CA2086418A1 - Cocondensed urea resin - Google Patents
Cocondensed urea resinInfo
- Publication number
- CA2086418A1 CA2086418A1 CA002086418A CA2086418A CA2086418A1 CA 2086418 A1 CA2086418 A1 CA 2086418A1 CA 002086418 A CA002086418 A CA 002086418A CA 2086418 A CA2086418 A CA 2086418A CA 2086418 A1 CA2086418 A1 CA 2086418A1
- Authority
- CA
- Canada
- Prior art keywords
- resin
- mol
- urea
- cocondensed
- resorcin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
- C08G14/08—Ureas; Thioureas
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
[ABSTRACT]
It is the object of the present invention to improve the resistances to water, weather and boiling water and the workability of cocondensed resins. According to the present invention, the foregoing object is attained by providing a cocondensation resin which entails cocondensing urea with a polyvalent phenol. It is generally difficult to cocondense urea with a polyvalent phenol. According to the present invention, nevertheless, a cocondensed resin is easily able to be produced by reacting 1 mol of urea with 0.2 to 2.0 mol of a polyvalent phenol and 0.1 to 2.0 mol of an aldehyde donor by heating in a pH range from 4 to 9.
It is the object of the present invention to improve the resistances to water, weather and boiling water and the workability of cocondensed resins. According to the present invention, the foregoing object is attained by providing a cocondensation resin which entails cocondensing urea with a polyvalent phenol. It is generally difficult to cocondense urea with a polyvalent phenol. According to the present invention, nevertheless, a cocondensed resin is easily able to be produced by reacting 1 mol of urea with 0.2 to 2.0 mol of a polyvalent phenol and 0.1 to 2.0 mol of an aldehyde donor by heating in a pH range from 4 to 9.
Description
` 2086418 [SPECIFICATION]
COCONDENSED UREA RESIN
[EIELD OF T~IE INVENTION ]
The present invention relates to an inexpensive cocondensed condensation resin with advanced resistances to water, weather and boiling water, and with high workability. It is useful as an additive, binder, coating, material and the like for organic and inorganic materials including wood, fiber, paper and glass fiber.
[DESCRIPTION OF THE PRIOR ART]
Hitherto, the urea resin used for adhering materials including wood has a poor resistance to water, and a cocondensed resin produced by cocondensing urea with a comonomer including melamine and phenol to improve the water resistance has been provided. Nevertheless, even though the wa~er resistance of such a cocondnsed urea resin has been improved, the resistances to boiling water and weather are still insufficient. After the above, although the cocondensation of urea with a polyvalent phenol including resorcin has been investigated, it is very difficult to cocondense urea with a polyvalent phenol monomer because both the reaction rates with aldehyde are much different from each other. It has been considered so far, therefore, that the cocondensation of urea with a polyvalent phenol is practically impossible.
Accordingly, instead of a urea polyvalent phenol ~ ' 2086~1~
cocondensed resin, a mixture of urea resin with a polyvalent phenol monomer (e.g. Tokko Sho No. 57-9600) and a mixture of urea resin with a polyvalen-t phenol resin (e.g. Tokko Sho No. S8-23425) have been provided.
Although the resistances to water and boiling water of the said mixture and the resin mixture are therefore improved, additives including a modifier resin, organic and inorganic fillers, a thickening agent and a curing agent are not necessarily compatible with the said mixtures, so the compounds are thickened and finally become immiscible, and if the worst should happen, the pot life of the said mixtures, after compounding is shortened and the workability is lowered.
Further, a process for condensing the primary condensation product of urea with a polyvalent phenol and formaldehyde when required (Tokkai Sho No. 48-54148) has been provided. In this process, nevertheless, the addition of the polyvalent phenol is as low as 0.05 to 0.2 mol to 1 mol of the urea because the primary condensation product of the urea is used. The effect of the cocondensation with the said polyvalent phenol is, therefore, not necessarily sufficient for improving the resistances to boiling water and weather.
~DISCLOSURE OF THE INVENTION]
As a means to disclose the above-described problems in the prior art, the present invention provides a cocondensed urea resin which is produced by cocondensing 1 mol of urea with 0.2 to 2.0 mol of a polyvalent phenol and 0.1 to 2.0 mol of an aldehyde donor by heating in a pH range from 4 to 9.
