CA1177992A - Water repellent adhesive composition for wooden material - Google Patents
Water repellent adhesive composition for wooden materialInfo
- Publication number
- CA1177992A CA1177992A CA000404859A CA404859A CA1177992A CA 1177992 A CA1177992 A CA 1177992A CA 000404859 A CA000404859 A CA 000404859A CA 404859 A CA404859 A CA 404859A CA 1177992 A CA1177992 A CA 1177992A
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- paraffin
- parts
- resin
- emulsion
- water
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Abstract
ABSTRACT OF THE DISCLOSURE: Water-repellent adhesive composition for wooden material which consists essentially of a paraffin emulsion and a resin material selected from the group consisting of urea resin, urea-melamine resin, and phenol resin, wherein said paraffin emulsion contains oxidized paraffin.
Description
This invention relates to a water repellent adhesive composition for wooden material which consists of a particular paraffin emulsion and a resin component, such as urearesin, urea-melamine resin, or phenol resin. More particularly, the invention is concerned with a single liquid type adhesive composition which has excellent blendability and storage stability, and, moreover, is capable of imparting high degrees of water-repellently to the wooden material to be joined together.
There have so far been known, as the adhesive agent for wooden material, various resins such as urea resin, urea-melamine resin, and phenol resin. Wooden material such as particle board and fiber board obtained by using such adhesive agent, however, cannot be said to have sufficient water-resistance, hence their utility has been fairly limited.
With a view to avoiding this, there has been proposed the co-use of a water-repellency imparting agent, such as paraffin emulsion. However, when the conventional paraffin emulsion is pre-mixed with an adhesive agent, such as urea resin, to prepare a single liquid type water-repellent adhesive composition, segregation occurs in the mixture within several hours, or at the most in a few days, which makes the blending stability of the mixture extremely poor. Such instability also causes non-uniformity in the water-repellency in the wooden material as joined. To avoid such problem, therefore, it has so far been e~ --2--1~7799Z
an established practice to adopt a method, in which, at the time of applying or coating the adhesive agent on wooden pieces, wood cuttings, fibre dust, chips, etc., the paraffin emulsion is additionally added or applied to these materials.
Accordingly, in the course of manufacturing the wooden mate-rials, the adhesive agent and the water-repellent agent should be stored in separate storage vessels for each of them, which leaves a problem in rationalization of the manufac-turing steps.
It has now been found that, when the paraffin emulsion containing oxidized paraffin as the water-repellency imparting agent is used, the emulsion is superior in its blendability and storage stability which is from several tens to a few hundred times as high as the conventionally used paraffin emulsion, and is capable of imparting sufficient water-repellency to the wooden material as joined, in spite of its being of a single liquid type.
Thus, the present invention provides a water-repel-lent adhesive composition for wooden material consisting essentially of a paraffin emulsion and a resin component such as urea resin, urea-melamine resin, or phenol resin, wherein the paraffin emulstion contains oxidized paraffin.
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The paraffin emulsion of the present invention contains, as its constituent elements, paraffin type hydrocar-bon and oxidized paraffin.
The paraffin type hydrocarbons for use in the present invention should be those that do not cause evaporation and scattering during the hot-press forming process of the wooden material. Otherwise, any kind of hydrocarbon that is capable of existing properly throughout the wooden material to impart favourable water-repellency to the material can be used. Usually, those paraffin type hydrocarbons having a melting point range of from 40 to 80C, or preferably from 50 to 70C, are used.
For the oxidized paraffin, those having an acid value of from 10 to 70 and a melting point of from 30 to 90C are preferably used. In particular, an oxidized paraffin having the acid value of from 20 to 45 and the melting point of from 40 to 80C is preferable. If the acid value of the oxidized paraffin is too small, emulsification becomes difficult, which lowers the storage stability of the resulting emulsion per se, hence inferior blendability with the resin component for the adhesive agent and its storage stability.
If the acid value is too large, the water-repellency imparting property of the adhesive composition becomes lowered.
The mixing quantity of the above-m~ntioned paraffin type hydrocarbon and oxidized paraffin may be appropriately selected from a range of the oxidized paraffin, which is from 3 to 50 parts by weight, or preferably from 5 to 30 parts by weight, with respect to the paraffin type hydrocarbon, which is from 50 to 97 parts by weight, or preferably from 70 to 95 parts by weight.
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A difference in the melting point between the paraffin type hydrocarbon and the oxidized paraffin should preferably not exceed 20C in consideration of the miscibility between the emulsion and the adhesive resin component and the storage stability of the adhesive composition.
The paraffin emulsion of the present invention is obtained by emulsifying the above-mentioned paraffin type hydrocarbon and oxidized paraffin in the presence of a surfactant and/or a water-soluble alkaline alkali metal compound, ammonia water, or morpholine (hereinafter simply referred to as "water-soluble alkali compound").
