CA1127952A - Flame retardant laminate of resin impregnated paper - Google Patents
Flame retardant laminate of resin impregnated paperInfo
- Publication number
- CA1127952A CA1127952A CA322,495A CA322495A CA1127952A CA 1127952 A CA1127952 A CA 1127952A CA 322495 A CA322495 A CA 322495A CA 1127952 A CA1127952 A CA 1127952A
- Authority
- CA
- Canada
- Prior art keywords
- paper
- formaldehyde resin
- flame retardant
- plastic
- weight percent
- 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.)
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Abstract
Abstract of the Disclosure A laminated material comprises surface layers of paper impregnated with amino formaldehyde resin and inner layers of paper containing a flame retardant material and impregnated with phenol formaldehyde resin. The flame retardant material is a product of interaction of aluminium or copper compound with phosphoric acid and nitrogen bases and contains, in weight percent:
P2O5 total 37 to 63 P2O5 water-soluble O to 6 NH3 3.5 to 11 MO 18 to 43 where MO is at least one metallic oxide, the flame retardant material content ranging from 4 to 8 weight percent, with the following ratio of the laminated material components, in weight percent:
paper for surface layers 9 to 26 paper for inner layers 26 to 49 phenol-formaldehyde resin 16 to 30 amino-formaldehyde resin 5 to 26 The laminated material according to the invention has a combustibility index in the range of 0.1 to 0.5.
P2O5 total 37 to 63 P2O5 water-soluble O to 6 NH3 3.5 to 11 MO 18 to 43 where MO is at least one metallic oxide, the flame retardant material content ranging from 4 to 8 weight percent, with the following ratio of the laminated material components, in weight percent:
paper for surface layers 9 to 26 paper for inner layers 26 to 49 phenol-formaldehyde resin 16 to 30 amino-formaldehyde resin 5 to 26 The laminated material according to the invention has a combustibility index in the range of 0.1 to 0.5.
Description
112~795-Z
The present invention relates to the field of plastic production, and more particularly to fabrication of laminated materiai.
The invention can be most advantageously used under the conditions of heightened fire hazard, namely in aircraft, shipbuilding, carriage building etc., where laminated materials are applied as facing or construction-facing materials.
When used in the fields indicated above, laminated materials must possess a number of features the most important of which are fire resistance, strength, water resistance, thermostability, abrasive resistance of the surface, and provision of high-quality decorative facing.
Known in the art (cf. the USSR Inventor's Certificate No. 269,476, issued April 17, 1970, inventors L.F. Tomchina, G.B. Shalun, V.V. Razumovsky and A.~. Frost, Int. Cl. B29a) is a laminated material of the following composition in weight percent:
paper for outer layers 21.0 paper for inner layers 37.0 phenol-formaldehyde resin13.8 urea-formaldehyde resin 22.2 phosphoric acid 6.0 The disadvantage of such material evident in the process of its fabrication is that phosphoric acid used as flame retardant makes it difficult to carry out both the process of impregnating papers with resins and that of drying the impregnated papers. The disadvantage evident in the application of the plastic of such a composition is its combustibility index K ranging from 1.2 to 1.3.
The fire resistance of laminated plastic is known to be deper.dent mainly on the presence of flame retardant in its ~Z7952 composition, on the amount and chemical composition of the flame retardant introduce,d, on the composition of binding agents, as well as on the thickness and components of the plastic.
The extent of fire resistance of a material might be evaluated by its combustibility index (K) using the calorimetric method.
The combustibility index (K) is determined as a ratio of the amount of heat released during the combustibility test to that obtained by the sample from the firing source during the test period.
Following such method, materials may be classified by fire resistance according to their K values as combustible K above 2.1 hard-to-inflame K ranging of 0.5 to 2.1 hard-to-burn K ranging of 0.1 to O.S
incombustible K below 0.1 Under the conditio~sof heightened fire hazard, a plastic material having the combustibility index of not ab~ve 0.5 should be used.
The extent of fire resistance ensured by the above method is directly dependent on the plastic thickness. Thus the thickness decrease results in changes among the plastic components, i.e. number of the plastic inner layers becomes lower. Fireproofing of thin plastics is difficult to be attained, however the thickness decrease is necessary to make lower the weight of construction details covered with laminated plastics.
~ trength of a plastic is known to be determined by the value of bending strength at failure, which should be no less than 1,000 kgf/cm .
Water resistance of a plastic is known to be determined b~ the type of binding material used for protective
The present invention relates to the field of plastic production, and more particularly to fabrication of laminated materiai.
The invention can be most advantageously used under the conditions of heightened fire hazard, namely in aircraft, shipbuilding, carriage building etc., where laminated materials are applied as facing or construction-facing materials.
When used in the fields indicated above, laminated materials must possess a number of features the most important of which are fire resistance, strength, water resistance, thermostability, abrasive resistance of the surface, and provision of high-quality decorative facing.