20~6~18 [DETAILED DESCRIPTION OF THE INVENTION]
The present invention is described in detail hereafter.
[POLYVALENT PHENOL]
The polyvalent phenol in the present invention is a mixture of one or two or more of the polyvalent phenols including resorcin, alkyl resorcin, pyrogallol, catéchol, alkyl catechol, hydroquinone, alkyl hydroquinone, phloroglucinol, bisphenol and dihydroxynaphthalene, preferably resorcin or alkyl resorcin, particularly preferably alkyl resorcin, with a higher reaction rate with aldehyde than resorcin.
The alkyl resorcin in the present invention is 5-methyl resorcin, 5-ethyl resorcin, 5 propyl resorcin, 5-n-butyl resorcin, 4,5-dimethyl resorcin, 2,5-dimethyl resorcin, 4,5-diethyl resorcin, 2,5-diethyl resorcin, 4,5-dipropyl resorcin, 2,5-dipropyl resorcin, 4-methyl-5-ethyl resorcin, 2-methyl-5-ethyl resorcin, 2-methyl-5-propyl resorcin, 2,4,5-trimethyl resorcin and 2,4,5-triethyl resorcin. Particularly, 5-methyl resorcin cocondenses easily with the urea and produces a low-temperature curable, water, weather and boiling water-resistant cocondensed urea resin. Since mixed polyvalent phenols produced by the dry distillation of oil shale from Estonia are inexpensive and contain much reactive alkyl resorcins as well as 5-methyl resorcin, they are some of the most adequate polyvalent phenols for the present invention.
[ALDEHYDE DONOR]
COCONDENSED UREA RESIN
[EIELD OF T~IE INVENTION ]
The present invention relates to an inexpensive cocondensed condensation resin with advanced resistances to water, weather and boiling water, and with high workability. It is useful as an additive, binder, coating, material and the like for organic and inorganic materials including wood, fiber, paper and glass fiber.
[DESCRIPTION OF THE PRIOR ART]
Hitherto, the urea resin used for adhering materials including wood has a poor resistance to water, and a cocondensed resin produced by cocondensing urea with a comonomer including melamine and phenol to improve the water resistance has been provided. Nevertheless, even though the wa~er resistance of such a cocondnsed urea resin has been improved, the resistances to boiling water and weather are still insufficient. After the above, although the cocondensation of urea with a polyvalent phenol including resorcin has been investigated, it is very difficult to cocondense urea with a polyvalent phenol monomer because both the reaction rates with aldehyde are much different from each other. It has been considered so far, therefore, that the cocondensation of urea with a polyvalent phenol is practically impossible.
Accordingly, instead of a urea polyvalent phenol ~ ' 2086~1~
cocondensed resin, a mixture of urea resin with a polyvalent phenol monomer (e.g. Tokko Sho No. 57-9600) and a mixture of urea resin with a polyvalen-t phenol resin (e.g. Tokko Sho No. S8-23425) have been provided.
Although the resistances to water and boiling water of the said mixture and the resin mixture are therefore improved, additives including a modifier resin, organic and inorganic fillers, a thickening agent and a curing agent are not necessarily compatible with the said mixtures, so the compounds are thickened and finally become immiscible, and if the worst should happen, the pot life of the said mixtures, after compounding is shortened and the workability is lowered.
Further, a process for condensing the primary condensation product of urea with a polyvalent phenol and formaldehyde when required (Tokkai Sho No. 48-54148) has been provided. In this process, nevertheless, the addition of the polyvalent phenol is as low as 0.05 to 0.2 mol to 1 mol of the urea because the primary condensation product of the urea is used. The effect of the cocondensation with the said polyvalent phenol is, therefore, not necessarily sufficient for improving the resistances to boiling water and weather.
~DISCLOSURE OF THE INVENTION]
As a means to disclose the above-described problems in the prior art, the present invention provides a cocondensed urea resin which is produced by cocondensing 1 mol of urea with 0.2 to 2.0 mol of a polyvalent phenol and 0.1 to 2.0 mol of an aldehyde donor by heating in a pH range from 4 to 9.
20~6~18 [DETAILED DESCRIPTION OF THE INVENTION]
The present invention is described in detail hereafter.
[POLYVALENT PHENOL]
The polyvalent phenol in the present invention is a mixture of one or two or more of the polyvalent phenols including resorcin, alkyl resorcin, pyrogallol, catéchol, alkyl catechol, hydroquinone, alkyl hydroquinone, phloroglucinol, bisphenol and dihydroxynaphthalene, preferably resorcin or alkyl resorcin, particularly preferably alkyl resorcin, with a higher reaction rate with aldehyde than resorcin.
The alkyl resorcin in the present invention is 5-methyl resorcin, 5-ethyl resorcin, 5 propyl resorcin, 5-n-butyl resorcin, 4,5-dimethyl resorcin, 2,5-dimethyl resorcin, 4,5-diethyl resorcin, 2,5-diethyl resorcin, 4,5-dipropyl resorcin, 2,5-dipropyl resorcin, 4-methyl-5-ethyl resorcin, 2-methyl-5-ethyl resorcin, 2-methyl-5-propyl resorcin, 2,4,5-trimethyl resorcin and 2,4,5-triethyl resorcin. Particularly, 5-methyl resorcin cocondenses easily with the urea and produces a low-temperature curable, water, weather and boiling water-resistant cocondensed urea resin. Since mixed polyvalent phenols produced by the dry distillation of oil shale from Estonia are inexpensive and contain much reactive alkyl resorcins as well as 5-methyl resorcin, they are some of the most adequate polyvalent phenols for the present invention.
[ALDEHYDE DONOR]
2~86~18 The aldehyde donor used in the present invention i.s one or two or more mixtures of compounds which have aldehyde group(s) or liberate aldehyde group(s) by such a treatment as heating including formalin, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, fulfural, glyoxal, n-butyl aldehyde, capronaldehyde, benzaldehyde, acrolein, tetraoxymethylene, phenyl acetaldehyde, o-tolylaldehyde and salicylaldehyde.
~COMPLEXING AGENT]
In the present invention, a complexing agent may be used for moderating the reaction because the reactivity of the polyvalent phenol, particularly such an alkyl resorcin as 5-methyl resorcin, with aldehyde is extremely high. The complexing agent in the present invention is a compound which has ketone or amide group(s) capable of complexing the phenol group in the polyvalent phenol including acetone and caprolactam, preferably acetone. Although the addition of the complexing agent is not specially limited, it is usually preferable to add approximately 0.4 to 0.~ mol of the complexing agent to 1 mol of the polyvalent phenol.
[THIRD COMPONENT]
In addition to urea, a polyvalent phenol, an aldehyde donor and a complexing agent in the cocondensation reaction for manufacturing the cocondensed resin in the present invention, one or two or more of the cocondensing or modifying agents including melamine, 208~8 thiourea, phenol, alkyl phenol, benzoguanamine, toluene, coumarone, cyclohexane, cashew nut oil, tannins, dammar, shellac, a rosin or rosin derivative, petroleum resin, methanol, ethanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, furfurl alcohol, linseed oil, tung oil, or castor oil may be added.
[MANUFACTURING OF COCONDENSATION RESIN]
The process for manufacturing the cocondensed resin of the present invention involves adding 0.2 to 2.0 mol, preferably 0.4 to 2.0 mol, of a polyvalent phenol and 0.16 to 1.6 mol of a complexing agent as required to 1 mol of urea, ad~usting the pH to 4.0 to 9.0, preferably to 8.0 to 8.5, with an acid or alkali, adding 0.1 to 2.0 mol of an aldehyde donor to the mixture and heating it usually at a temperature of 75 to 80C . It is desirable to cool -the reaction product down to room temperature after the reaction and adjust the pH to approximately 8Ø
Since a large quantity of unreacted urea remains in the product resin in the case of the addition of 0.2 mol or more of a polyvalent phenol, the resistances to water and boiling water of the resin are low and the stability of low in the case of an addition of 2.0 mol or more of said polyvalent phenl. The performance of the product resin is sometimes deteriorated by adding 0.4 mol or less of said polyvalent phenol depending upon the type of it because the unreacted urea easily remains in the cocondensation product. It is, therefore, usually preferable to add 0.4 to 2.0 mol of said polyvalent phenol.
208~41c~
In the present invention, a third component may be added to the reaction system either before the condensation reaction or after the reaction if the third component does not participate in the cocondensation.
[ COMPO~NDI NG ]
The products including adllesive, binder and coating material from the cocondensed resin of the present invention are usually manufactured in such a way -that 15 to 80 parts by weight of the aldehyde donor is added to 100 parts by weight of the cocondensed resin of the present invention, and if necessary, a third component including natural rubber and its derivatives, synthetic rubber such as SBR, NBR and CR, synthetic resin such as vinyl acetate resin, acrylic resin and urethane resin, filler such as CMC, PVA, starch, glue, gelatin, powdered blood, walnut powder, coconut shell flour, wheat flour, calcium carbonate, talc and gypsum, pigment, dye, flame retardant, insecticide or an antiseptic agent is added.
[APPLICATIONS]
The adhesives, binders and coating materials manufactured using the cocondensation product of the present invention are cured at normal temperature or by heating. Since they are rapidly cured by heating at 100 C or higher, cured resins adhesive to woody and fibrous materials are produced.
The cocondensed resin of the present invention is, therefore, applicable to adhesives, binders and coa-ting materials for organic and inorganic materials including 2086~18 wood such as plywood, laminated lumber and particle board, paper such as corrugated board, fiber such as felt and non-woven fabric, glass fiber, rock wool, ceramic fiber and carbon fiber.
Since the acidic curing catalyst required for curing conventional cocondensed resins is not used for curing the cocondensed resin of the present invention, it is kept neutral. Accordingly, even afer a long time, the cured resin is not hydrolyzed by the remaining acid and an adhered woody material does not deteriorate, whereupon high durability can be expected. In a case of necessity, nevertheless, an acidic catalyst may be used.
Unlike the conventional cocondensed resin, the resistances to water, boiling water and weather of the cocondensed resin of the present invention produced by cocondensation with a polyvalent phenol are equal to those of polyvalent phenol-based resins including resorcin and alkyl resorcin-based resins.
Since the curing rate of a resorcin-based resin using paraformaldehyde as the curing agent is so high that its pot life is short, hexamethylenetetramine must be used as the curing agent. Meanwhile, the pot life of the cocondensed resin of the present invention is as long as two hours in a case using paraformaldehyde and it is cured at normal temperature. Moreover, it is able to be cured in a remarkably short time by heating at a temperature as relatively low as 100 to 120C -Consequently, the workability of the cocondensed resin of the present invention is very high.
` 2086418 The density of the crosslinkings between urea and aldehyde produced by cocondensation with a polyvalent phenol is so low in the cocondensed resin of the present invention that the hardness of the resin is decreased, thereby reducing the stress caused by cure shirinkage.
The layers in the cured resin product are hardly cracked or deformed, as well as the resin being is durable.
[EXAMPLE 1]
60 parts by weight (1 mol) of urea 62 parts by weight (0.5 mol) of 5-methyl resorcin and 14.5 parts by weight (0.25 mol) of acetone as the complexing agent are put into a reaction flask. The pH value of the mixture is adjusted to 8.0 with a 40%-caustic soda solution.
Then, 40.5 parts by weight (0.5 mol) of 37~-formalin is added drop by drop to the stirred solution at 50 to 55C
for 30 minutes and successively heated up to 75 to 85C
for 90 minutes to accelerate the reaction. After cooling it down, the pH of the solution is adjusted to 8.0 again to produce the cocondensed resin (Sample 1) which is stable at room temperature for two to three months or longer.
An adhesive agent is prepared by adding 20 parts by weight of coconut shell flour as the filler and 20 parts by weight of paraformaldehyde as the curing agent to 100 parts by weight of Sample 1 and mixing them. A
sheet of plywood is manufactured using the adhesive agent under the under-mentioned conditions and the adhesive strength is measured. The results are shown in Table 1.
Composition: 3-ply (1.5-3.0-1.5 mm) lauan 2086~18 Application: 35 g/300 x 300 mm2 Hot pressing: 10 kg/c~ at 105C for 4 mins.
[TABLE 1]
Adhesivity Wood failure (kg/cm2) rate (%) Ordinary adhesion 11.4 100 . Boiling for 72 hrs 8.3 98 :.
(Adhesion test: In compliance with the Test Method ! for Structural Plywood of JAS) ~EXAMPLE 2]
The cocondensed resin (Sample 2) is prepared using 55 parts by weight (0.5 mol) of resorcin instead of the 5-methyl resorcin as used in Example 1, using the same recipe and under the same reaction conditions as in Example 1. A sheet of the same plywood as in Example 1 is manufactured and an adhesive strength test is carried out. The results are shown in Table 2.
[TABLE 2]
_ Adhesivity Wood failure . (kg/cm2) rate (~) . Ordinary adhesion 11.0 Boiling for 72 hrs 8 0 95 [EXAMPLE 3]
20 parts by weight of paraformaldehyde is added to 100 _ g _ ;, ~
parts each by weight of Samples 1 and 2 of the cocondensed resin used in Examples 1 and 2, respectively. 10 wt% of broadleaf-tree fibrillated chips is added to each of the mixtures, and they are respectively mixed. The mixtures are respectively heated under pressure at 140C for 2 minutes to fabricate fiberboards 3 mm thick with a specific gravity of 0.8. The performance of the said fiberboards is shown in Table 3.
[COMPARISON 1]
For comparison with Example 3, 0.6 parts by weight of ammonium chloride as the curing agent is added to 100 parts by weight of urea resin corresponding to 50% of the normal condition to manufacture an adhesive agent.
A sample of this is tested in the same way as in Example 3. The test results are shown in Table 3.
[TABLE 3]
sending strength Flexibility _ ~kg/~ ) Sample 1 200 O
Sample 2 180 Comparison 1 170 X
Flexibility;
O : When a test piece 50 mm wide and 300 mm long is bent in the center at 20 degrees, the flexibility remains unchanged.
: The test piece is cracked by the bending though it is not broken.
:, X : The test piece is broken by the bending.
[EXAMPLE 4]
parts by weight (1 mol) of urea, 74 parts by weight (0.5 mol) of alkyl resorcin obtained by the dry distillation of oil shale, and 14.5 parts by weight (0.25 mol) oE acetone as the complexing agent are put into a reaction flask. The pH value of the mixture is adjusted to 8.0 with a 40~-aqueous solution of caustic soda and 40.5 parts by weight (0.5 mol) of 37~-formalin is added drop by drop to the stirred solution at a temperature of 50 to 52C for 30 minutes. Then the solution is heated at 80 to 85 C for 100 minutes to accelerate the reaction. After cooling the solution down to room temperature, the pH of the said solution is adjusted to 8.5 to produce the cocondensed resin (Sample 3). A sample of the said resin is stable for three months or longer.
An adhesive agent is prepared by adding 15 parts by weight each of walnut powder and paraformaldehyde to 100 parts by weight of the sample resin and mixing them. A
sheet of plywood is fabricated in the same way as in Example 1. The pot life and adhesion tests for the test piece are then carried out. The test results are shown in Table 4.
[COMPARISON 2]
For comparison with Example 4, 15 parts by weight of walnut powder and 3 parts by weight of paraformaldehyde as the curing agent are added to a mixture of 80 parts by weight of urea resin corresponding to 50% of the normal condition with 20 parts by weight of 50%-alkyl resorcin to prepare an adhesive agent. The same tests as in Example 4 are then carried out. The test results are shown in Table 4.
[TABLE 4]
Sample 3 Comparison Sample 2 Pot life (hrs) 3.8 1.0 Ordinary adhesion Adhesivity (kg/cn~) 12.5 11.2 Wood failure rate (~) 100 80 Boiling for 72 hrs Adhesivity (kg/cn~) 8.5 7.5 Wood failure rate (%) 100 70 (Pot life: In accordance with the JIS K6840 Test Method) The test results in ~xamples 1 to 3 indicate that the adhesivity and the resistances to water and boiling water of the cocondensed resin of the present invention are high and that an alkyl resorcin gives higher flexibility to the boards than resorcin from among the polyvalent phenols. The results of Example 4 indicate that the pot life and workability of the resin of Sample 3 are superior to -those of a blend of urea resin and a polyvalent phenol.