For the surfactant, there may be used any type of surfactants, i.e., anionic type, nonionic type, cationic type and amphoteric type surfactants. Examples of these surfactants are; anionic type surfactants, such as sodium oleate soap, potassium fatty acid soap, lauryl sodium sulfate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, polyoxy-ethylene alkylether sulfonate, and alkyl amine oxide; nonionictype surfactants, such as polyethylene glycol alkyl ether, polyethylene glycol, polypropylene glycol ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyethy-lene glycol sorbitan fatty acid ester, sucrose fatty acid ester, and glycerine fatty acid ester; cationic type surfac-tants such as alkyl amine, polyoxyethylene alkylamine, alkyl-amine acetate, alkylamine hydrochlorate, alkyl trimethyl ammonium chloride, and alkyl picolinium chloride; and amphote-ric type surfactants, such as alkyl glycine, alkyl betaine, and alkyl imidazoline. Particularly preferred are nonionic and cationic type surfactants.
Because an oxidized paraffin is present, the surfac-tant may be present in a very small amount in comparison with that used in ordinary emulsification. ~sually, it is sufficient to use 0 to 5% by weight of such surfactant with respect to the ~.
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total quantity of the above-mentioned paraffin type hydrocarbon and oxidized paraffin.
Examples of water-soluble alkali compounds are:
water-soluble alkaline alkali metal compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate; and ammonia water; amines and morpholine. These water-soluble alkali compounds may be used in an appropriate quantity in accordance with a pH value of the adhesive agent and its gelling time. The quantity is usually selected from a range sufficient to neutralize the acid radical present in the oxidized paraffin in an amount of from 0 to 300%, or preferably from 40 to 130~. When the above-mentioned surfactant is not used, the acid radical in the oxidized paraffin should essentially be neutralized, in which case a range of from 40 to 150%, or preferably from 50 to 130%, of the acid radical should preferably be neutralized.
The emulsifying method may be effected in a homogen-izing mixer, a valve homogenizer, a colloid mill, an ultra-sonic wave emulsifer, and other mechanical emulsifying methods may be used, as well as the phase converting emulsifying method, and so on. The emulsification is usually carried 25 out sufficiently at a temperature higher, by 5 to 10C
or above, than the melting point of the paraffin type hydrocar-bon and the oxidized paraffin to be used and for a time period of from ten minutes to three hours.
The paraffin emulsion according to the present - invention may also be used together with water-soluble synthe-tic high polymer compounds such as polyvinyl alcohol, polyethy-lene imine, polyacryl amide, and polyacrylic acid; cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, 35 and hydroxypropyl cellulose; and natural high polymer compounds such as starch, gum arabic, guar gum, locust bean gum and sodium alginate.
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, The adhesive resin used for the present invention may be selected from urea resin, urea-melamine resin, and phenol resin. Usually any kind of resins, which are used for joining wooden materials, are feasible in the present invention.
Urea resin can be obtained by reacting urea and a formaldehyde donor such as formalin, and paraformaldehyde at a mol ratio of a range of from l~ 2, in the presence of an acid catalyst, such as formic acid and an alkaline catalyst such as ammonia water, and sodium hydroxide, in a conventional manner. Such urea resin usually contains a non-volatile component of from 50 to 70% by weight, and has a viscosity of from about lO to 600 cp.(centipoise).
Urea-melamine resin is obtained by reacting urea, melamine and a formaldehyde donor at a mol ratio in a range of from 1:0.1-0.4:1.5-3 under the above-mentioned conditions.
The thus obtained urea-melamine resin usually contains a non-volatile component of from 50 to 70~ by weight, and has a viscosity of from about lO to 600 cp.
Phenol resin is obtained by reacting phenols such as phenol, cresol and xylenol, and a formaldehyde donor in a mol ratio in a range of 1:1.5-3 in the presence of alkaline catalyst such as sodium hydroxide, in a conventional manner. The thus obtained phenol resin usually contains a non-volatile component of from 35 to 50% by weight, and has a viscosity of from about 50 to 600 cp.
The adhesive composition of the present invention can be prepared by mixing the above-mentioned paraffin emulsion and urea resin (or urea-melamine resin, or penol resin) in a weight ratio between them in a range of from 0.5:99.5 to 20:80, or preferably, from 1:99 to 10:90. In this case, it should be understood that the quantities of the adhesive resin and paraffin emulsion are in terms of their solids content by conversion. If the quantity of the paraffin emulsion is too small, its water-repellency imparting property to the wooden material as joined becomes lowered. If the quantity is too large, various mechanical properties of the wooden material as joined are unfavorably impaired.
For the method of blending the paraffin emulsion - and the adhesive resin, there is no particular device required.
Usually, they may be simply blended in an ordinary blending vessel with an agitator under normal pressure, at a temperature of from normal temperature to 60C, for a time period of from ten minutes to six hours or so. It is preferable in this case that the paraffin emulsion be dripped into the vessel during the blending. At this time, there may also be added, depending on necessity, various well known additives such as viscosity adjusting agent, an extending agent, and a filling agent.
The thus obtained adhesive composition according to the present invention could maintain its stability at a normal temperature for 10 to 40 days without segregation and coagulation, and exhibit excellent water-repellent property In the following, the present invention will be explained more concretely with reference to several preferred embodiments. Note should be taken that, in the following examples, "part(s)" and "~" are meant by "parts(s) by weight"
and "% by weight", unless otherwlse specified.
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Manufacturin~ Example 1:
Preparation of Paraffin Emulsion.