Known in the art (cf. the USSR Inventor's Certificate No. 269,476, issued April 17, 1970, inventors L.F. Tomchina, G.B. Shalun, V.V. Razumovsky and A.~. Frost, Int. Cl. B29a) is a laminated material of the following composition in weight percent:
paper for outer layers 21.0 paper for inner layers 37.0 phenol-formaldehyde resin13.8 urea-formaldehyde resin 22.2 phosphoric acid 6.0 The disadvantage of such material evident in the process of its fabrication is that phosphoric acid used as flame retardant makes it difficult to carry out both the process of impregnating papers with resins and that of drying the impregnated papers. The disadvantage evident in the application of the plastic of such a composition is its combustibility index K ranging from 1.2 to 1.3.
The fire resistance of laminated plastic is known to be deper.dent mainly on the presence of flame retardant in its ~Z7952 composition, on the amount and chemical composition of the flame retardant introduce,d, on the composition of binding agents, as well as on the thickness and components of the plastic.
The extent of fire resistance of a material might be evaluated by its combustibility index (K) using the calorimetric method.
The combustibility index (K) is determined as a ratio of the amount of heat released during the combustibility test to that obtained by the sample from the firing source during the test period.
Following such method, materials may be classified by fire resistance according to their K values as combustible K above 2.1 hard-to-inflame K ranging of 0.5 to 2.1 hard-to-burn K ranging of 0.1 to O.S
incombustible K below 0.1 Under the conditio~sof heightened fire hazard, a plastic material having the combustibility index of not ab~ve 0.5 should be used.
The extent of fire resistance ensured by the above method is directly dependent on the plastic thickness. Thus the thickness decrease results in changes among the plastic components, i.e. number of the plastic inner layers becomes lower. Fireproofing of thin plastics is difficult to be attained, however the thickness decrease is necessary to make lower the weight of construction details covered with laminated plastics.
~ trength of a plastic is known to be determined by the value of bending strength at failure, which should be no less than 1,000 kgf/cm .
Water resistance of a plastic is known to be determined b~ the type of binding material used for protective
- 2 -~795Z
layers, by the grade of paper impregnation, and by extent of the binding agent solidification in the process of pressing. Water absorption for a period of 24 hours usually is not above 4 to 6%, according to the plastic thickness. In addition, a plastic must withstand l-hour boiling in water without formation of any swellings or stratifications, thus featuring the grade of paper impregnation with the binding agent and the necessary extent of its solidification.
Thermostability and wear resistance of a plastic surface is known to be determined by the type of binding agent used for protective layers. Thus, the plastic based on melamine-formaldehyde resin is shown to have higher wear resistance and thermostability characteristics as co.npared to those of the plastic based on urea-melamine-formaldehyde resin, which makes it possible to classify it as hard-to-inflame.
Also known in the art is a laminated plastic (cf.
the book "Fireproofing of Wood Boards and Laminated Plastics"
by A.A. Leonovitch et al. Moscow, Publishing House "Lesnaya Promyshlennost", 1974, pp. 98-115) composed of surface layers of paper, amino-formaldehyde resin and inner layers of paper including flame retardant, and phenol formaldehyde resin.
Ferriammonium phosphate used as flame retardant in this type of laminated plastic enters into che composition of the paper for inner layers.
Indicated components enter into the composition of the laminated plastic in the followins ratio (weight percent):
paper for surface layers 15 to 22 paper for inner layers 30 to 37 urea-melamine-formaldehyde resin 16 to 22 phenol-formaldehyde resin 20 tv 25 flame retardant 6 to 7 ~ - 3 -: .~
~z Such a composition ensures a laminated plastic of 2 to
layers, by the grade of paper impregnation, and by extent of the binding agent solidification in the process of pressing. Water absorption for a period of 24 hours usually is not above 4 to 6%, according to the plastic thickness. In addition, a plastic must withstand l-hour boiling in water without formation of any swellings or stratifications, thus featuring the grade of paper impregnation with the binding agent and the necessary extent of its solidification.
Thermostability and wear resistance of a plastic surface is known to be determined by the type of binding agent used for protective layers. Thus, the plastic based on melamine-formaldehyde resin is shown to have higher wear resistance and thermostability characteristics as co.npared to those of the plastic based on urea-melamine-formaldehyde resin, which makes it possible to classify it as hard-to-inflame.
Also known in the art is a laminated plastic (cf.
the book "Fireproofing of Wood Boards and Laminated Plastics"
by A.A. Leonovitch et al. Moscow, Publishing House "Lesnaya Promyshlennost", 1974, pp. 98-115) composed of surface layers of paper, amino-formaldehyde resin and inner layers of paper including flame retardant, and phenol formaldehyde resin.
Ferriammonium phosphate used as flame retardant in this type of laminated plastic enters into che composition of the paper for inner layers.
Indicated components enter into the composition of the laminated plastic in the followins ratio (weight percent):
paper for surface layers 15 to 22 paper for inner layers 30 to 37 urea-melamine-formaldehyde resin 16 to 22 phenol-formaldehyde resin 20 tv 25 flame retardant 6 to 7 ~ - 3 -: .~
~z Such a composition ensures a laminated plastic of 2 to
3 mm thick.
Disadvantages of the plastic mentioned above are as follows. It has a combustibility index K ranging from 1.2 to 1.4, i.e. the plastic falls into the category of the hard-to-inflame materials. Therefore such plastic is of limited application, in particular its use being unadvisable under the conditions of increased fire hazard. In addition, the above described lamina-ted plastic cannot be provided with a thickness of below 2 mm in case its fireproof characteristics are to be retained, since otherwise inadequate efficiency of ferriammonium phosphate as flame retardant would result in a combustibility index of greater than 2.1 thus causing the plastic to fall into the category of combustible materials.
It is an object of the present invention to provide a laminated plastic possessing an increased fire resistance while maintaining the required physical-and-mechanical and waterproof characteristics.
Another object of the present invention is to provide a fire-resistant laminated plastic having a reduced thickness while maintaining the required physical-and-mechanical and waterproof characteristics.
With these and other objects in view, there is proposed a 1 minated material consisting of the surface layers composed of paper and amino-formaldehyde resin and the inner layers composed of paper containing flame retardant and phenol-formaldehyde resin, which plastic, according to the invention, features the following composition, in weight percent:
paper for surface layers9 to 26 paper for inner layers26 to 49 phenol-formaldehyde resin16 to 30 .
1~27g5z amino-formaldehyde resin 5 to 26 flame retardant 4 to 8 where the flame retardant represents a product of the inter-action of aluminium or copper compounds with phosphoric acid and nitrogen bases, containing (in weight percent):
P205 total 37 to 63 P2O5 water-soluble 0 to 6 NH3 3.5 to 11 M0 18 to 43 where M0 - at least one metallic oxide.
The reduction of the flame retardant content to below 4% fails to provide the desired fire resistance of the plastic, whereas the increase of flame retardant content to above ~h results in worse physical-and-mechanical, as well as waterproof characteristics of the plastic.
An advantage of the invention consists in that due to the flame retardant of the above composition the laminated plastic has a combustibility index K in the range of 0.1 to 0.5 which conforms to the category of hard-to-burn materials, according to the calorimetric method used to evaluate fire-proof characteristics of the plastic. The improved fire resistance of the proposed laminated plastic can be accounted for by the fact that when exposed to the effect of elevated temperatures, the flame retardant is decomposed releasing the decom~osition products which prevent the flame from spreading over the paper and thermoreactive resin.
Another advantage of the proposed laminated plastic is the possibility to reduce its thickness, while retaining its physical-and-mechanical, waterproof and decorative character-istics.
~.~.'~
1~7g52 The indicated limits imposed on the contents of total phosphorus pentoxide and metallic oxides are defined by the chemical composition of the flame retardant. An increase in the content of water-soluble phosphorus pentoxide to above 6 weight percent results in drastic deterioration of fireproof and waterproof characteristics of the plastic. The ammonia content of less than 3.5 weight percent results in unsatisfactory fireproof characteristics of the plastic, while the upper limit of the ammonia content is limited by chemical composition of the flame retardant. The ammonia content of above 3.5 weight per-cent ensures improved fireproof characteristics of the flame-retardant.
Amino-formaldehyde resin should be preferably in the form of melamine-formaldehyde resin.
The use of melamine-formaldehyde resin in combination with the flame retardant of the proposed composition provides further reduction of the thickness of the fireproof laminated plastic, and improves its operational characteristics, such as abrasive resistance, water resistance and thermostability.
It is advisable that a product of interaction of nepheline with phosphoric acid and nitrogen bases be used as flame retardant.
This ensures cheaper process for manufacturing paper for inner layers of the plastic and as a result reduces the production cost of the plastic.
Adoption of the present invention on industrial scale does not require any revision of the technological processes for fabrication of paper and laminated plastic.
The fire resistance of the proposed plastic is three times greater than that of the known plastic, while retaining main waterproof and mechanical strength characteristics. In addition, the proposed plastic is non-toxic both under service ~i2 conditions and when exposed to heat.
Thus, possessing necessary physical-and-mechanical and waterproof characteristics the proposed laminated plastic falls into the category of hard-to-burn materials (K~ 0.5) and can be fabricated with a wide range of thickness, con-sequently meeting the requirements for aircraft and shipbuilding applications.
Melamine-formaldehyde resin used to impregnate surface layers of the plastic, in combination with a novel-type of flame retardant employed in the paper for inner layers made it possible to produce a hard-to-burn plastic of 1 mm thick.
Besides, nepheline flame retardant having slightly worse fire-resistant characteristics may be used together with melamine-formaldehyde resin.
The use of nepheline fire retardant ensures both a more efficient technological process of manufacturing paper and plastic and a low production cost of the plastic.
Nepheline flame retardant is a product of interaction of nepheline with phosphoric acid and nitrogen bases.
These and other objects, as well as advantages of the present invention will be more apparent from the following detailed description of the em~odiment thereof.
According to the invention, the laminated plastic is manufactured using an established practice of making up packs of paper sheets previously impregnated with synthetic thermo-reactive resins and compressing the packs between polished steel plates at a temperature of 135 to 150 C and under pressure of 100 kg/cm for 4 to 6 min per 1 mm of the plastic thickness, followed by cooling to 50C under pressure. Paper impregnated with amino-formaldehyde resin is intended for using as outer decorative layer of the plastic. The inner layers are made of paper containing finely dispersed water-insoluble flame retardant and phenol-formaldehyde resin. As flame retardant a product i5 ~127952 used resulting from interaction of aluminum or copper compounds with phosphoric acid and nitrogen bases and containing, in weight percent:
P205 total 37 to 63 P205 water-soluble 0 to 6 NH3 3.5 to 11 MO 18 to 43 where M0 - at least one metallic oxide.
Paper impregnated with amino-formaldehyde resin and intended to compensate for the plastic shrinkage and to prevent it from warping is used for the outer compensative layer of the plastic.
In certain cases, in order to protect the outer decorative layer from the effect of phenol-formaldehyde resin in the process of plastic fabrication, as well as to improve its decorative characteristics and to reduce the cost, a barrier layer made similarly to the compensative one is inserted between the outer decorative layer and the inner layers of the plastic. The decorative, compensative, and barrier (if any) layers form surface layers of the plastic, the total number of paper sheets in the decorative and barrier layers in the pack being equal to that of the compensative layer.
Depending on the required thickness of the laminated plastic, the indicated components are used therein at the follow-ing ratio, in weight percent:
paper for surface layers 9 to 26 paper for inner layers26 to 49 phenol-formaldehyde resin 16 to 30 amino-formaldehyde resin 5 to 26 flame retardant 4 to 8 The above procedure was used to manufacture several samples of laminated plastic which composition and character-~i~79~Z
istics can be seen from the examples given below. In all the cases the amino-formaldehyde resin content of the impregnated paper for surface layers of the plastic is 50 weight percent, and the phenol-formaldehyde resin content of the impregnated paper for inner layers is 35 weight percent. By the initial weight of paper is meant the weight of non-impregnated paper.
Example 1 A pack was made up of 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m .
1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the barrier layer, of the initial weight of 150 g/m 5 sheets of paper impregnated with phenol-form-aldehyde resin and intended for the inner layers, of the initial weight of 150 g/m2, the paper including flame retardant represent-ing a product of interaction of aluminum phosphate with phosplloric acid and urea, containing (in weight percent):
P205 48.4 P205 water-soluble 0 NH3 4.75 A123 20.7 the flame retardant content of the paper being 16.4 weight percent, and 2 sheets of paper impregnated with urea-melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m2.
The laminated plastic produced using the above process was 1.5 mm thick and had the following composition, in weight percent:
~,, ~,~, .
~127952 paper for surface layers 26.5 paper for inner layers 26.0 phenol-formaldehyde resin 16.5 urea-melamine-formaldehyde resin 26.0 flame retardant 5.0 The resulting plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.87%
strength limit at static bending 1,298 kgf/cm resistance to boiling in water for one hour no change in appearance combustibility index K 0.49 Example 2 A pack was composed of 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m .
1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the barrier layer, of the initial weight of 150 g/m .
7 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/m2, the paper including flame retardant representing a product of interaction of aluminium hydroxide with phosphoric acid and urea, containing (in weight percent):
P205 62.0 P205 water-soluble 0.9 NH3 5.8 A123 19. 1 the flame retardant content of the paper being 18.3 weight percent, and 2 sheets of paper impregnated with urea-melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m2.
~27952 The resulting laminated plastic was 2 mm thick and had the following composition, in weight percent:
paper for surface layers 21.5 paper for inner layers 30.0 phenol-formaldehyde resin 19.8 urea-melamine-formaldehyde resin 21.9 flame retardant 6.8 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.95%
strength limit at static bending 1,764 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 0.39 Example 3 A pack was made up of 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the outer 0 decorative layer, of the initial weight of 160 g/m .
Disadvantages of the plastic mentioned above are as follows. It has a combustibility index K ranging from 1.2 to 1.4, i.e. the plastic falls into the category of the hard-to-inflame materials. Therefore such plastic is of limited application, in particular its use being unadvisable under the conditions of increased fire hazard. In addition, the above described lamina-ted plastic cannot be provided with a thickness of below 2 mm in case its fireproof characteristics are to be retained, since otherwise inadequate efficiency of ferriammonium phosphate as flame retardant would result in a combustibility index of greater than 2.1 thus causing the plastic to fall into the category of combustible materials.
It is an object of the present invention to provide a laminated plastic possessing an increased fire resistance while maintaining the required physical-and-mechanical and waterproof characteristics.
Another object of the present invention is to provide a fire-resistant laminated plastic having a reduced thickness while maintaining the required physical-and-mechanical and waterproof characteristics.
With these and other objects in view, there is proposed a 1 minated material consisting of the surface layers composed of paper and amino-formaldehyde resin and the inner layers composed of paper containing flame retardant and phenol-formaldehyde resin, which plastic, according to the invention, features the following composition, in weight percent:
paper for surface layers9 to 26 paper for inner layers26 to 49 phenol-formaldehyde resin16 to 30 .
1~27g5z amino-formaldehyde resin 5 to 26 flame retardant 4 to 8 where the flame retardant represents a product of the inter-action of aluminium or copper compounds with phosphoric acid and nitrogen bases, containing (in weight percent):
P205 total 37 to 63 P2O5 water-soluble 0 to 6 NH3 3.5 to 11 M0 18 to 43 where M0 - at least one metallic oxide.
The reduction of the flame retardant content to below 4% fails to provide the desired fire resistance of the plastic, whereas the increase of flame retardant content to above ~h results in worse physical-and-mechanical, as well as waterproof characteristics of the plastic.
An advantage of the invention consists in that due to the flame retardant of the above composition the laminated plastic has a combustibility index K in the range of 0.1 to 0.5 which conforms to the category of hard-to-burn materials, according to the calorimetric method used to evaluate fire-proof characteristics of the plastic. The improved fire resistance of the proposed laminated plastic can be accounted for by the fact that when exposed to the effect of elevated temperatures, the flame retardant is decomposed releasing the decom~osition products which prevent the flame from spreading over the paper and thermoreactive resin.
Another advantage of the proposed laminated plastic is the possibility to reduce its thickness, while retaining its physical-and-mechanical, waterproof and decorative character-istics.
~.~.'~
1~7g52 The indicated limits imposed on the contents of total phosphorus pentoxide and metallic oxides are defined by the chemical composition of the flame retardant. An increase in the content of water-soluble phosphorus pentoxide to above 6 weight percent results in drastic deterioration of fireproof and waterproof characteristics of the plastic. The ammonia content of less than 3.5 weight percent results in unsatisfactory fireproof characteristics of the plastic, while the upper limit of the ammonia content is limited by chemical composition of the flame retardant. The ammonia content of above 3.5 weight per-cent ensures improved fireproof characteristics of the flame-retardant.
Amino-formaldehyde resin should be preferably in the form of melamine-formaldehyde resin.
The use of melamine-formaldehyde resin in combination with the flame retardant of the proposed composition provides further reduction of the thickness of the fireproof laminated plastic, and improves its operational characteristics, such as abrasive resistance, water resistance and thermostability.
It is advisable that a product of interaction of nepheline with phosphoric acid and nitrogen bases be used as flame retardant.
This ensures cheaper process for manufacturing paper for inner layers of the plastic and as a result reduces the production cost of the plastic.
Adoption of the present invention on industrial scale does not require any revision of the technological processes for fabrication of paper and laminated plastic.
The fire resistance of the proposed plastic is three times greater than that of the known plastic, while retaining main waterproof and mechanical strength characteristics. In addition, the proposed plastic is non-toxic both under service ~i2 conditions and when exposed to heat.
Thus, possessing necessary physical-and-mechanical and waterproof characteristics the proposed laminated plastic falls into the category of hard-to-burn materials (K~ 0.5) and can be fabricated with a wide range of thickness, con-sequently meeting the requirements for aircraft and shipbuilding applications.
Melamine-formaldehyde resin used to impregnate surface layers of the plastic, in combination with a novel-type of flame retardant employed in the paper for inner layers made it possible to produce a hard-to-burn plastic of 1 mm thick.
Besides, nepheline flame retardant having slightly worse fire-resistant characteristics may be used together with melamine-formaldehyde resin.
The use of nepheline fire retardant ensures both a more efficient technological process of manufacturing paper and plastic and a low production cost of the plastic.
Nepheline flame retardant is a product of interaction of nepheline with phosphoric acid and nitrogen bases.
These and other objects, as well as advantages of the present invention will be more apparent from the following detailed description of the em~odiment thereof.
According to the invention, the laminated plastic is manufactured using an established practice of making up packs of paper sheets previously impregnated with synthetic thermo-reactive resins and compressing the packs between polished steel plates at a temperature of 135 to 150 C and under pressure of 100 kg/cm for 4 to 6 min per 1 mm of the plastic thickness, followed by cooling to 50C under pressure. Paper impregnated with amino-formaldehyde resin is intended for using as outer decorative layer of the plastic. The inner layers are made of paper containing finely dispersed water-insoluble flame retardant and phenol-formaldehyde resin. As flame retardant a product i5 ~127952 used resulting from interaction of aluminum or copper compounds with phosphoric acid and nitrogen bases and containing, in weight percent:
P205 total 37 to 63 P205 water-soluble 0 to 6 NH3 3.5 to 11 MO 18 to 43 where M0 - at least one metallic oxide.
Paper impregnated with amino-formaldehyde resin and intended to compensate for the plastic shrinkage and to prevent it from warping is used for the outer compensative layer of the plastic.
In certain cases, in order to protect the outer decorative layer from the effect of phenol-formaldehyde resin in the process of plastic fabrication, as well as to improve its decorative characteristics and to reduce the cost, a barrier layer made similarly to the compensative one is inserted between the outer decorative layer and the inner layers of the plastic. The decorative, compensative, and barrier (if any) layers form surface layers of the plastic, the total number of paper sheets in the decorative and barrier layers in the pack being equal to that of the compensative layer.
Depending on the required thickness of the laminated plastic, the indicated components are used therein at the follow-ing ratio, in weight percent:
paper for surface layers 9 to 26 paper for inner layers26 to 49 phenol-formaldehyde resin 16 to 30 amino-formaldehyde resin 5 to 26 flame retardant 4 to 8 The above procedure was used to manufacture several samples of laminated plastic which composition and character-~i~79~Z
istics can be seen from the examples given below. In all the cases the amino-formaldehyde resin content of the impregnated paper for surface layers of the plastic is 50 weight percent, and the phenol-formaldehyde resin content of the impregnated paper for inner layers is 35 weight percent. By the initial weight of paper is meant the weight of non-impregnated paper.
Example 1 A pack was made up of 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m .
1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the barrier layer, of the initial weight of 150 g/m 5 sheets of paper impregnated with phenol-form-aldehyde resin and intended for the inner layers, of the initial weight of 150 g/m2, the paper including flame retardant represent-ing a product of interaction of aluminum phosphate with phosplloric acid and urea, containing (in weight percent):
P205 48.4 P205 water-soluble 0 NH3 4.75 A123 20.7 the flame retardant content of the paper being 16.4 weight percent, and 2 sheets of paper impregnated with urea-melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m2.
The laminated plastic produced using the above process was 1.5 mm thick and had the following composition, in weight percent:
~,, ~,~, .
~127952 paper for surface layers 26.5 paper for inner layers 26.0 phenol-formaldehyde resin 16.5 urea-melamine-formaldehyde resin 26.0 flame retardant 5.0 The resulting plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.87%
strength limit at static bending 1,298 kgf/cm resistance to boiling in water for one hour no change in appearance combustibility index K 0.49 Example 2 A pack was composed of 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m .
1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the barrier layer, of the initial weight of 150 g/m .
7 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/m2, the paper including flame retardant representing a product of interaction of aluminium hydroxide with phosphoric acid and urea, containing (in weight percent):
P205 62.0 P205 water-soluble 0.9 NH3 5.8 A123 19. 1 the flame retardant content of the paper being 18.3 weight percent, and 2 sheets of paper impregnated with urea-melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m2.
~27952 The resulting laminated plastic was 2 mm thick and had the following composition, in weight percent:
paper for surface layers 21.5 paper for inner layers 30.0 phenol-formaldehyde resin 19.8 urea-melamine-formaldehyde resin 21.9 flame retardant 6.8 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.95%
strength limit at static bending 1,764 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 0.39 Example 3 A pack was made up of 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the outer 0 decorative layer, of the initial weight of 160 g/m .
4 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/cm2, the paper including flame retardant comprising a product of interaction of cuprous sulphate with phosphoric acid and urea, containing (in weight percent):
P205 37.1 P205 water-soluble 0 ~H3 10.8 CuO 42.2 the flame retardant content of the paper being lO.S weight percent, and 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m .
i~2795Z
The resulting laminated plastic was 1 mm thick and had the following composition, in weight percent:
paper for surface layers22.0 paper for inner layers 38.0 phenol-formaldehyde resin23.0 melamine-formaldehyde resin 12.4 flame retardant 4.6 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm water absorption 2.9%
strength limit at static bending 1.551 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 0.43 Example 4 A pack was composed of 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m2, 7 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/m , the paper including flame retardant representing a product of interaction of nepheline with phosphoric acid, urea, and melamlne, containing (in weight percent):
P205 50.5 P205 water-soluble 5 7 NH3 10.4 A1203, Fe203 ~ ~a20 ~ K20 and other oxides 18.7 the flame retardant content of the paper being 9.2 weight percent, and 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the compensative layer, of the initial weight o~ 150 g~m~.
~1;~52 The resulting plastic was 1.5 mm thick and had the following composition, in weight percent:
paper for surface layers 14.7 paper for inner layers 45.4 phenol-formaldehyde resin 27.0 melamine-formaldehyde resin 8.3 flame retardant 4.6 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.8h strength limit at static bending 1,528 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 0.29 Example 5 A pack was composed of 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m2.
13 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/m2, the paper including flame retaxdant comprising a product of interaction of nepheline with phosphoric acid and urea, containing (in weight percent):
P2O5 49.0 P2O5 water-soluble 3.0 NH3 4.3 123, Fe2O3~ Na2O, K20 and other oxides 18.3 the flame retardant content of the paper bein~ 12.0 weight percent, and 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g~m .
_ 13 -llz7gsz The resulting plastic was 3 mm thick and had the following composition, in weight percent:
paper for surface layers 9.0 paper for inner layers 49.3 phenol-formaldehyde resin 30.0 urea-melamine-formaldehyde resin 5.0 flame retardant 6.7 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.3%
strength limit at static bending 1,800 kgf/cm2 resistance to boiling in water for one hour nG change in appearance combustibility index K 0.35 Example 6 A pack was composed of 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m2.
7 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers of the initial weight of 150 g/m2, the paper including flame retardant representing a product of interaction of nepheline with phosphoric acid and urea, containing (in weight percent):
P205 total 49.3 P205 water-soluble 3.0 NH3 4.3 A1203, Fe203, Na2, K20 and other oxides 18.3 the flame retardant content of the paper being 14.0 weight percent, and 1 sheet of paper impregnated with ur~a-melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m2.
1~27952 The resulting plastic was 1.5 mm thick and had the following composition, in weight percent:
paper for surface layers 14.7 paper for inner layers 43.0 phenol-formaldehyde resin 27.0 urea-melamine-formaldehyde resin 8.3 flame retardant 7.0 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.~/o strength limit at static bending 1,340 kgf/cm2 resistance to boiling in water for one hour no change in appearance com~ustibility index K 0.41 ExamPle 7 A pack was composed of 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 150 g/m2.
1 sheet of paper impregnated with melamine-form-aldehyde resin and intended for the barrier layer, of the initial weight of 150 g/m2
P205 37.1 P205 water-soluble 0 ~H3 10.8 CuO 42.2 the flame retardant content of the paper being lO.S weight percent, and 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m .
i~2795Z
The resulting laminated plastic was 1 mm thick and had the following composition, in weight percent:
paper for surface layers22.0 paper for inner layers 38.0 phenol-formaldehyde resin23.0 melamine-formaldehyde resin 12.4 flame retardant 4.6 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm water absorption 2.9%
strength limit at static bending 1.551 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 0.43 Example 4 A pack was composed of 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m2, 7 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/m , the paper including flame retardant representing a product of interaction of nepheline with phosphoric acid, urea, and melamlne, containing (in weight percent):
P205 50.5 P205 water-soluble 5 7 NH3 10.4 A1203, Fe203 ~ ~a20 ~ K20 and other oxides 18.7 the flame retardant content of the paper being 9.2 weight percent, and 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the compensative layer, of the initial weight o~ 150 g~m~.
~1;~52 The resulting plastic was 1.5 mm thick and had the following composition, in weight percent:
paper for surface layers 14.7 paper for inner layers 45.4 phenol-formaldehyde resin 27.0 melamine-formaldehyde resin 8.3 flame retardant 4.6 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.8h strength limit at static bending 1,528 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 0.29 Example 5 A pack was composed of 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m2.
13 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/m2, the paper including flame retaxdant comprising a product of interaction of nepheline with phosphoric acid and urea, containing (in weight percent):
P2O5 49.0 P2O5 water-soluble 3.0 NH3 4.3 123, Fe2O3~ Na2O, K20 and other oxides 18.3 the flame retardant content of the paper bein~ 12.0 weight percent, and 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g~m .
_ 13 -llz7gsz The resulting plastic was 3 mm thick and had the following composition, in weight percent:
paper for surface layers 9.0 paper for inner layers 49.3 phenol-formaldehyde resin 30.0 urea-melamine-formaldehyde resin 5.0 flame retardant 6.7 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.3%
strength limit at static bending 1,800 kgf/cm2 resistance to boiling in water for one hour nG change in appearance combustibility index K 0.35 Example 6 A pack was composed of 1 sheet of paper impregnated with urea-melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m2.
7 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers of the initial weight of 150 g/m2, the paper including flame retardant representing a product of interaction of nepheline with phosphoric acid and urea, containing (in weight percent):
P205 total 49.3 P205 water-soluble 3.0 NH3 4.3 A1203, Fe203, Na2, K20 and other oxides 18.3 the flame retardant content of the paper being 14.0 weight percent, and 1 sheet of paper impregnated with ur~a-melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m2.
1~27952 The resulting plastic was 1.5 mm thick and had the following composition, in weight percent:
paper for surface layers 14.7 paper for inner layers 43.0 phenol-formaldehyde resin 27.0 urea-melamine-formaldehyde resin 8.3 flame retardant 7.0 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2.~/o strength limit at static bending 1,340 kgf/cm2 resistance to boiling in water for one hour no change in appearance com~ustibility index K 0.41 ExamPle 7 A pack was composed of 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 150 g/m2.
1 sheet of paper impregnated with melamine-form-aldehyde resin and intended for the barrier layer, of the initial weight of 150 g/m2
5 sheets of paper impregnated with phenol-formalde aldehyde resin and intended for the inner layers, of the initial weight of 150 g/m2, the paper including flame retardant representing a product of interaction of nepheline with phosphoric acid and urea, containing (in weight percent):
P2O5 total 47.1 P205 water-soluble 4.03 NH3 3.71 A1203 ~ Fe203 ~ Na20 ~ K2 and other oxides 1~.8 the flame retardant content of the paper being 14.0 weight percent, and 2 sheets of paper impregnated with melamine formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m .
The resulting plastic was 1.5 mm thick and had the following composition, in weight percent:
paper for surface layers 26.5 paper for inner layers 26.7 phenol-formaldehyde resin 16.5 melamine-formaldehyde resin 26.0 flame retardant 4,3 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2. 01%
strength limit at static bending 1.347 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 0.36 Example 8 A pack was made up of 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m2.
4 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/m , the paper containing flame retardant representing a product of interaction of nepheline with phosphoric acid and urea, containing (in weight percent);
P205 total 48.0 P2O5 water-soluble 3.5 NH3 4.4 A1203, Fe203 ~ Na20 ~ X2 and other oxides 21.0 ~- - 16 -~1~95;~
the flame retardant content of the paper being 15 weight percent, and 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 160 g/m .
The resulting plastic was 1 mm thick and had the following composition, in weight percent:
paper for surface layers 22.0 paper for inner layers 36.2 phenol-formaldehyde resin 23.0 melamine-formaldehyde resin 12.4 flame retardant 6.4 The resulting plastic exhibited the following charactexistics:
specific gravity 1.45 g/cm3 water absorption 2.02%
strength limit at static bending 1,233 kgf/cm2 resistance to boiling in water no change in for one hour appearance combustibility index K 0.38 For the aim of comparison, characteristics of the known plastic with ferriammonium phosphate used as flame retardant are given minimum thickness 2 mm specific gravity 1.45 g/cm3 water absorption 2.5%
strength limit at static bending 1,250 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 1.3 B
~795Z
The aforementioned Examples are merely illustrative of specific embodiments of the invention. It should be under-stood that modifications of the plastic fabrication are possible according to its function and applications.
-- 1~ --
P2O5 total 47.1 P205 water-soluble 4.03 NH3 3.71 A1203 ~ Fe203 ~ Na20 ~ K2 and other oxides 1~.8 the flame retardant content of the paper being 14.0 weight percent, and 2 sheets of paper impregnated with melamine formaldehyde resin and intended for the compensative layer, of the initial weight of 150 g/m .
The resulting plastic was 1.5 mm thick and had the following composition, in weight percent:
paper for surface layers 26.5 paper for inner layers 26.7 phenol-formaldehyde resin 16.5 melamine-formaldehyde resin 26.0 flame retardant 4,3 The plastic exhibited the following characteristics:
specific gravity 1.45 g/cm3 water absorption 2. 01%
strength limit at static bending 1.347 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 0.36 Example 8 A pack was made up of 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the outer decorative layer, of the initial weight of 160 g/m2.
4 sheets of paper impregnated with phenol-formaldehyde resin and intended for the inner layers, of the initial weight of 150 g/m , the paper containing flame retardant representing a product of interaction of nepheline with phosphoric acid and urea, containing (in weight percent);
P205 total 48.0 P2O5 water-soluble 3.5 NH3 4.4 A1203, Fe203 ~ Na20 ~ X2 and other oxides 21.0 ~- - 16 -~1~95;~
the flame retardant content of the paper being 15 weight percent, and 1 sheet of paper impregnated with melamine-formaldehyde resin and intended for the compensative layer, of the initial weight of 160 g/m .
The resulting plastic was 1 mm thick and had the following composition, in weight percent:
paper for surface layers 22.0 paper for inner layers 36.2 phenol-formaldehyde resin 23.0 melamine-formaldehyde resin 12.4 flame retardant 6.4 The resulting plastic exhibited the following charactexistics:
specific gravity 1.45 g/cm3 water absorption 2.02%
strength limit at static bending 1,233 kgf/cm2 resistance to boiling in water no change in for one hour appearance combustibility index K 0.38 For the aim of comparison, characteristics of the known plastic with ferriammonium phosphate used as flame retardant are given minimum thickness 2 mm specific gravity 1.45 g/cm3 water absorption 2.5%
strength limit at static bending 1,250 kgf/cm2 resistance to boiling in water for one hour no change in appearance combustibility index K 1.3 B
~795Z
The aforementioned Examples are merely illustrative of specific embodiments of the invention. It should be under-stood that modifications of the plastic fabrication are possible according to its function and applications.
-- 1~ --
Claims (4)
1. A laminated material comprising surface layers of paper impregnated with amino-formaldehyde resin and inner layers of paper containing a flame retardant material in an amount of 4 to 8 percent of the total laminate and impregnated with phenol-formaldehyde resin, said flame retardant material being a product of interaction of an aluminium or copper compound with phosphoric acid and nitrogen bases, containing in weight percent:
P2O5 total 37 to 63 P2O5 water-soluble O to 6 NH3 3.5 to 11 MO 18 to 43 where MO is at least one metallic oxide, said components of the laminated material being contained therein in the follow-ing ratio, in weight percent:
paper for surface layers 9 to 26 paper for inner layers 26 to 49 phenol-formaldehyde resin 16 to 30 amino-formaldehyde resin 5 to 26 said laminated material having a combustibility index in the range of 0.1 to 0.5.
P2O5 total 37 to 63 P2O5 water-soluble O to 6 NH3 3.5 to 11 MO 18 to 43 where MO is at least one metallic oxide, said components of the laminated material being contained therein in the follow-ing ratio, in weight percent:
paper for surface layers 9 to 26 paper for inner layers 26 to 49 phenol-formaldehyde resin 16 to 30 amino-formaldehyde resin 5 to 26 said laminated material having a combustibility index in the range of 0.1 to 0.5.
2. A laminated material as defined in Claim 1, wherein said amino-formaldehyde resin is melamine-formaldehyde resin.
3. A laminated material as defined in Claim 1, wherein said flame retardant is a product of interaction of nepheline with phosphoric acid and nitrogen bases.
4. A laminated material as defined in Claim 2, wherein said flame retardant is a product of interaction of nepheline with phosphoric acid and nitrogen bases.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA322,495A CA1127952A (en) | 1979-02-28 | 1979-02-28 | Flame retardant laminate of resin impregnated paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA322,495A CA1127952A (en) | 1979-02-28 | 1979-02-28 | Flame retardant laminate of resin impregnated paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127952A true CA1127952A (en) | 1982-07-20 |
Family
ID=4113646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA322,495A Expired CA1127952A (en) | 1979-02-28 | 1979-02-28 | Flame retardant laminate of resin impregnated paper |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1127952A (en) |
-
1979
- 1979-02-28 CA CA322,495A patent/CA1127952A/en not_active Expired
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