~COMPLEXING AGENT]
In the present invention, a complexing agent may be used for moderating the reaction because the reactivity of the polyvalent phenol, particularly such an alkyl resorcin as 5-methyl resorcin, with aldehyde is extremely high. The complexing agent in the present invention is a compound which has ketone or amide group(s) capable of complexing the phenol group in the polyvalent phenol including acetone and caprolactam, preferably acetone. Although the addition of the complexing agent is not specially limited, it is usually preferable to add approximately 0.4 to 0.~ mol of the complexing agent to 1 mol of the polyvalent phenol.
[THIRD COMPONENT]
In addition to urea, a polyvalent phenol, an aldehyde donor and a complexing agent in the cocondensation reaction for manufacturing the cocondensed resin in the present invention, one or two or more of the cocondensing or modifying agents including melamine, 208~8 thiourea, phenol, alkyl phenol, benzoguanamine, toluene, coumarone, cyclohexane, cashew nut oil, tannins, dammar, shellac, a rosin or rosin derivative, petroleum resin, methanol, ethanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin, furfurl alcohol, linseed oil, tung oil, or castor oil may be added.
[MANUFACTURING OF COCONDENSATION RESIN]
The process for manufacturing the cocondensed resin of the present invention involves adding 0.2 to 2.0 mol, preferably 0.4 to 2.0 mol, of a polyvalent phenol and 0.16 to 1.6 mol of a complexing agent as required to 1 mol of urea, ad~usting the pH to 4.0 to 9.0, preferably to 8.0 to 8.5, with an acid or alkali, adding 0.1 to 2.0 mol of an aldehyde donor to the mixture and heating it usually at a temperature of 75 to 80C . It is desirable to cool -the reaction product down to room temperature after the reaction and adjust the pH to approximately 8Ø
Since a large quantity of unreacted urea remains in the product resin in the case of the addition of 0.2 mol or more of a polyvalent phenol, the resistances to water and boiling water of the resin are low and the stability of low in the case of an addition of 2.0 mol or more of said polyvalent phenl. The performance of the product resin is sometimes deteriorated by adding 0.4 mol or less of said polyvalent phenol depending upon the type of it because the unreacted urea easily remains in the cocondensation product. It is, therefore, usually preferable to add 0.4 to 2.0 mol of said polyvalent phenol.
208~41c~
In the present invention, a third component may be added to the reaction system either before the condensation reaction or after the reaction if the third component does not participate in the cocondensation.
[ COMPO~NDI NG ]
The products including adllesive, binder and coating material from the cocondensed resin of the present invention are usually manufactured in such a way -that 15 to 80 parts by weight of the aldehyde donor is added to 100 parts by weight of the cocondensed resin of the present invention, and if necessary, a third component including natural rubber and its derivatives, synthetic rubber such as SBR, NBR and CR, synthetic resin such as vinyl acetate resin, acrylic resin and urethane resin, filler such as CMC, PVA, starch, glue, gelatin, powdered blood, walnut powder, coconut shell flour, wheat flour, calcium carbonate, talc and gypsum, pigment, dye, flame retardant, insecticide or an antiseptic agent is added.
[APPLICATIONS]
The adhesives, binders and coating materials manufactured using the cocondensation product of the present invention are cured at normal temperature or by heating. Since they are rapidly cured by heating at 100 C or higher, cured resins adhesive to woody and fibrous materials are produced.
The cocondensed resin of the present invention is, therefore, applicable to adhesives, binders and coa-ting materials for organic and inorganic materials including 2086~18 wood such as plywood, laminated lumber and particle board, paper such as corrugated board, fiber such as felt and non-woven fabric, glass fiber, rock wool, ceramic fiber and carbon fiber.
Since the acidic curing catalyst required for curing conventional cocondensed resins is not used for curing the cocondensed resin of the present invention, it is kept neutral. Accordingly, even afer a long time, the cured resin is not hydrolyzed by the remaining acid and an adhered woody material does not deteriorate, whereupon high durability can be expected. In a case of necessity, nevertheless, an acidic catalyst may be used.
Unlike the conventional cocondensed resin, the resistances to water, boiling water and weather of the cocondensed resin of the present invention produced by cocondensation with a polyvalent phenol are equal to those of polyvalent phenol-based resins including resorcin and alkyl resorcin-based resins.
Since the curing rate of a resorcin-based resin using paraformaldehyde as the curing agent is so high that its pot life is short, hexamethylenetetramine must be used as the curing agent. Meanwhile, the pot life of the cocondensed resin of the present invention is as long as two hours in a case using paraformaldehyde and it is cured at normal temperature. Moreover, it is able to be cured in a remarkably short time by heating at a temperature as relatively low as 100 to 120C -Consequently, the workability of the cocondensed resin of the present invention is very high.
` 2086418 The density of the crosslinkings between urea and aldehyde produced by cocondensation with a polyvalent phenol is so low in the cocondensed resin of the present invention that the hardness of the resin is decreased, thereby reducing the stress caused by cure shirinkage.
The layers in the cured resin product are hardly cracked or deformed, as well as the resin being is durable.
[EXAMPLE 1]
60 parts by weight (1 mol) of urea 62 parts by weight (0.5 mol) of 5-methyl resorcin and 14.5 parts by weight (0.25 mol) of acetone as the complexing agent are put into a reaction flask. The pH value of the mixture is adjusted to 8.0 with a 40%-caustic soda solution.
Then, 40.5 parts by weight (0.5 mol) of 37~-formalin is added drop by drop to the stirred solution at 50 to 55C
for 30 minutes and successively heated up to 75 to 85C
for 90 minutes to accelerate the reaction. After cooling it down, the pH of the solution is adjusted to 8.0 again to produce the cocondensed resin (Sample 1) which is stable at room temperature for two to three months or longer.
An adhesive agent is prepared by adding 20 parts by weight of coconut shell flour as the filler and 20 parts by weight of paraformaldehyde as the curing agent to 100 parts by weight of Sample 1 and mixing them. A
sheet of plywood is manufactured using the adhesive agent under the under-mentioned conditions and the adhesive strength is measured. The results are shown in Table 1.
Composition: 3-ply (1.5-3.0-1.5 mm) lauan 2086~18 Application: 35 g/300 x 300 mm2 Hot pressing: 10 kg/c~ at 105C for 4 mins.
[TABLE 1]
Adhesivity Wood failure (kg/cm2) rate (%) Ordinary adhesion 11.4 100 . Boiling for 72 hrs 8.3 98 :.
(Adhesion test: In compliance with the Test Method ! for Structural Plywood of JAS) ~EXAMPLE 2]
The cocondensed resin (Sample 2) is prepared using 55 parts by weight (0.5 mol) of resorcin instead of the 5-methyl resorcin as used in Example 1, using the same recipe and under the same reaction conditions as in Example 1. A sheet of the same plywood as in Example 1 is manufactured and an adhesive strength test is carried out. The results are shown in Table 2.
[TABLE 2]
_ Adhesivity Wood failure . (kg/cm2) rate (~) . Ordinary adhesion 11.0 Boiling for 72 hrs 8 0 95 [EXAMPLE 3]
20 parts by weight of paraformaldehyde is added to 100 _ g _ ;, ~
parts each by weight of Samples 1 and 2 of the cocondensed resin used in Examples 1 and 2, respectively. 10 wt% of broadleaf-tree fibrillated chips is added to each of the mixtures, and they are respectively mixed. The mixtures are respectively heated under pressure at 140C for 2 minutes to fabricate fiberboards 3 mm thick with a specific gravity of 0.8. The performance of the said fiberboards is shown in Table 3.
[COMPARISON 1]
For comparison with Example 3, 0.6 parts by weight of ammonium chloride as the curing agent is added to 100 parts by weight of urea resin corresponding to 50% of the normal condition to manufacture an adhesive agent.
A sample of this is tested in the same way as in Example 3. The test results are shown in Table 3.
[TABLE 3]
sending strength Flexibility _ ~kg/~ ) Sample 1 200 O
Sample 2 180 Comparison 1 170 X
Flexibility;
O : When a test piece 50 mm wide and 300 mm long is bent in the center at 20 degrees, the flexibility remains unchanged.
: The test piece is cracked by the bending though it is not broken.
:, X : The test piece is broken by the bending.
[EXAMPLE 4]
parts by weight (1 mol) of urea, 74 parts by weight (0.5 mol) of alkyl resorcin obtained by the dry distillation of oil shale, and 14.5 parts by weight (0.25 mol) oE acetone as the complexing agent are put into a reaction flask. The pH value of the mixture is adjusted to 8.0 with a 40~-aqueous solution of caustic soda and 40.5 parts by weight (0.5 mol) of 37~-formalin is added drop by drop to the stirred solution at a temperature of 50 to 52C for 30 minutes. Then the solution is heated at 80 to 85 C for 100 minutes to accelerate the reaction. After cooling the solution down to room temperature, the pH of the said solution is adjusted to 8.5 to produce the cocondensed resin (Sample 3). A sample of the said resin is stable for three months or longer.
An adhesive agent is prepared by adding 15 parts by weight each of walnut powder and paraformaldehyde to 100 parts by weight of the sample resin and mixing them. A
sheet of plywood is fabricated in the same way as in Example 1. The pot life and adhesion tests for the test piece are then carried out. The test results are shown in Table 4.
[COMPARISON 2]
For comparison with Example 4, 15 parts by weight of walnut powder and 3 parts by weight of paraformaldehyde as the curing agent are added to a mixture of 80 parts by weight of urea resin corresponding to 50% of the normal condition with 20 parts by weight of 50%-alkyl resorcin to prepare an adhesive agent. The same tests as in Example 4 are then carried out. The test results are shown in Table 4.
[TABLE 4]
Sample 3 Comparison Sample 2 Pot life (hrs) 3.8 1.0 Ordinary adhesion Adhesivity (kg/cn~) 12.5 11.2 Wood failure rate (~) 100 80 Boiling for 72 hrs Adhesivity (kg/cn~) 8.5 7.5 Wood failure rate (%) 100 70 (Pot life: In accordance with the JIS K6840 Test Method) The test results in ~xamples 1 to 3 indicate that the adhesivity and the resistances to water and boiling water of the cocondensed resin of the present invention are high and that an alkyl resorcin gives higher flexibility to the boards than resorcin from among the polyvalent phenols. The results of Example 4 indicate that the pot life and workability of the resin of Sample 3 are superior to -those of a blend of urea resin and a polyvalent phenol.
Claims
1. A cocondensed resin, which entails mixing 1 mol of urea, 0.2 to 2.0 mol of a polyvalent phenol and 0.1 to 2.0 mol of an aldehyde donor and reacting them by heating in a pH range from 4 to 9 .
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP1991/000590 WO1992019661A1 (en) | 1991-04-30 | 1991-04-30 | Cocondensed urea resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2086418A1 true CA2086418A1 (en) | 1992-10-31 |
Family
ID=4150917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002086418A Abandoned CA2086418A1 (en) | 1991-04-30 | 1991-04-30 | Cocondensed urea resin |
Country Status (3)
| Country | Link |
|---|---|
| CA (1) | CA2086418A1 (en) |
| DE (1) | DE4193551T1 (en) |
| WO (1) | WO1992019661A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE790891R (en) * | 1971-11-03 | 1973-05-03 | Basf Ag | STICK TO |
| JPS5823425B2 (en) * | 1975-10-21 | 1983-05-14 | ナゴヤユカガクコウギヨウ カブシキガイシヤ | Setuchiyakuzaisoseibutsu |
| JPS53117032A (en) * | 1977-03-23 | 1978-10-13 | Nagoya Yukagaku Kogyo Kk | Adhesive composition |
| DE3124089A1 (en) * | 1981-06-19 | 1983-01-05 | Basf Ag, 6700 Ludwigshafen | NITROGEN BASED GROUPS AND POLYADDITION POLYCONDENSATION PRODUCT AND ITS USE |
| DE3123968A1 (en) * | 1981-06-19 | 1983-01-13 | Basf Ag, 6700 Ludwigshafen | NITROGEN-BASED GROUPS CARRYING POLYADDITIONS / POLYCONDENSATION PRODUCTS AND THEIR USE |
-
1991
- 1991-04-30 CA CA002086418A patent/CA2086418A1/en not_active Abandoned
- 1991-04-30 DE DE4193551T patent/DE4193551T1/de not_active Withdrawn
- 1991-04-30 WO PCT/JP1991/000590 patent/WO1992019661A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| DE4193551T1 (en) | 1993-05-13 |
| WO1992019661A1 (en) | 1992-11-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |