin curable with an acid catalyst and sub~jecting the resultant mixture t,o expansion and hardening at room ~emperature or under heating.
The thermosetting resin in the inorganic--; organic comblned expanded product of the present invention is required to be contained in an amount of 1 to 400 parts by wei~ht based on 100 parts by weight of the hardened product of the phosphoric acid salt.
An amount less than one part by weight will be insuffi-cient to give significant effect by introduction of the organic componentg while an amount in excess of 400 parts by wei~ht will worsen noticeably the non flammability to an extent comparable with that Of the expanded product made of the thermosettin~ resin alone.
For practicing the present invention more preferably, both of the phosphoric acid salt and the thermosetting resin are used in the state of liquids or solutionsg whereby more complete compatibility can be obtained to a great advantageO According to this odimerlt 9 the solutions of' the phosphoric acid salt and the thermosetting resin are completely mixed together to be made compatlbleg followed by mixing with hardening agent and~ if necessary~ the blowing agent to give desired inorganic~organic combined materialO
According to another preferred embodiment, the hardening agent and9 if` necessary, the blowing agent are prevlously dispersed in the solution of the thermoset-ting resin and the resultant dispersion is then mixed with the afore said solution of the phosphoric acid salt. This embodiment enables production o~ the desired inorganic~
organic combined material by way of two--liquid mixing~
and there~ore it is most suitable for moldirlg at the site or injection molding.
For practicing the present prccess according to the above embodiment by way of two-liquid mixing~
it is convenient to use a set of materials~ comprising ~(A) an aqueous solut,ion of the phosphoric acid salt as - 20 mentioned above containing 30 to ~5 wt,% of said phos-phoric acid salt, (B) a slurry containing 30 to 80 wt.
of solids in which a hardening agent as mentioned above is dispersed in an aqueous solution of a thermo~
setting resin as mentioned above at a weight ratio of 25 hardening agent to thermosetting resin of 1/1 to 1/40, and optionally (C) a blowing agent. By use of such a set of materials~ the inorganic-organic combined material can readily be prepared at the site at which - it is used by formulating the materials according to `~ , . - ~
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tile~ composition of the desired pLocluc.t.
In practicing -the present invent.ion, there may also be used additives such as reinforcing materials, aggregates, f.illers, water repellan-ts, stabilizers, pigments, surfactants, e-tc. In particular, as wa-ter repellants, there may be advantageously used in the present inventiP~, other than paraffin or silicone oil, those compounds having both hydrophobic groups and functional groups :reactive with the metal salt of phosphor.ic ac:id.
- As mentioned above, the inorganic-o.rganic combined expanded product can provide useful materials for light weigh-t construction materials or lagging ln ma-terials. In particular, i-t i9 possible to form.the expanded produc-t at the site at which it is applied to a grea-t commercial advantage.
The inorganic-organic combined e~panded productJ when it con-tains l to 20 parts by weight of the organic componen-t, can be improved in brittleness inherent in the inorganic material substantia].ly wi.thout impa~ing nonflammabili:ty.
When the organic content is in the range from 20 to 120 parts by weight, mechanical strength, water resistance and other properties are noticeably improved, and inflammability is extremely l~wer due to the cell wall st~ucture as mentio~ed above in which the lnorganic and organic components e~ist e~ masse, whereby there is obtained an e~panded product comparable to semi..no~1am~able materials~
12 - 1.
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~ 13 The expanded products with or~r!anic content in the range ~rom 120 to lloo parts by weight are also lower in in--flammabillty and have oxygen lndex values by far hi~her than conventional organic expanded products. In addition9 they are by far superior in mechanical strength to the organic expanded products of prior art in which inor~anic components such as inorganic fillers are merely dispersed.
As described above~ the inorganic-organic combined expanded product provided according to the present invention has excellent characteristlcs which are not found in inorganic foams, organic ~oams or organic-inorganic mixed foams in which organic and inorganic components are inhomogeneously mixed.
The present invention is further illustrated below with reference to the following Examples.
In the Examples~ thermal conductivity is measured by ASTM--C518. The oxygen index is measured by means of Inflammability Tester ON~1 (produced by Suga Testin~ Machine Co., I.td.)~ using test strip of 5 mm x 5 mm x 100 mm.
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Exampl~ 1 Phosphoric acid (75% aqlleous solution) 160 wt. parts Aluminum hydroxide 20 WtD parts Zinc oxide 35 wto parts The above components are mixed to carry out the reaction~ whereb~ there is obtained a transparent viscous solution having E-value=0.44 and M/P-value=0.56.
On the other hand~ -there ls also prepared a slurry having 30 wt. parts of fused ma~nesiurn oxide dispersed in 50 wt. parts of a commercial]y available aqueous urea resln solution (solid content 70%~ Ply~
amine P-364 BL~ trade mark3 produced by Dainippon Ink CO~g l,td.).
The above solution and the slurry are mixed - together and sufficiently stirred. The resultant mixture is cast into a mold~ng frame of 2 cm x 2 cm x 10 cm. A~ter 6 hours~ hardening is found ko be completed to give a block of hardened product having R-value of 20 o . 81~ and M/P value of 1.5. This product is found to be semi--kransparent and have specific gravity of 1.9~
compression strength of 650 kg/cm2 and oxygen index of 90 or more.
Example 2 Phosphoric acid (75% aqueous solution~ ~0 wt. parts Aluminum hydroxide 10 wt. parts Zinc oxide 17.5 wt. parts .
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, ~ 15 -l`he above componen~s are mixed to carry out the reaction9 whereby there is obtained a ~ransparent ~iscous solution h~lvinK E--value=0,44 and M/P-value=0.56.
On the other hand~ there is a]so prepared a slurry havln~ 15 wt. parts of' dead-burned magnesium oxide dispersed in 500 wt. parts of the same commercially available aqueous urea resin solution as used in Example 1.