A. Paraffin Emulsion A of the Present Invention:
Paraffin having a melting point of 52C 90 parts Oxidized paraffin having an acid value of 28 and melting point of 67C 10 parts Sodium hydroxide 0.2 part Sorbitan monostearate 0. 25 part Polyethylene glycol oleyl ether 0.75 part Deionized water 125 parts The above-listed ingredients were charged in a emulsifying vessel, warmed to a temperature of 75C, and emulsified, while vigorously agitating the batch with a homogenizer, thereby obtaining the paraffin emulsion A having a solid content of 44.7%.
B. Paraffin Emulsion B for Comparative Example:
The same procedures as in A above were followed with the exception that the oxidized paraffin and sodium hydroxide were not used, and that the quantity of paraffin was made 100 parts, thereby obtaining the paraffin emulsion B having a solid content of 44.7%.
C. Paraffin Emulsion C for Comparative Example:
The same procedures as in B above were followed with the exception that sorbitan monostearate used in B was made 2.5 parts, poly-ethylene glycol oleyl ether was made 7.5 parts, both being made ten times as large as in the previous ones, and the quantity of deionized water was made 135 parts, whereby the paraffin emulsion C having a solid content of 44.9% was obtained.
D. Paraffin Emulsion D of the Present invention:
Paraffin having a melting point of 68C 80 parts Oxidized paraffin having an acid value of 40 and a melting point of 73C 20 parts Sodium hydroxide 0.27 part Sorbitan monolaurate 0.3 part Polyethylene glycol tetradecyl ether 0.7 part Deionized water 145 parts The abovementioned raw material preparation was charged in the emulsifying vessel, warmed to 76C, and emulsified, while vigorously 10 agitating the reaction mixture with a homogenizer, after which 0~73 part of hydroxy propyl cellulose was added to the reaction mixture to thereby obtain the paraffin emulsion D having a solid content of 41.3%.
E. Paraf~m Emulsion E of the Present Invention:
Paraffin having a melting point of 57C 90 parts Oxidized paraffin having.an acid value of 28 and a melting point of 67C10 parts Sodium hydroxide 0.2 part Polyoxyethylene oleyl ether 3.7 parts Monoglyceride stearate 1.3 parts Deionized water 125 parts The above-listed ingredients were charged in the emulsifying vessel, warmed to a temperature of 80C, and emulsified, while vigorously agitating the reaction mixture with a homogenizer, thereby obtaining the paraffin emulsion E having a solid content of 45.7%.
F. Paraffin Emulsion F of the Present Invention:
The exactly same procedures were followed as in E above with the exception that saccharose palmitate was used in place of polyoxyethylene oleyl ether in E., and saccharose stearate in place of monoglyceride stearate, whereby the paraffin emulsion F having a solid content of 45. 7% was obtained.
G. Paraffin Emulsion G of the Present Invention:
Paraffin having a melting point of 57C 90 parts Oxidized paraffin having an acid value of 28 and a melting point of 67C10 parts Ethylene oxide added substance of hexadecyl amine 5 parts Acetic anhydride 0.8 part Deionized water 125 parts The above-listed ingredients were charged in the emulsifying vessel, warmed to a temperature of 80(:, and emulsified, while vigorously agitating the batch with a homogenizer, thereby obtaining the paraffin 15 emulsion G having a solid content of 45.8%.
~: H. Paraffin Emulsion H for Comparative Example:
Paraffin having a melting point of 57C 90 parts Stearic acid 10 parts Polyoxyethylene monostearate3 parts Triethanolamine 1 parts Deionized water 150 parts The above-listed ingredients were charged in the emulsifying vessel, warmed to a temperature of 75C, and emulsified, while vigorously agitnting the batch with a homogenizer, thereby obtaining the paraffin 25 emulsion H having a solid content of 40.9%.
,, 1. Paraf~n Emulsion I of the Present Invention:
Paraffin having a melting point of 52C 80 parts Oxidized paraffin having an acid value of 28 and a melting point of 67C 20 parts Sodium hydroxide 0. 4 part Deionized water 125 parts The above-listed ingredients were emulsified in the same manner as in A above, thereby obtaining the paraffin emulsion I having a so]id content of 44.5%.
Manufacturing Example 2:
a. Urea Resin a:
100 parts of urea was added to 257 parts of 37% conc. formalin, and both were mixed well under agitation. To this mixture, ammonia water was added to adjust its pH value to 7. The batch was then heated to raise its temperature to 90C in 30 minutes, at which temperature the reaction was continued. At a point where the pH value of the reaction liquid gradually lowered to 4.8, sodium carbonate was added to adjust its pH
value to 7 with further addition of 26 parts of urea to continue the reaction for about 30 minutes. After this, the reaction liquid was dehydrate and cooled to thereby obtain urea resin a containing approximately 67% of a non-volatile component.
b. Urea-Melamine Resin b:
60 parts of urea and 32 parts of melamine were added to 203 parts of 37% conc. formalin, and they were mi~ed well under agitation.
To this mixture, ammonia water was added to adjust its pH value to 7.
The batch was then heated to raise its temperature to 90C in 30 minutes, at which temperature the reaction was continued. At a point where the pH value of the reaction liquid gradually lowered to 9. 8, sodium carbonate was added to adjust its pH value to 7 with further additon of 15 parts of urea. After sufficient reaction having been conducted, the reaction liquid was dehydrated and cooled to thereby obtain urea-melamine resin b con-taining approximately 65% of a non-volatile component.
c. Phenol Resin c:
94 parts of phenol was added to 162 parts of 37% conc. formalin, and both were mixed well under agitation. To this reaction mixture, 60 parts of 30% aqueous solution of sodium hydroxide was added, and the batch was heated to elevate its temperature to 90C in approximately 60 minutes, at which temperature the reaction was continued. After the reaction for 150 minutes at 90C, 98 parts of water was added to the reac-tion system to further continue the reaction for 30 minutes at 90C.
After completion of the reaction, the reaction liquid was cooled, thereby obtaining phenol resin c containing approximately 35% of a non-volatile component .
Examp]es 1 to 9 and Comparative Examples 1 to S:
-The paraffin emulsion and adhesive resin shown in Table 1 below were respectively weighed for predetermined quantities, and were well mixed under agitation to obtain the adhesive composition. The compo-sition was then introduced into a hermetically sealed vessel. The vessel was maintained at a temperature of 20C, and changes in the outer appearance of the adhesive composition with lapse of time was observed.
The evaluation of the result of observation is also shown in Table 1, wherein O denotes no change recognized at all on the outer appearance of the composition; /\ represents the composition which has slightly increased its viscosity or slightly segregated; X indicates the composition which has segregated completely; and denotes the composition which has coagulated or solidi~led.
T able _ P-r~t~ Adhesive I w ~igl~ ti~l After After Aiter 'Afot hr Example 1 A b 1/10 O O O O
Example 2 D b 1/10 O O O 0 Comparative B b 1/10 ~ ~ X X _ _ Compatative C b 1/10 ~ ~'~ X X X
Example 3 A a 1/10 O O O O
Example 4 E a 1/10 O O 0~~
Example S F a 1/10 O O 0 Example 6 G a 1/10 O O O 0 Example 7 I a 1/10 O O OO ' Example 3 . H a 1/10 0~ l~ ~ X X
Example 8 A c O. 5/10 O O0~ ~
Example 9 G c O. 5/10 O O 0~ A
Comparative C . c o. 5/10 X X _ _ Example 4 CxammPpalet5Ve H c X X
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EXAMPLE 10.
10 parts of paraffin emulsion A and 90 parts of the adhesive resin a were weighed and placed in two tall beakers, each having 300 cc capacity, and the components were well mixed under agitation, and kept in a hermetically sealed condition at respective temperature levels of 20C and 35C. After lapse of 20 days, the concentration of the solid content in the upper and lower parts in the tall beakers were measured, the results of which are shown in the following Table 2. From this, it was found that the mixture liquid was uniform. Further, variations in viscosity during storage of the mixture liquid at 20C (in accordance with B-type viscometer) are as shown.in Table 3. No substantial variations in viscosity could be recogni zed .
Table 2 Concentration of solid content Storage Storagein tall beakers %
temperature period UPPer part Lower part . ~ , 20C 20 days64. 7 63. 4 35C 20 days65.4 65.0 Table 3 Storage time at 20C Viscosity by B-type viscometer (60 rPm/hr.) . .-- _ _ Immediately after mixing 2.0 poise After 168 hours 2.8 poise . After 336 hours 3.1 poise 5.5 parts of paraffin emulsion A and 100 parts of adhesive resin a were sufficiently mixed, and the mixture was stored under tight seal for 14 days at 20C. At the end of the fourteenth day, the mixture 5 liquid was sprayed onto coniferous wood chips at a rate of adhesion of 10%
by weight in terms of the solid content of the adhesive composition, followed by hot-press forming of the wooden material under the initial pressure of 30 kg/cm2 for 10 minutes at 155C. As the result of this, there was obtained a single-layered particle board having a thickness of 15 mm and 10 a specific gravity of 0. 7. The thus obtained particle board was measured in accordance with JIS A-5908 for its bending strength in an ordinary condition as well as its bending strength in a wet condition, water absorp-tion ratio, and rate of increase in thickness due to water abs~rption, after the particle board had been immersed in water for 24 hours at 25C.
15 The results obtained are as shown in Figure 4 below.
Comparative Example 6:
The exactly same procedures as in Example 11 above were followed with the exception that the paraffin emulsion C was used in place of the paraffin emulsion A, which was well mixed with the adhesive resin a 20 immediately before the spraying. The results as shown in Tble 4 were obtained. Incidentally, this mixture liquid was found to have been segregat-ed and coagulated to a considerable extent after lapse of 14 days, and to have been impossibly sprayed.
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Tab~e 4 _ _ Example 11 Comparatlve Specific gravity of board 0.7 0.7 Bending strength in normal state (Kg/cm2) 260 250 . __ _ ___ Bending strength in 175 130 wet state (kg/cm2 ) Water absorption ratio ( 96) 35 55 _ . . _ ._ ... _ ___ ._ Rate of increase in thickness due to water 7 18 absorption ( ~6) _.
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There have so far been known, as the adhesive agent for wooden material, various resins such as urea resin, urea-melamine resin, and phenol resin. Wooden material such as particle board and fiber board obtained by using such adhesive agent, however, cannot be said to have sufficient water-resistance, hence their utility has been fairly limited.
With a view to avoiding this, there has been proposed the co-use of a water-repellency imparting agent, such as paraffin emulsion. However, when the conventional paraffin emulsion is pre-mixed with an adhesive agent, such as urea resin, to prepare a single liquid type water-repellent adhesive composition, segregation occurs in the mixture within several hours, or at the most in a few days, which makes the blending stability of the mixture extremely poor. Such instability also causes non-uniformity in the water-repellency in the wooden material as joined. To avoid such problem, therefore, it has so far been e~ --2--1~7799Z
an established practice to adopt a method, in which, at the time of applying or coating the adhesive agent on wooden pieces, wood cuttings, fibre dust, chips, etc., the paraffin emulsion is additionally added or applied to these materials.
Accordingly, in the course of manufacturing the wooden mate-rials, the adhesive agent and the water-repellent agent should be stored in separate storage vessels for each of them, which leaves a problem in rationalization of the manufac-turing steps.
It has now been found that, when the paraffin emulsion containing oxidized paraffin as the water-repellency imparting agent is used, the emulsion is superior in its blendability and storage stability which is from several tens to a few hundred times as high as the conventionally used paraffin emulsion, and is capable of imparting sufficient water-repellency to the wooden material as joined, in spite of its being of a single liquid type.
Thus, the present invention provides a water-repel-lent adhesive composition for wooden material consisting essentially of a paraffin emulsion and a resin component such as urea resin, urea-melamine resin, or phenol resin, wherein the paraffin emulstion contains oxidized paraffin.
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The paraffin emulsion of the present invention contains, as its constituent elements, paraffin type hydrocar-bon and oxidized paraffin.
The paraffin type hydrocarbons for use in the present invention should be those that do not cause evaporation and scattering during the hot-press forming process of the wooden material. Otherwise, any kind of hydrocarbon that is capable of existing properly throughout the wooden material to impart favourable water-repellency to the material can be used. Usually, those paraffin type hydrocarbons having a melting point range of from 40 to 80C, or preferably from 50 to 70C, are used.
For the oxidized paraffin, those having an acid value of from 10 to 70 and a melting point of from 30 to 90C are preferably used. In particular, an oxidized paraffin having the acid value of from 20 to 45 and the melting point of from 40 to 80C is preferable. If the acid value of the oxidized paraffin is too small, emulsification becomes difficult, which lowers the storage stability of the resulting emulsion per se, hence inferior blendability with the resin component for the adhesive agent and its storage stability.
If the acid value is too large, the water-repellency imparting property of the adhesive composition becomes lowered.
The mixing quantity of the above-m~ntioned paraffin type hydrocarbon and oxidized paraffin may be appropriately selected from a range of the oxidized paraffin, which is from 3 to 50 parts by weight, or preferably from 5 to 30 parts by weight, with respect to the paraffin type hydrocarbon, which is from 50 to 97 parts by weight, or preferably from 70 to 95 parts by weight.
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A difference in the melting point between the paraffin type hydrocarbon and the oxidized paraffin should preferably not exceed 20C in consideration of the miscibility between the emulsion and the adhesive resin component and the storage stability of the adhesive composition.
The paraffin emulsion of the present invention is obtained by emulsifying the above-mentioned paraffin type hydrocarbon and oxidized paraffin in the presence of a surfactant and/or a water-soluble alkaline alkali metal compound, ammonia water, or morpholine (hereinafter simply referred to as "water-soluble alkali compound").
For the surfactant, there may be used any type of surfactants, i.e., anionic type, nonionic type, cationic type and amphoteric type surfactants. Examples of these surfactants are; anionic type surfactants, such as sodium oleate soap, potassium fatty acid soap, lauryl sodium sulfate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, polyoxy-ethylene alkylether sulfonate, and alkyl amine oxide; nonionictype surfactants, such as polyethylene glycol alkyl ether, polyethylene glycol, polypropylene glycol ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, polyethy-lene glycol sorbitan fatty acid ester, sucrose fatty acid ester, and glycerine fatty acid ester; cationic type surfac-tants such as alkyl amine, polyoxyethylene alkylamine, alkyl-amine acetate, alkylamine hydrochlorate, alkyl trimethyl ammonium chloride, and alkyl picolinium chloride; and amphote-ric type surfactants, such as alkyl glycine, alkyl betaine, and alkyl imidazoline. Particularly preferred are nonionic and cationic type surfactants.
Because an oxidized paraffin is present, the surfac-tant may be present in a very small amount in comparison with that used in ordinary emulsification. ~sually, it is sufficient to use 0 to 5% by weight of such surfactant with respect to the ~.
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total quantity of the above-mentioned paraffin type hydrocarbon and oxidized paraffin.
Examples of water-soluble alkali compounds are:
water-soluble alkaline alkali metal compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, and potassium carbonate; and ammonia water; amines and morpholine. These water-soluble alkali compounds may be used in an appropriate quantity in accordance with a pH value of the adhesive agent and its gelling time. The quantity is usually selected from a range sufficient to neutralize the acid radical present in the oxidized paraffin in an amount of from 0 to 300%, or preferably from 40 to 130~. When the above-mentioned surfactant is not used, the acid radical in the oxidized paraffin should essentially be neutralized, in which case a range of from 40 to 150%, or preferably from 50 to 130%, of the acid radical should preferably be neutralized.
The emulsifying method may be effected in a homogen-izing mixer, a valve homogenizer, a colloid mill, an ultra-sonic wave emulsifer, and other mechanical emulsifying methods may be used, as well as the phase converting emulsifying method, and so on. The emulsification is usually carried 25 out sufficiently at a temperature higher, by 5 to 10C
or above, than the melting point of the paraffin type hydrocar-bon and the oxidized paraffin to be used and for a time period of from ten minutes to three hours.
The paraffin emulsion according to the present - invention may also be used together with water-soluble synthe-tic high polymer compounds such as polyvinyl alcohol, polyethy-lene imine, polyacryl amide, and polyacrylic acid; cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, 35 and hydroxypropyl cellulose; and natural high polymer compounds such as starch, gum arabic, guar gum, locust bean gum and sodium alginate.
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, The adhesive resin used for the present invention may be selected from urea resin, urea-melamine resin, and phenol resin. Usually any kind of resins, which are used for joining wooden materials, are feasible in the present invention.
Urea resin can be obtained by reacting urea and a formaldehyde donor such as formalin, and paraformaldehyde at a mol ratio of a range of from l~ 2, in the presence of an acid catalyst, such as formic acid and an alkaline catalyst such as ammonia water, and sodium hydroxide, in a conventional manner. Such urea resin usually contains a non-volatile component of from 50 to 70% by weight, and has a viscosity of from about lO to 600 cp.(centipoise).
Urea-melamine resin is obtained by reacting urea, melamine and a formaldehyde donor at a mol ratio in a range of from 1:0.1-0.4:1.5-3 under the above-mentioned conditions.
The thus obtained urea-melamine resin usually contains a non-volatile component of from 50 to 70~ by weight, and has a viscosity of from about lO to 600 cp.
Phenol resin is obtained by reacting phenols such as phenol, cresol and xylenol, and a formaldehyde donor in a mol ratio in a range of 1:1.5-3 in the presence of alkaline catalyst such as sodium hydroxide, in a conventional manner. The thus obtained phenol resin usually contains a non-volatile component of from 35 to 50% by weight, and has a viscosity of from about 50 to 600 cp.
The adhesive composition of the present invention can be prepared by mixing the above-mentioned paraffin emulsion and urea resin (or urea-melamine resin, or penol resin) in a weight ratio between them in a range of from 0.5:99.5 to 20:80, or preferably, from 1:99 to 10:90. In this case, it should be understood that the quantities of the adhesive resin and paraffin emulsion are in terms of their solids content by conversion. If the quantity of the paraffin emulsion is too small, its water-repellency imparting property to the wooden material as joined becomes lowered. If the quantity is too large, various mechanical properties of the wooden material as joined are unfavorably impaired.
For the method of blending the paraffin emulsion - and the adhesive resin, there is no particular device required.
Usually, they may be simply blended in an ordinary blending vessel with an agitator under normal pressure, at a temperature of from normal temperature to 60C, for a time period of from ten minutes to six hours or so. It is preferable in this case that the paraffin emulsion be dripped into the vessel during the blending. At this time, there may also be added, depending on necessity, various well known additives such as viscosity adjusting agent, an extending agent, and a filling agent.
The thus obtained adhesive composition according to the present invention could maintain its stability at a normal temperature for 10 to 40 days without segregation and coagulation, and exhibit excellent water-repellent property In the following, the present invention will be explained more concretely with reference to several preferred embodiments. Note should be taken that, in the following examples, "part(s)" and "~" are meant by "parts(s) by weight"
and "% by weight", unless otherwlse specified.
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Manufacturin~ Example 1:
Preparation of Paraffin Emulsion.
A. Paraffin Emulsion A of the Present Invention:
Paraffin having a melting point of 52C 90 parts Oxidized paraffin having an acid value of 28 and melting point of 67C 10 parts Sodium hydroxide 0.2 part Sorbitan monostearate 0. 25 part Polyethylene glycol oleyl ether 0.75 part Deionized water 125 parts The above-listed ingredients were charged in a emulsifying vessel, warmed to a temperature of 75C, and emulsified, while vigorously agitating the batch with a homogenizer, thereby obtaining the paraffin emulsion A having a solid content of 44.7%.
B. Paraffin Emulsion B for Comparative Example:
The same procedures as in A above were followed with the exception that the oxidized paraffin and sodium hydroxide were not used, and that the quantity of paraffin was made 100 parts, thereby obtaining the paraffin emulsion B having a solid content of 44.7%.
C. Paraffin Emulsion C for Comparative Example:
The same procedures as in B above were followed with the exception that sorbitan monostearate used in B was made 2.5 parts, poly-ethylene glycol oleyl ether was made 7.5 parts, both being made ten times as large as in the previous ones, and the quantity of deionized water was made 135 parts, whereby the paraffin emulsion C having a solid content of 44.9% was obtained.
D. Paraffin Emulsion D of the Present invention:
Paraffin having a melting point of 68C 80 parts Oxidized paraffin having an acid value of 40 and a melting point of 73C 20 parts Sodium hydroxide 0.27 part Sorbitan monolaurate 0.3 part Polyethylene glycol tetradecyl ether 0.7 part Deionized water 145 parts The abovementioned raw material preparation was charged in the emulsifying vessel, warmed to 76C, and emulsified, while vigorously 10 agitating the reaction mixture with a homogenizer, after which 0~73 part of hydroxy propyl cellulose was added to the reaction mixture to thereby obtain the paraffin emulsion D having a solid content of 41.3%.
E. Paraf~m Emulsion E of the Present Invention:
Paraffin having a melting point of 57C 90 parts Oxidized paraffin having.an acid value of 28 and a melting point of 67C10 parts Sodium hydroxide 0.2 part Polyoxyethylene oleyl ether 3.7 parts Monoglyceride stearate 1.3 parts Deionized water 125 parts The above-listed ingredients were charged in the emulsifying vessel, warmed to a temperature of 80C, and emulsified, while vigorously agitating the reaction mixture with a homogenizer, thereby obtaining the paraffin emulsion E having a solid content of 45.7%.
F. Paraffin Emulsion F of the Present Invention:
The exactly same procedures were followed as in E above with the exception that saccharose palmitate was used in place of polyoxyethylene oleyl ether in E., and saccharose stearate in place of monoglyceride stearate, whereby the paraffin emulsion F having a solid content of 45. 7% was obtained.
G. Paraffin Emulsion G of the Present Invention:
Paraffin having a melting point of 57C 90 parts Oxidized paraffin having an acid value of 28 and a melting point of 67C10 parts Ethylene oxide added substance of hexadecyl amine 5 parts Acetic anhydride 0.8 part Deionized water 125 parts The above-listed ingredients were charged in the emulsifying vessel, warmed to a temperature of 80(:, and emulsified, while vigorously agitating the batch with a homogenizer, thereby obtaining the paraffin 15 emulsion G having a solid content of 45.8%.
~: H. Paraffin Emulsion H for Comparative Example:
Paraffin having a melting point of 57C 90 parts Stearic acid 10 parts Polyoxyethylene monostearate3 parts Triethanolamine 1 parts Deionized water 150 parts The above-listed ingredients were charged in the emulsifying vessel, warmed to a temperature of 75C, and emulsified, while vigorously agitnting the batch with a homogenizer, thereby obtaining the paraffin 25 emulsion H having a solid content of 40.9%.
,, 1. Paraf~n Emulsion I of the Present Invention:
Paraffin having a melting point of 52C 80 parts Oxidized paraffin having an acid value of 28 and a melting point of 67C 20 parts Sodium hydroxide 0. 4 part Deionized water 125 parts The above-listed ingredients were emulsified in the same manner as in A above, thereby obtaining the paraffin emulsion I having a so]id content of 44.5%.
Manufacturing Example 2:
a. Urea Resin a:
100 parts of urea was added to 257 parts of 37% conc. formalin, and both were mixed well under agitation. To this mixture, ammonia water was added to adjust its pH value to 7. The batch was then heated to raise its temperature to 90C in 30 minutes, at which temperature the reaction was continued. At a point where the pH value of the reaction liquid gradually lowered to 4.8, sodium carbonate was added to adjust its pH
value to 7 with further addition of 26 parts of urea to continue the reaction for about 30 minutes. After this, the reaction liquid was dehydrate and cooled to thereby obtain urea resin a containing approximately 67% of a non-volatile component.
b. Urea-Melamine Resin b:
60 parts of urea and 32 parts of melamine were added to 203 parts of 37% conc. formalin, and they were mi~ed well under agitation.
To this mixture, ammonia water was added to adjust its pH value to 7.
The batch was then heated to raise its temperature to 90C in 30 minutes, at which temperature the reaction was continued. At a point where the pH value of the reaction liquid gradually lowered to 9. 8, sodium carbonate was added to adjust its pH value to 7 with further additon of 15 parts of urea. After sufficient reaction having been conducted, the reaction liquid was dehydrated and cooled to thereby obtain urea-melamine resin b con-taining approximately 65% of a non-volatile component.
c. Phenol Resin c:
94 parts of phenol was added to 162 parts of 37% conc. formalin, and both were mixed well under agitation. To this reaction mixture, 60 parts of 30% aqueous solution of sodium hydroxide was added, and the batch was heated to elevate its temperature to 90C in approximately 60 minutes, at which temperature the reaction was continued. After the reaction for 150 minutes at 90C, 98 parts of water was added to the reac-tion system to further continue the reaction for 30 minutes at 90C.
After completion of the reaction, the reaction liquid was cooled, thereby obtaining phenol resin c containing approximately 35% of a non-volatile component .
Examp]es 1 to 9 and Comparative Examples 1 to S:
-The paraffin emulsion and adhesive resin shown in Table 1 below were respectively weighed for predetermined quantities, and were well mixed under agitation to obtain the adhesive composition. The compo-sition was then introduced into a hermetically sealed vessel. The vessel was maintained at a temperature of 20C, and changes in the outer appearance of the adhesive composition with lapse of time was observed.
The evaluation of the result of observation is also shown in Table 1, wherein O denotes no change recognized at all on the outer appearance of the composition; /\ represents the composition which has slightly increased its viscosity or slightly segregated; X indicates the composition which has segregated completely; and denotes the composition which has coagulated or solidi~led.
T able _ P-r~t~ Adhesive I w ~igl~ ti~l After After Aiter 'Afot hr Example 1 A b 1/10 O O O O
Example 2 D b 1/10 O O O 0 Comparative B b 1/10 ~ ~ X X _ _ Compatative C b 1/10 ~ ~'~ X X X
Example 3 A a 1/10 O O O O
Example 4 E a 1/10 O O 0~~
Example S F a 1/10 O O 0 Example 6 G a 1/10 O O O 0 Example 7 I a 1/10 O O OO ' Example 3 . H a 1/10 0~ l~ ~ X X
Example 8 A c O. 5/10 O O0~ ~
Example 9 G c O. 5/10 O O 0~ A
Comparative C . c o. 5/10 X X _ _ Example 4 CxammPpalet5Ve H c X X
il~799Z
EXAMPLE 10.
10 parts of paraffin emulsion A and 90 parts of the adhesive resin a were weighed and placed in two tall beakers, each having 300 cc capacity, and the components were well mixed under agitation, and kept in a hermetically sealed condition at respective temperature levels of 20C and 35C. After lapse of 20 days, the concentration of the solid content in the upper and lower parts in the tall beakers were measured, the results of which are shown in the following Table 2. From this, it was found that the mixture liquid was uniform. Further, variations in viscosity during storage of the mixture liquid at 20C (in accordance with B-type viscometer) are as shown.in Table 3. No substantial variations in viscosity could be recogni zed .
Table 2 Concentration of solid content Storage Storagein tall beakers %
temperature period UPPer part Lower part . ~ , 20C 20 days64. 7 63. 4 35C 20 days65.4 65.0 Table 3 Storage time at 20C Viscosity by B-type viscometer (60 rPm/hr.) . .-- _ _ Immediately after mixing 2.0 poise After 168 hours 2.8 poise . After 336 hours 3.1 poise 5.5 parts of paraffin emulsion A and 100 parts of adhesive resin a were sufficiently mixed, and the mixture was stored under tight seal for 14 days at 20C. At the end of the fourteenth day, the mixture 5 liquid was sprayed onto coniferous wood chips at a rate of adhesion of 10%
by weight in terms of the solid content of the adhesive composition, followed by hot-press forming of the wooden material under the initial pressure of 30 kg/cm2 for 10 minutes at 155C. As the result of this, there was obtained a single-layered particle board having a thickness of 15 mm and 10 a specific gravity of 0. 7. The thus obtained particle board was measured in accordance with JIS A-5908 for its bending strength in an ordinary condition as well as its bending strength in a wet condition, water absorp-tion ratio, and rate of increase in thickness due to water abs~rption, after the particle board had been immersed in water for 24 hours at 25C.
15 The results obtained are as shown in Figure 4 below.
Comparative Example 6:
The exactly same procedures as in Example 11 above were followed with the exception that the paraffin emulsion C was used in place of the paraffin emulsion A, which was well mixed with the adhesive resin a 20 immediately before the spraying. The results as shown in Tble 4 were obtained. Incidentally, this mixture liquid was found to have been segregat-ed and coagulated to a considerable extent after lapse of 14 days, and to have been impossibly sprayed.
.~ .
Tab~e 4 _ _ Example 11 Comparatlve Specific gravity of board 0.7 0.7 Bending strength in normal state (Kg/cm2) 260 250 . __ _ ___ Bending strength in 175 130 wet state (kg/cm2 ) Water absorption ratio ( 96) 35 55 _ . . _ ._ ... _ ___ ._ Rate of increase in thickness due to water 7 18 absorption ( ~6) _.
,. ..
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1) Water-repellent adhesive composition for wooden material which consists essentially of a paraffin emulsion and a resin material selected from the group consisting of urea resin, urea-melamine resin, and phenol resin, wherein said paraffin emulsion contains oxidized paraffin.
2) The composition as set forth in Claim 1, wherein said paraffin emulsion consists of 50 to 97 parts by weight of a paraffin type hydrocarbon and 3 to 50 parts by weight of oxidized paraffin.
3) The composition as set forth in Claim 2, wherein said paraffin type hydrocarbon has a melting point range of from 40 to 80°C.
4) The composition as set forth in Claim 2, wherein said oxidized paraffin has an acid value of from 10 to 70.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000404859A CA1177992A (en) | 1982-06-10 | 1982-06-10 | Water repellent adhesive composition for wooden material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000404859A CA1177992A (en) | 1982-06-10 | 1982-06-10 | Water repellent adhesive composition for wooden material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1177992A true CA1177992A (en) | 1984-11-13 |
Family
ID=4122976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000404859A Expired CA1177992A (en) | 1982-06-10 | 1982-06-10 | Water repellent adhesive composition for wooden material |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1177992A (en) |
-
1982
- 1982-06-10 CA CA000404859A patent/CA1177992A/en not_active Expired
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