The above solution and the slurry are mixed together~ followed by sufficient stirring~ and cast into a moldin~ frame of 2 cm x 2 cm x 10 cm. The molded product is found to be completely hardened after 6 hours to give a block of a hardened product having E-value of 0.84 and M/P-value of~ 1.5g comprising 100 wt. parts of 15 a hardened product of the phosphoric acid salt and -350 wt. parts of a hardened product of the urea resin.
This co-hardened product is semi-transparent and has specific gravity cf 1.5~ compression strength of 1050 kg/cm2 and oxygen lndex of 55Ø Fig. 1 shows the appearance of this product.
Comparison example 1 Aaueous urea resin solution 500 wt.parts (Solid content 70 wt.~ 3 Plyamine P-364 BL, trade markg produced by Dainippon Ink Co.g l.td.~
Anhydrous calcium sulfate powders 100 wt.parts To a slurry prepared by mixin~ the above `; components are added 10 wt. parts of a 10 % aqueous - phosphoric acid solution. The resultant mixture is cast in a moldlng f'rame of 2 cm x 2 cm x 10 cm.
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~- After 3 hours, complete hardening is effected.
The thus prepared hardened productg containing 100 wt. par-ts of anhydrous calcium sulfate powders and 350 wt. parts of a hardened product of' the urea resin, is found to have specific gravlty of 1.5 7 compression strength of 850 kg/cm2 and oxygen index of 25Ø
Fi~. 2 shows the appearance of this product.
Example 3 Phosphoric acid (75~ aqueous solution) 160 wt. parts Aluminum hydroxide20 wt. parts Zinc oxide 35 wt, parts The above components are mixed and allowed to react to obtain a transparent viscous solutlon having E-value of 0.44 and M/P-value of 0,56.
To the above solution are added 100 wt. parts of an aqueous solution of a commercially available urea resin (solid content:70~ Plyamine P 364 BL, trade mark~
Dainippon Ink Co.~ Ltd.) to obkain a further vlscous~
transparent solution. Immediatelyg 70 wt. parts of' powdery basic magnesium carbonate are added to the solution to be completely mixed therein. Foaming begins immediately until the mixture is completely hardened after 6 hours. The E value after expansion and hardening is found to be o.84 3 and the M/P--value 1.5~
This expanded product is found to have a bulk density of 0.099 an average cell diameter of 1.9 mm and thermal conductivity of 0.035 kcal/m,hr.C.
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~ 17 -Examples 4 ~ 5 3 Comparison examples 2 - 3 Example 1 i5 repeated except that the amount o~ the aqueous urea resin solution is varied as shown in Table 1.
Table 1 Comparison Comparison _xample 2 Example 4 ~ example 3 Urea resin 2.0 50 600 1500 (wt~ parts) Urea resin o.6 14.3 171 429 content*l ~1) Urea resin contentO solid urea resin(wt.parts) per 100 wt. parts of hardened phosphoric acid salt Each of the expanded product obtained has the properties as shown in Table 2.
Table 2 .... __ Avera~Je Thermal cell conduc- Compres- !
dia~ tivity sive Bulk meter kcal/ 0xy~en strength density (mm) m.hr C index k~/cm Comparison more less example 2 0.06 2.1 0.039than than 0,5 Example 4 0,07 1.0 0.038more 1.5 than Example 5 0.17 1.5 0'0LI3 62.5 17.8 Comparison example 3 0.61 1.0 0.08828.0 35.0 Examples 6 - 7 9 Comparison examples 4 - 5 There are prepared the phosphoric acid solutions havin~ the compositions as shown in Table 3.
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Table 3 Comparison Comparison _am~le 4 Example 6 Fxample 7 example 5 75~ aqueous phosphoric 160 wt. 160 wt. 160 wt. 160 wt.
acid parts parts parts parts solution Aluminum None 20 wt. 25 wt. 20 wt.
hydroxide parts parts parts Magnesium 2.5 wt. None 10 wt. 10 wt.
oxide parts parts parts Zinc oxide 5 wt. 20 wt. 20 wto 20 wt.
parts parts parts parts Sodium None None None 20 wto hydroxide parts E value 0.07 0O34 0.53 oO85 M/P-value 0.10 0.41 o.66 1.17 State Colorless Colorless Colorless White trans trans- trans-- turbid parent parent parent Two solutions~ namely each of the phosphoric acid salt solutions having the above compositions and 200 wt. parts of a urea resin solution (solid contento 70%) having completely dispersed 50 wt. parts of aluminum silicateg 40 wto parts of magnesium oxide and 15 wt. parts of pentane dispersed therein, are mixed together and left to stand. The results are set forth in Table 4.
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Table 9 Foaming Comparison Extreme heat generation with a great shri~kage example 4 until hardening Example 6 Foaming with mild heat generation;.
Specific gravity = 0.13 Example 7 Foaming with mild heat generation;
Specific gravity = 0.18 Comparison Neither heat generat.ion nor foaming occurs.
example 5 Comparison example 6 The same procedure as in Example 3 is repeated except 70 wtS
parts of the basic magnesium carbonate are changed to 35 wt, parts~ The resultant expanded and hardened product is found to have E -value-0~64 and M/P-value=0.86.
The expanded product obtained is very hygroscopi:c and ~:
exhibits acidity even aEter 4i3 hours.
Example 8 Primary aluminum phosphate .150 wt, parts :. 20 (50% aqueous solution, E-value=0.33, . M~P-value-0.33) Resol type phenol resin125 wt. parts (80% aqueous solution, ; BRL-lll, trade mark, produced by Showa Kobunshi.
Co., Ltd.) Aluminum powders 20 wt. parts After mixing the above components, the mixture is left to stand at 80 C for 30 mimltes in a hot air drier. After hardening, the expanded product obtained is found to have E-value=l.0, M/P-value=l.0 and specific gravity of 0.08. Fig. 3 shows the appearance of this product.
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~ 20 -This expancled product is :Lef't to stand in an electric furnace set at 800C ~or one hour. After the calcinationg the expanded product is discoloured in dark but its ori~inal cell structure is maintained (see Fig. 4~.
Comparison example 7 Resol type phenol resin 125 wt. parts (80P aqueous solution, B~L-1119 trade mark~
produced by Showa Kobunshi Co.g I.td.) Tertiary aluminurn phosphate 95 wt. parts powders Pehtane 5 wt. parts To the slurr~ having mixed -the above components are added 20 wto parts of a 10 % aqueous phosphoric acid solution in which 2.0 wt. parts of p'toluene sulfonic acid are dissolved. The m~xture is left to stand at room temperature and, after one minute, foamlng begins with generation of heat to give an expanded product having specific gravit~ of 0012.
This expanded product is left to stand in an electric furnace set at 800C for one hour. After the calcinationg only powdery carbonized product is remained.
Example 9 Phosphoric acid 160 wt. parts (75% aqueous solution) Aluminum hydroxide20 wt. parts Zinc oxide 20 WtD parts The above components are mixe~ and allowed to react to obtain a transparent and viscous solution.
After further adding 1.0 wt. paFt o~ lauryl amine as ., , .
21 ~
water rer,ellanl; and 2.0 wt. parts of' paper pulp as reillforcing materlal to the so:lution~ 100 wt. parts of an aqueous melamine resin solution (Nikalac~ trade mark~ produced by Sanwa Chemlcal Co. 7 Ltd.) having dispersed 20 wt. parts of metallic aluminum powders therein are added thereto. After complete mixing~
the mixture is left to stand in a hot air drier set at 100C for 30 minutes.
- The resultant e~panded product is found to have specific gravity of 0.16 and also to be endowed with perfect water repellency.
.
. ., . ~ .
This invention relates to a novel inorganic-or~anic comblned material and an expanded product CQmprisin~ cell walls constituted of said material and also to a process for producin~ said material and expanded product thereof.
Organic expanded products of prior art such as polyurethane foams, polystyrene foams or polye-thylene foams have been known to have excellent thermal insulating property as well as excellent water resistanCe and mechanical strength and therefore they have widely been used as construction materialsg various lagging materials 9 etc. Since they are organic in nature~ however, they are very inflammable to the vital de~ect which has recently been deemed as serious problem, especially at the time of flre. As organic expanded products slightly improved in fire-retardant property 3 there have been also developed such expanded products of thermosetting resins as phenol foams 3 urea foams~ etc. But these materials are not substantially changed in inflammability and have only insufficient fire-retardant property.
On the other hand, as nonflammable expanded products~ there have been developed various inorFanic expanded products such as cernent foams, gypsum foarns or glass foams. All of these are brittle and have only insufficient water resistance due to the inor~anic nature.
For improvement of these drawbacks~ there are man~ attempts to incorporate inorganic components into . ~
~ ir ~;
~,~, 3 .~ ~
OrganiC ~XI)LIIId~d prod~lcts. Thes~ components, however, are generally incompatib]e with ~ach other and, especicllly when a large amount of inorgan:;c component is incorporated, mechanical strength is noticeably lowered ~o give no excellent expanded product. It is also well known to those skilled in the art that improvement of nonElammability is smaller than is expected even when a large amount of inorganic components may be incorpo~ated.
In one particular aspect ~he present invent:ion prov:ides an inorganic-organic combined material comprising a co-hardened product containing 100 parts by weight of a hardened product of at least one polyvalent metal phosphori.c aci.d salt and 1 to 400 parts by weight of a hardened product of a thermosetting resin curable with an acid catalyst, the . equivalent ratio of the said metal to the phosp~oric acid groups in said phosphoric salt being larger than 0.65, whlle the atomic ratio of the metal atoms to the phosphorus atoms being larger than 0.67, said polyvalent metal being at least one selected from the group consisting of magnesium, calcium, strontium, barium, zinc, manganese (II), copper (II), iron (II), aluminum, iron (III), titanium (III), cobalt, and zirconium and said thermosetting resin being at least one selecLed from the group consisting of resol type phenol.
resin, melamine resin~ urea resin, furan resin, melamine- ;
urea copolymer resin, furan-phenol copolymer resin and phenol-urea copolymer resin.
In another particular aspect the present invention provi.des a process ~or producing an inorganic-organic combined material, which comprises mixing (a~ a water soluble acidic pllosphoric acid salt of at least one polyvalent metal wherein the `~
~ jl/i ~3- ~
equ-Lvalellt ratio of the metai :ions to the phosphate ions is in the range of ~rom 1/9 to 3/4 ancl the atomic rat:io of the metal atoms to the phosphorus atoms i9 in the range of from 1/6 to 3/2, (b) a hardening agent capable of hardening said phosphoric acid salt and (c~ a thermosetting resin curable with an acid catalyst at a mix:ing ratio of 1 to 400 parts by weight oE (c) to 100 parts by weight of (a)-l-(b), said thermosetting resin being at least one selected from the group consistLilg of resol type phenol resin, melamine res:Ln, urea res:in, f-lran resin, melamine-urea copolymer resin, Euran-phenol copolymer resin and phenol-urea copolymer resin, and then allowing the resultant mixture to harden.
.
,~
3a-; ~
. ~:
.. ..
: . ' . ' ~ : ::
~ : , ~ . -,: .
. 4 According to a preferred embodiment of the present invention, there is provided an expanded product havin~ cell walls constltuted o~ the novel inorganic-or~,anic combined material as mentioned above, having an average cell diameter of less than 3 mm and a bulk densit~ of less tha.n 0.5 3 which can readily be prepared by carryin~ out the above process in the presence of a blowing a~ent~ thereby effectin~ expansion of the mixture simultaneously with hardenin~.
In the accompanyin~ drawings:
~ ig. 1 shows a mi.croscopic photograph (magnifi-cation:xlOO) of the surface of the molded co-hardened product according to the present invention (Example 2), Fig. 2 a microscopic photograph (magnifi--cation:xlOO) of the surface of the molded organic-inorganic combined material of prior art (Comparison example l);
~ ig. 3 a microscopic photograph (magnifi-cationoxl3) of an expanded co-hardened product according to the present invention (Example 8);
Fig. 4 a microscopic photograph (m~nifi-- cation x13) of the expanded co--hardened product as sh~wn in Fig. 3 a~ter it is subjected to burning to remove the organic hardened product.
I'he specific feature of the inorganic~organic combined expanded product provided according to the preferred embodiment of the present invention resides in the cell walls which are constituted of the integrall,y combined inorganic and organic components~
as substarltially distlnguished over the organic--inorganic mixed expandecl product of prior art in whlch powclery inorganic components are dispersed on cell walls made of organic components. The difference can evidentl~
been seen lrom inflammability~ mechanical strength, water resistance, foaming or others of these products.
The novel inorganic-organic combine(l material of the present invention has a specific structure~ in which both inorganic and organic hardened components, each being formed into a three dimensional network as the result of simultaneous hardening~ exist in a homogeneous mixture~ being bound by or intertwined in one another. Such a structure can be obtained by the specific co-hardening of the both components. The starting materials (A) and (C) to be used in the - present invention are both aqueous solutions, one bein~ an aqueous solution of a water-soluble acidic phosphoric acid salt of at least one polyvalent metal and the other being an aqueous solution of a thermo-setting resin curable with an acid catalystO These solutions are completely compatible and mixed to form a completely homogeneous mixtureO By initiating hardening of the phosphoric acid salt wlth a hardening agent (B) simultaneously with hardening of the thermosetting resin with an acid catalyst~ provided by the acidic phosphoric acid salt~ there ensues co-hardening of the both components whereby the molecules of each component are crosslinked to form segments of a three-dimensionally crosslinked network.
.~..... . . ~ -' '; '~
_ r, As the result of simultaneous hardening of the homo-geneQusl~ mixecl solution~9 the resultant hardened produc~s of each component are cons~dered to be such that the,y are present in a completely homogeneous matrix in whlch both segments of the three dimensional network are uniforml,y distributed~ one being bound by the other. While details of such a structure remain to be elucidated~ it, can rairly be distinguishecl over the well-known inor~anic--organlc combined material structure of prior art9 in which one component is present as i'islandsl1 dispersed in the "sea" or matrix of the other component. This can be evidenced at least b,y the residue of the materialg when one component is removed from the material. In the accompanying drawings, Fig. 4 shows the microscopic photograph of the residue of the expanded product of the inorganic~-organic combined material of the present invention~
when the organic component is removed by burnin~ the expanded product. As is clearly shown, the lnor~anic component remained retains the original shape of the expanded productg indicating that the inorganic component as well as the organic component are present throu~hout the entire matrix of the expanded product 3 ~orming individually by skeltons which are bound by each other. Thus~ the or~anic-inorganic combined material of the present invention is a mixture of organic and inorganic components having single solid phase~ having an appearance as if' it were made of`
single component. The excellent ph,ysical properties ., , , , - , , - : . - .
such as rnechanical strength as compared with the material of the prior art are reflected in the inor~anic--or~anic comblned material of the present invention due to such a structure.
The hardened product Or the phosph~ric acid salt in the present invention is a hardened product of a phosphoric acid salt of at least one polyvalent metals selected from the ~roup conslstin~ o~ magnesium~ calcium, strontium, barlum~ æinc9 manganese(II), copper(II) 1~ iron(II), aluminumg iron(III), titanlum(III) 3 cobaltg and zirconium or a phosphoric acid salt of said poly-valent metals in which a part of the pol~valent metals is substituted with an alkali metal such as lithium9 sodium, potassium or the like~ or quaternary ammonium salt. The equivalent ratio (hereinafter referred to as i'E-valuel') of the metals to phosphoric acid gr~ups i.n said phosphoric salt is desirably larger than o.659 while the atomic ratio (hereinafter referred to as - ~IM/P-value'')of the metal atoms to the phosphorus atoms is desirably larger than o.67. The E value and the M/P-value herein mentioned are defined by the following formulas~
~i x ~i E - -3~
~Ei M/P = N
, .
.
.
wherein i indicates val.ence o:f the metals, Ei the number of atoms of .he rnetals in the phosphoric acid salt with valence i and Np the number of phosphorus atoms in the phosphoric acid salt~ When the E value is smaller than o.65 or the M/P-value smaller than 0.679 the phosphor~c acid salt cannot completely be hardened to give unfavorably in~erior properties as ko water resistance9 heat resistance 9 hardness and mechanical strength.
The hardenecl product o r the phosphoric acid salt can be formed by reacting a hardenin~ agent with a phosphoric acid salt havin~ E-value in the range from 1/9 to 3/4 and M/P~value in the range from 1/6 to 3/2 or an aqueous solution thereof. The hardening agent to be u.sed in the present i.nvention may include at least one selected from the group consistlng of the metals havin~ two or more valences such as magnesium~ calciumg . strontium~ barium, zinc9 manganese(II~g coppertII)g iron(II), aluminumg iron(lII)g titanium(III)g cobalt and zirconium, and hydroxidesg oxidesg silicates, titanates and carbonates of said metals. In order to allow the hardening reaction of the phosphoric acid : or an aqueous solution thereof to proceed smoothly to :. ~ive favorable hardened productg the E value is required to be in the ran~e rrom 1/9 to 3/LI and the M/P-v~lue in the range from 1/6 to 3/2. If the R-value is smaller than 1/9 or the M/P-value smaller than 1/6; the acidity .~ of said phosphoric acid salt is too highg whereby the reaction with the hardening agent is uncontrollably too vigorous. On the contrary9 if the E-value is larger , _ 9 ~
than 3~4 or ~he ~1/P~value larger than 3/2, thermoplasticity or water solubility Qf said phosphoric acid salt ls unfavourably poor to give no Kood hardened produc-t.
Further~ in this case, the acidity is too weak to have catal,ytic activit,y sufficient for hardenin~ of the thermosetting resin curahle with an acid catalyst as hereinafter descrlbed. Of course~ as mentioned above 3 the E value after hardening is required t,o be greater than o.65~ whîle the M/P^value great;er than o.67~
10 Thus~ the amount of the hardening agent can be deter- ~, mined corresponding to these requirements.
When an expanded product i,s desired to be obtainedg this hardening reaction is conducted in the presence of a blowing agent. As blowing agents, there may be employed water~ low boiling point fluoro-carbons or hydrocarbons (e.g. ~reon, pentane~ etc.)~
hydrogen peroxide3 metallic powders or carbonates.
Further~ compressed gas such as nitrogen~ argon or air ma~ also be available. Especially when carbonates or metallic powders of a metal having two or more valences are used as hardening agent, they can function as blowing a~ent simultaneously as hardening agent to a great advantage.
The thermosettin~; resins curable with an acid catal,yst to be used in the present invention may preferably be water~-soluble resins, includin~ resol type phenol resins, melamine resins, urea resins~ furan resins9melamine--urea copolymer resins~ furan-urea copolymer resins~ phenol-urea copolymer resins and `~A
..
, ''~ ', ' ~ ' ', ' ~, ~
1 o . . ~ ff ~
ketone res3.ns, ~s descr~bed above, the acidic phosphoric acid salt under~oes p~l charl~e with lapse ol' time in the course of the reactio~ with the hardening agent and the blowillg a~ent until it ls changed to neutral region org in some cases, to alkaline re~ion. During this procedure~
the aforesaid thermosetti.ng resin curable with an acid catalyst is hardened to give an inorganic-organic combined material having integrally--formed inorganic and organic components, I.1sua.11yg an expanded product is prepared by mixing the .four components of the phosphoric acid saltg the hardening agent, the blowing agent and the thermosetting resin curable with an acid catalyst and sub~jecting the resultant mixture t,o expansion and hardening at room ~emperature or under heating.
The thermosetting resin in the inorganic--; organic comblned expanded product of the present invention is required to be contained in an amount of 1 to 400 parts by wei~ht based on 100 parts by weight of the hardened product of the phosphoric acid salt.
An amount less than one part by weight will be insuffi-cient to give significant effect by introduction of the organic componentg while an amount in excess of 400 parts by wei~ht will worsen noticeably the non flammability to an extent comparable with that Of the expanded product made of the thermosettin~ resin alone.
For practicing the present invention more preferably, both of the phosphoric acid salt and the thermosetting resin are used in the state of liquids or solutionsg whereby more complete compatibility can be obtained to a great advantageO According to this odimerlt 9 the solutions of' the phosphoric acid salt and the thermosetting resin are completely mixed together to be made compatlbleg followed by mixing with hardening agent and~ if necessary~ the blowing agent to give desired inorganic~organic combined materialO
According to another preferred embodiment, the hardening agent and9 if` necessary, the blowing agent are prevlously dispersed in the solution of the thermoset-ting resin and the resultant dispersion is then mixed with the afore said solution of the phosphoric acid salt. This embodiment enables production o~ the desired inorganic~
organic combined material by way of two--liquid mixing~
and there~ore it is most suitable for moldirlg at the site or injection molding.
For practicing the present prccess according to the above embodiment by way of two-liquid mixing~
it is convenient to use a set of materials~ comprising ~(A) an aqueous solut,ion of the phosphoric acid salt as - 20 mentioned above containing 30 to ~5 wt,% of said phos-phoric acid salt, (B) a slurry containing 30 to 80 wt.
of solids in which a hardening agent as mentioned above is dispersed in an aqueous solution of a thermo~
setting resin as mentioned above at a weight ratio of 25 hardening agent to thermosetting resin of 1/1 to 1/40, and optionally (C) a blowing agent. By use of such a set of materials~ the inorganic-organic combined material can readily be prepared at the site at which - it is used by formulating the materials according to `~ , . - ~
.
. . , .
tile~ composition of the desired pLocluc.t.
In practicing -the present invent.ion, there may also be used additives such as reinforcing materials, aggregates, f.illers, water repellan-ts, stabilizers, pigments, surfactants, e-tc. In particular, as wa-ter repellants, there may be advantageously used in the present inventiP~, other than paraffin or silicone oil, those compounds having both hydrophobic groups and functional groups :reactive with the metal salt of phosphor.ic ac:id.
- As mentioned above, the inorganic-o.rganic combined expanded product can provide useful materials for light weigh-t construction materials or lagging ln ma-terials. In particular, i-t i9 possible to form.the expanded produc-t at the site at which it is applied to a grea-t commercial advantage.
The inorganic-organic combined e~panded productJ when it con-tains l to 20 parts by weight of the organic componen-t, can be improved in brittleness inherent in the inorganic material substantia].ly wi.thout impa~ing nonflammabili:ty.
When the organic content is in the range from 20 to 120 parts by weight, mechanical strength, water resistance and other properties are noticeably improved, and inflammability is extremely l~wer due to the cell wall st~ucture as mentio~ed above in which the lnorganic and organic components e~ist e~ masse, whereby there is obtained an e~panded product comparable to semi..no~1am~able materials~
12 - 1.
.
g~
~ 13 The expanded products with or~r!anic content in the range ~rom 120 to lloo parts by weight are also lower in in--flammabillty and have oxygen lndex values by far hi~her than conventional organic expanded products. In addition9 they are by far superior in mechanical strength to the organic expanded products of prior art in which inor~anic components such as inorganic fillers are merely dispersed.
As described above~ the inorganic-organic combined expanded product provided according to the present invention has excellent characteristlcs which are not found in inorganic foams, organic ~oams or organic-inorganic mixed foams in which organic and inorganic components are inhomogeneously mixed.
The present invention is further illustrated below with reference to the following Examples.
In the Examples~ thermal conductivity is measured by ASTM--C518. The oxygen index is measured by means of Inflammability Tester ON~1 (produced by Suga Testin~ Machine Co., I.td.)~ using test strip of 5 mm x 5 mm x 100 mm.
.
.
Exampl~ 1 Phosphoric acid (75% aqlleous solution) 160 wt. parts Aluminum hydroxide 20 WtD parts Zinc oxide 35 wto parts The above components are mixed to carry out the reaction~ whereb~ there is obtained a transparent viscous solution having E-value=0.44 and M/P-value=0.56.
On the other hand~ -there ls also prepared a slurry having 30 wt. parts of fused ma~nesiurn oxide dispersed in 50 wt. parts of a commercial]y available aqueous urea resln solution (solid content 70%~ Ply~
amine P-364 BL~ trade mark3 produced by Dainippon Ink CO~g l,td.).
The above solution and the slurry are mixed - together and sufficiently stirred. The resultant mixture is cast into a mold~ng frame of 2 cm x 2 cm x 10 cm. A~ter 6 hours~ hardening is found ko be completed to give a block of hardened product having R-value of 20 o . 81~ and M/P value of 1.5. This product is found to be semi--kransparent and have specific gravity of 1.9~
compression strength of 650 kg/cm2 and oxygen index of 90 or more.
Example 2 Phosphoric acid (75% aqueous solution~ ~0 wt. parts Aluminum hydroxide 10 wt. parts Zinc oxide 17.5 wt. parts .
.
, ~ 15 -l`he above componen~s are mixed to carry out the reaction9 whereby there is obtained a ~ransparent ~iscous solution h~lvinK E--value=0,44 and M/P-value=0.56.
On the other hand~ there is a]so prepared a slurry havln~ 15 wt. parts of' dead-burned magnesium oxide dispersed in 500 wt. parts of the same commercially available aqueous urea resin solution as used in Example 1.
The above solution and the slurry are mixed together~ followed by sufficient stirring~ and cast into a moldin~ frame of 2 cm x 2 cm x 10 cm. The molded product is found to be completely hardened after 6 hours to give a block of a hardened product having E-value of 0.84 and M/P-value of~ 1.5g comprising 100 wt. parts of 15 a hardened product of the phosphoric acid salt and -350 wt. parts of a hardened product of the urea resin.
This co-hardened product is semi-transparent and has specific gravity cf 1.5~ compression strength of 1050 kg/cm2 and oxygen lndex of 55Ø Fig. 1 shows the appearance of this product.
Comparison example 1 Aaueous urea resin solution 500 wt.parts (Solid content 70 wt.~ 3 Plyamine P-364 BL, trade markg produced by Dainippon Ink Co.g l.td.~
Anhydrous calcium sulfate powders 100 wt.parts To a slurry prepared by mixin~ the above `; components are added 10 wt. parts of a 10 % aqueous - phosphoric acid solution. The resultant mixture is cast in a moldlng f'rame of 2 cm x 2 cm x 10 cm.
:
.
-- 16 ~
~- After 3 hours, complete hardening is effected.
The thus prepared hardened productg containing 100 wt. par-ts of anhydrous calcium sulfate powders and 350 wt. parts of a hardened product of' the urea resin, is found to have specific gravlty of 1.5 7 compression strength of 850 kg/cm2 and oxygen index of 25Ø
Fi~. 2 shows the appearance of this product.
Example 3 Phosphoric acid (75~ aqueous solution) 160 wt. parts Aluminum hydroxide20 wt. parts Zinc oxide 35 wt, parts The above components are mixed and allowed to react to obtain a transparent viscous solutlon having E-value of 0.44 and M/P-value of 0,56.
To the above solution are added 100 wt. parts of an aqueous solution of a commercially available urea resin (solid content:70~ Plyamine P 364 BL, trade mark~
Dainippon Ink Co.~ Ltd.) to obkain a further vlscous~
transparent solution. Immediatelyg 70 wt. parts of' powdery basic magnesium carbonate are added to the solution to be completely mixed therein. Foaming begins immediately until the mixture is completely hardened after 6 hours. The E value after expansion and hardening is found to be o.84 3 and the M/P--value 1.5~
This expanded product is found to have a bulk density of 0.099 an average cell diameter of 1.9 mm and thermal conductivity of 0.035 kcal/m,hr.C.
. ~
.
~ 17 -Examples 4 ~ 5 3 Comparison examples 2 - 3 Example 1 i5 repeated except that the amount o~ the aqueous urea resin solution is varied as shown in Table 1.
Table 1 Comparison Comparison _xample 2 Example 4 ~ example 3 Urea resin 2.0 50 600 1500 (wt~ parts) Urea resin o.6 14.3 171 429 content*l ~1) Urea resin contentO solid urea resin(wt.parts) per 100 wt. parts of hardened phosphoric acid salt Each of the expanded product obtained has the properties as shown in Table 2.
Table 2 .... __ Avera~Je Thermal cell conduc- Compres- !
dia~ tivity sive Bulk meter kcal/ 0xy~en strength density (mm) m.hr C index k~/cm Comparison more less example 2 0.06 2.1 0.039than than 0,5 Example 4 0,07 1.0 0.038more 1.5 than Example 5 0.17 1.5 0'0LI3 62.5 17.8 Comparison example 3 0.61 1.0 0.08828.0 35.0 Examples 6 - 7 9 Comparison examples 4 - 5 There are prepared the phosphoric acid solutions havin~ the compositions as shown in Table 3.
,, .
~ .
Table 3 Comparison Comparison _am~le 4 Example 6 Fxample 7 example 5 75~ aqueous phosphoric 160 wt. 160 wt. 160 wt. 160 wt.
acid parts parts parts parts solution Aluminum None 20 wt. 25 wt. 20 wt.
hydroxide parts parts parts Magnesium 2.5 wt. None 10 wt. 10 wt.
oxide parts parts parts Zinc oxide 5 wt. 20 wt. 20 wto 20 wt.
parts parts parts parts Sodium None None None 20 wto hydroxide parts E value 0.07 0O34 0.53 oO85 M/P-value 0.10 0.41 o.66 1.17 State Colorless Colorless Colorless White trans trans- trans-- turbid parent parent parent Two solutions~ namely each of the phosphoric acid salt solutions having the above compositions and 200 wt. parts of a urea resin solution (solid contento 70%) having completely dispersed 50 wt. parts of aluminum silicateg 40 wto parts of magnesium oxide and 15 wt. parts of pentane dispersed therein, are mixed together and left to stand. The results are set forth in Table 4.
:~.
' 3 ~ ~
Table 9 Foaming Comparison Extreme heat generation with a great shri~kage example 4 until hardening Example 6 Foaming with mild heat generation;.
Specific gravity = 0.13 Example 7 Foaming with mild heat generation;
Specific gravity = 0.18 Comparison Neither heat generat.ion nor foaming occurs.
example 5 Comparison example 6 The same procedure as in Example 3 is repeated except 70 wtS
parts of the basic magnesium carbonate are changed to 35 wt, parts~ The resultant expanded and hardened product is found to have E -value-0~64 and M/P-value=0.86.
The expanded product obtained is very hygroscopi:c and ~:
exhibits acidity even aEter 4i3 hours.
Example 8 Primary aluminum phosphate .150 wt, parts :. 20 (50% aqueous solution, E-value=0.33, . M~P-value-0.33) Resol type phenol resin125 wt. parts (80% aqueous solution, ; BRL-lll, trade mark, produced by Showa Kobunshi.
Co., Ltd.) Aluminum powders 20 wt. parts After mixing the above components, the mixture is left to stand at 80 C for 30 mimltes in a hot air drier. After hardening, the expanded product obtained is found to have E-value=l.0, M/P-value=l.0 and specific gravity of 0.08. Fig. 3 shows the appearance of this product.
.,.`' .
, : ~ 19 ..... ' :
.
3~
~ 20 -This expancled product is :Lef't to stand in an electric furnace set at 800C ~or one hour. After the calcinationg the expanded product is discoloured in dark but its ori~inal cell structure is maintained (see Fig. 4~.
Comparison example 7 Resol type phenol resin 125 wt. parts (80P aqueous solution, B~L-1119 trade mark~
produced by Showa Kobunshi Co.g I.td.) Tertiary aluminurn phosphate 95 wt. parts powders Pehtane 5 wt. parts To the slurr~ having mixed -the above components are added 20 wto parts of a 10 % aqueous phosphoric acid solution in which 2.0 wt. parts of p'toluene sulfonic acid are dissolved. The m~xture is left to stand at room temperature and, after one minute, foamlng begins with generation of heat to give an expanded product having specific gravit~ of 0012.
This expanded product is left to stand in an electric furnace set at 800C for one hour. After the calcinationg only powdery carbonized product is remained.
Example 9 Phosphoric acid 160 wt. parts (75% aqueous solution) Aluminum hydroxide20 wt. parts Zinc oxide 20 WtD parts The above components are mixe~ and allowed to react to obtain a transparent and viscous solution.
After further adding 1.0 wt. paFt o~ lauryl amine as ., , .
21 ~
water rer,ellanl; and 2.0 wt. parts of' paper pulp as reillforcing materlal to the so:lution~ 100 wt. parts of an aqueous melamine resin solution (Nikalac~ trade mark~ produced by Sanwa Chemlcal Co. 7 Ltd.) having dispersed 20 wt. parts of metallic aluminum powders therein are added thereto. After complete mixing~
the mixture is left to stand in a hot air drier set at 100C for 30 minutes.
- The resultant e~panded product is found to have specific gravity of 0.16 and also to be endowed with perfect water repellency.
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Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An inorganic-organic combined material comprising a co-hardened product containing 100 parts by weight of a hardened product of at least one polyvalent metal phosphoric acid salt and 1 to 400 parts by weight of a hardened product of a thermo-setting resin curable with an acid catalyst, the equivalent ratio of the said metal to the phosphoric acid groups in said phosphoric salt being larger than 0.65, while the atomic ratio of the metal atoms to the phosphorus atoms being larger than 0.67, said polyvalent metal being at least one selected from the group consisting of magnesium, calcium, strontium, barium, zinc, manganese (II), copper (II), iron (II), aluminum, iron (III), titanium (III), cobalt, and zirconium and said thermosetting resin being at least one selected from the group consisting of resol type phenol resin, melamine resin, urea resin, furan resin, melamine-urea copolymer resin, furan-phenol copolymer resin and phenol-urea copolymer resin.
2. An inorganic-organic combined material according to Claim 1, further including at least one additive selected from the group consisting of reinforcing materials, aggregates, fillers, water repellants, stabilizers, pigments and surfactants.
3. An inorganic-organic combined material according to Claims 1 or 2, wherein said material is expanded to form cell walls with average diameter of less than 3 mm and have a bulk density of less than 0.5.
4. A process for producing an inorganic-organic combined material, which comprises mixing (a) a water soluble acidic phosphoric acid salt of at least one polyvalent metal wherein the equivalent ratio of the metal ions to the phosphate ions is in the range of from 1/9 to 3/4 and the atomic ratio of the metal atoms to the phosphorus atoms is in the range of from 1/6 to 3/2, (b) a hardening agent capable of hardening said phosphoric acid salt and (c) a thermosetting resin curable with an acid catalyst at a mixing ratio of 1 to 400 parts by weight of (c) to 100 parts by weight of (a)+(b), said thermosetting resin being at least one selected from the group consisting of resol type phenol resin, melamine resin, urea resin, furan resin, melamine-urea copolymer resin, furan-phenol copolymer resin and phenol-urea copolymer resin, and then allowing the resultant mixture to harden.
5. A process for producing an inorganic-organic combined material according to Claim 4, wherein the hardening is effected in the present of a blowing agent to effect expansion simultaneously with hardening.
6. A process for producing an inorganic-organic combined material according to Claim 4 or Claim 5, wherein the equivalent ratio of the metal to the phosphoric acid groups is controlled at greater than 0.65 and the atomic ratio of the metal atoms to the phosphorus atoms at greater than 0.67 in the expanded and hardened product.
7. A process for producing an inorganic-organic combined material according to Claim 4, wherein the polyvalent metal is at least one selected from the group consisting of di-valent metals and tri-valent metals.
8. A process for producing an inorganic-organic combined material according to Claim 7, wherein the di-valent metal is at least one selected from the group consisting of magnesium, calcium, strontium, barium, zinc, manganese (II), copper (II) and iron (II).
9. A process for producing an inorganic-organic combined material according to Claim 7, wherein the tri-valent metal is at least one selected from the group consisting of aluminum, iron (III) and titanium (III).
10. A process for producing an inorganic-organic combined material according to Claim 4, wherein the hardening agent (b) is at least one selected from the group consisting of metals having two or more valences, and hydroxides, oxides, silicates and titanates thereof.
11. A process for producing an inorganic-organic combined material according to Claim 5, wherein the blowing agent is at least one selected from the group consisting of water, fluorocarbons or hydrocarbons having low boiling points, hydrogen peroxide, metallic powders and carbonates.
12. A process for producing an inorganic-organic combined material according to Claim 5, wherein the hardening agent and the blowing agent are both carbonates or metallic powders of a metal having two or more valences.
13. A process for producing an inorganic-organic combined material according to Claim 5, wherein the two liquids of a liquid, obtained by previously dispersing the hardening agent (b) and the blowing agent in a solution of the thermosetting resin (c), and an aqueous solution of the acidic phosphoric acid salt (a) are mixed.
14. A process for producing all inorganic-organic combined material according to Claims 4 or 5, wherein there is further contained in the mixture at least one additive selected from the group consisting of reinforcing materials, aggregates, fillers, water repellants, stabilizers, pigments and surfactants.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15654777A JPS5835532B2 (en) | 1977-12-27 | 1977-12-27 | Inorganic↓-organic bonded foam and its manufacturing method |
| JP156547 | 1977-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1108349A true CA1108349A (en) | 1981-09-01 |
Family
ID=15630172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA317,628A Expired CA1108349A (en) | 1977-12-27 | 1978-12-08 | Inorganic-organic combined material and preparation thereof |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5835532B2 (en) |
| CA (1) | CA1108349A (en) |
| DE (1) | DE2856137C3 (en) |
| FR (1) | FR2413440A1 (en) |
| GB (1) | GB2011926B (en) |
| SU (1) | SU1020007A3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS606032U (en) * | 1983-06-27 | 1985-01-17 | 三鈴金属商事株式会社 | gutter bracket |
| JPS606035U (en) * | 1983-06-27 | 1985-01-17 | 三鈴金属商事株式会社 | gutter bracket |
| JP2901537B2 (en) | 1995-09-27 | 1999-06-07 | 三洋化成工業株式会社 | Inorganic-organic composite foam and method for producing the same |
| WO1999002468A1 (en) * | 1997-07-08 | 1999-01-21 | Sanyo Chemical Industries, Ltd. | Inorganic/organic composite foam and process for producing the same |
| GB2505974B (en) * | 2012-09-18 | 2016-11-02 | Kingspan Holdings (Irl) Ltd | Phenolic foam |
-
1977
- 1977-12-27 JP JP15654777A patent/JPS5835532B2/en not_active Expired
-
1978
- 1978-12-08 CA CA317,628A patent/CA1108349A/en not_active Expired
- 1978-12-21 FR FR7835954A patent/FR2413440A1/en active Granted
- 1978-12-21 GB GB7849661A patent/GB2011926B/en not_active Expired
- 1978-12-27 SU SU782700103A patent/SU1020007A3/en active
- 1978-12-27 DE DE19782856137 patent/DE2856137C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2011926B (en) | 1982-08-25 |
| JPS5835532B2 (en) | 1983-08-03 |
| SU1020007A3 (en) | 1983-05-23 |
| GB2011926A (en) | 1979-07-18 |
| FR2413440A1 (en) | 1979-07-27 |
| DE2856137C3 (en) | 1982-03-25 |
| JPS5488925A (en) | 1979-07-14 |
| DE2856137B2 (en) | 1981-06-19 |
| FR2413440B1 (en) | 1983-12-09 |
| DE2856137A1 (en) | 1979-06-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |