CA1224598A - Paper sizing agent - Google Patents
Paper sizing agentInfo
- Publication number
- CA1224598A CA1224598A CA000446416A CA446416A CA1224598A CA 1224598 A CA1224598 A CA 1224598A CA 000446416 A CA000446416 A CA 000446416A CA 446416 A CA446416 A CA 446416A CA 1224598 A CA1224598 A CA 1224598A
- Authority
- CA
- Canada
- Prior art keywords
- sizing agent
- monoolefin
- mixture
- composition including
- carbon atoms
- 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.)
- Expired
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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
- D21H17/16—Addition products thereof with hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/567—Preparation of carboxylic acid anhydrides by reactions not involving carboxylic acid anhydride groups
Abstract
ABSTRACT OF THE DISCLOSURE
A paper sizing agent is disclosed which is comprised of a water soluble salt which is obtained by alkali saponification of a reaction product obtained by thermal addition reaction of a monoolefin having carbon atoms of 16 to 24 and the average ratio of the number of methylene groups to methyl groups of 0.9 or more or a mixture thereof with maleic anhydride. The resulting paper sizing agent gives excellent results with respect to being used as a paper sizing agent and causes sub-stantially no foaming when it receives a fixing obstruction.
A paper sizing agent is disclosed which is comprised of a water soluble salt which is obtained by alkali saponification of a reaction product obtained by thermal addition reaction of a monoolefin having carbon atoms of 16 to 24 and the average ratio of the number of methylene groups to methyl groups of 0.9 or more or a mixture thereof with maleic anhydride. The resulting paper sizing agent gives excellent results with respect to being used as a paper sizing agent and causes sub-stantially no foaming when it receives a fixing obstruction.
Description
~224598 PAPER SIZING AGENT
FIELD OF THE INVENTION
This invention relates to a paper sizing agent and, more particularly, it relates to a paper sizing agent which shows sizing efficiency superior to a rosin type sizing agent while hardly foaming during use.
BACKGROUND OF THE INVENTION
Hitherto, as an internal sizing agent, a so-called rosin type sizing agent which employs rosin as raw material has been generally used. However, rosin is a natural substance and has some problems such as fluctuation of price, instability of supply and the like. Therefore, as synthesized sizing agents which take the place of this, so-called petroleum resin sizing agents which employ, as raw material, petroleum resin obtained from a mixture of C5 and Cog fractions which can be obtained from naphtha cracked oil and other various synthesized sizing agents have been proposed.
However, until several years ago, such synthesized sizing agents, except the petroleum resin sizing agent, were hardly put to practical use due to problems related to efficiency an price, and the petroleum resin sizing agent practically used was also limited in use due to problems related to efficiency.
1~:24598 However, recently substantial use has been made of synthesized sizing agents superior in efficiency and price to the rosin type sizing agents. Such agents are water-soluble salts of alkenyl succinic acids which are made from highly branched olefins and malefic android.
The paper sizing process using water-soluble salts of alkenyl succinic acids as internal sizing agents has been well-known as described in Japanese Patent Publication No. 565/65 (corresponding to US. Patent 3,139,373).
In this Publication, it is described that water soluble salts of alkenyl succinic acids have an alkenyl group having 8 to 15 carbon atoms and those having an alkenyl group having 16 or more carbon atoms cannot afford a satisfactory sizing efficiency. Presently, there is no known sizing agent which is the water soluble salt of alkenyl succinic acid which has an alkenyl group having 16 or more carbon atoms or-a sizing agent containing this salt and which shows a sizing efficiency superior to the rosin type sizing agent.
Water-soluble salts of alkenyl succinic acids have been said to have a problem in practical use due to foaming as described in Japanese Patent Publication (unexamined) No. 27003/79. The present inventors have found that the foam is formed only when the sizing agent is obstructed from fixing on pulp during sizing and the us-fixed water-soluble salt of alkenyl succinic acid or a reaction product of alkenyl succinic acid with aluminum sulfate remains in a pulp slurry. Thus, the present inventors found that when fixing proceeds normally, there is no problem in practical use since there is almost no foaming. The undesirable obstruction to fixing of the sizing agent on pulp is herein referred to as "fixing obstruction".
However, though the obstruction to fixing of the sizing agent in the paper making process is a rare phenomenon, the foaming phenomenon caused by the unfixed sizing agent consisting of the water-soluble salt of alkenyl succinic acid causes serious damage to the process and the quality of the produced paper.
In this way, conventionally, when the water soluble salt of the reaction product of the monoolefin with malefic android was used as a sizing agent, the principal object was only the sizing efficiency.
Accordingly, this resulted in attention only being given to the relationship of the number of carbon atoms in the monoolefin used as raw material with the sizing efficiency.
However, the relationship of its structure with the sizing efficiency andthefoaming nature was not investigated.
Therefore, foaming problems were often caused during actual use as a sizing agent. Further, there were caused problems that satisfactory results could not be obtained when a ~224598 l monoolefin having 16 or more carbon atoms was used as raw material.
SUMMARY OF THE INVENTION
The present inventors carried out studies related to the relationship between the molecular structure of manliness used as raw materials and the sizing efficiency and foaming nature. These studies were carried out in order to develop a synthesized sizing agent which shows a sizing efficiency superior to the rosin type sizing agent and hardly foams even if it receives a fixing obstruction during use. As a result the present inventors have found that the sizing efficiency and foaming nature of the water soluble salt of alkenyl succinic acid remarkably depend on the macular structure of the olefin used as raw material, particularly, the condition of branching which is represented by a value of an average ratio of the number of ethylene groups to that of methyl groups According to the present invention there is provided a paper composition including a sizing agent comprising a water soluble salt obtained by a process comprising the steps of carrying out a thermal addition reaction of malefic android with a monoolefin having 16 to 24 carbon atoms and a ratio of the number of ~$~
1;~24598 - pa -1 ethylene groups (-SHEA-) to methyl groups (-SHEA of 0.9 or more or a mixture of monoolefins having 16 to 24 carbon atoms and an average ratio of the number of ethylene groups to methyl groups of O r or more;
and subjecting the reaction product to alkali saponification to obtain the water soluble salt.
More surprisingly the present inventors have .
found that even a monoolefin containing 16 or more carbon atoms (which was conventionally considered to be unsuitable as raw material for a sizing agent as it could not afford a satisfactory sizing efficiency) could be used as raw material for a sizing agent when the average ratio of the number of ethylene groups to that of methyl groups is OWE
or more. The present inventors found that such a monoolefin can afford a homogeneous transparent sizing agent by alkali saponification of a reaction product which is obtained by the thermal addition reaction with malefic android. Such a sizing agent causes substantially no foaming even when receiving a fixing obstruction and has a sizing efficiency superior to the rosin type sizing agent over a wide range of addition amounts.
In addition to this, as a result of further-studies based on the knowledge obtained from these results, the present inventors have found that a water soluble salt (A) which is obtained by alkali saponification of a reaction product obtained by reacting a monoolefin (having 16 to 24 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more) or a mixture thereof with malefic android reduces foaming without reducing the sizing efficiency when it is mixed with a conventional paper sizing agent which readily causes foaming when it receives a fixing obstruction.
1~:24598 The sizing agent containing the water soluble salt (A) related to this invention was developed as a result of clarifying the relationship of the foaming nature and sizing efficiency in using a sizing agent with the molecular structure of the olefin used as raw material.
This relationship was not previously known. The present invention is a paper sizing agent containing the water soluble salt (A) which is obtained by alkali saponification of a reaction product obtained by thermal addition reaction of a monoolefin having 16 to 24 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more, or the mixture thereof.
The monoolefins having 16 or more carbon atoms were previously considered to be unsuitable as raw material for a paper sizing agent consisting of a water soluble salt of alkenyl succinic acid. The sizing agent of the present invention not only shows a sizing efficiency superior to the rosin type sizing agent over a wide range of addition amounts but also causes substantially no foaming when receiving a fixing obstruction.
DETAILED DESCRIPTION OF THE INVENTION
The oligomer having 16 or more carbon atoms (which is obtained by polymerization of a monoolefin such as propylene, battalion and the like or a mixture thereof in the presence of an acid catalyst such as phosphoric acid, . - 6 -i2~4598 and the like or a Friedel-Crafts catalyst such as aluminum chloride and the Lucas generally known to have a highly branched structure, and the average ratio of the number of ethylene groups to that of methyl groups is generally less than 0.9 The sizing agent obtained from a malefic android adduce of such a highly branched oligomer having 16 or more carbon atoms is not preferable for purposes of this invention because the sizing efficiency is insufficient.
Contrary to this, the oligomer having 16 or more carbon atoms which is obtained by polymerization of a monoolefin such as propylene, battalion, Helene, octane and the like or a mixture thereof in the presence of, for example, an organic aluminum type catalyst has a structure less branched than that of the oligomers obtained by the acid catalyst mentioned above, and the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more.
As already mentioned above, the monoolefin or monoolefin mixture in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more and the number of carbon atoms is 16 to I preferably 16 to 20, can be suitably used for the purposes of this invention as paper sizing agent for all types of paper.
A monoolefin having 25 or more carbon atoms or the mixture thereof is not preferable because the reaction 1 product obtained from reacting it with malefic android does not easily afford a homogeneous aqueous solution by alkali saponification and the obtained sizing agent cannot afford a satisfactory sizing effect though it shows a low foaming nature.
Examples of the monoolefin or monoolefin mixture used in this invention in which the number of carbon atoms is 16 to 24 and the average ratio of the number of ethylene groups to methyl groups is 0.9 or more include oligomers obtained by polymerization of a monoolefin having 3 to 8 carbon atoms such as propylene, battalion, Helene, octane and the Lowe or a plurality thereof, straight chain inner olef.ins obtained by dehydrogenation of n-paraffin and the like - and straight chain ~-olefins obtained by polymerization of ethylene and the like/ and mixtures thereof ~11 of the sizing agents obtained from these monoo:Lefin$
or monoolefin mixtures causes little foaming when receiving a fixing obstruction. The oligomers of n-butylene or straight chain inner olefins are preferably used due to the particularly excellent sizing efficiency.
It is also possible to use a monoolefin mixtures prepared by mixing the monoolefins having 16 to 24 carbon atoms which has the average ratio of the number of ethylene groups to that of methyl groups of 0.9 or more with those having the average ratio of 0.9 or less. In this case, the thus prepared monoolefin mixture must be adjusted so that 1~245g8 the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more.
On the other hand, a monoolefin or monoolefin mix-lure in which the average ratio of the number of ethylene groups to that of methyl groups is 22 or more is not suit-able for the purposes of this invention because they are composed of a monoolefins having 25 or more carbon atoms.
Therefore, the average ratio of number of ethylene groups to that of methyl groups is preferably 0.9 or more and less than 22.
The reaction product of a monoolefin or mixture thereof with malefic android used in this invention can be obtained by thermal addition reaction of the monoolefin with malefic android in the absence of catalyst. The no-action is preferably carried out in an inert atmosphere swishes nitrogen under atmospheric or some increased pressure, at 180 to 250C, more preferably at 200 to 230C, followed by reacting at the same temperature for 1 to 30 hours, preferably for 3 to 20 hours. The mow ratio of the moo-olefin to the malefic android is not necessarily limited but is preferably used in an amount of 0.5 to 3 mow per mow of monoolefin. After the reaction is over, the us-reacted monoolefin and the malefic android are removed by distillation to afford a liquid reaction product having rather low viscosity. The saponification value (JIG K 5902) of the reaction product is about 250 to 350. Depending on the reaction conditions, a small amount of by-products may _ g _ i224598 be formed. The by-products can be removed as distillation residue by distillation under reduced pressure, but the amount of by-product is small and its removal is not alleges required, The reaction product thus obtained is saponified by alkali and made a transparent solution to afford the sizing agent of this invention, Examples of the alkali used for saponification in this invention include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like, ammonia, or water soluble amine such as trimethylamine, diethylamine and the lice, but the use of sodium hydroxide or potassium hydroxide is desirable. The amount of alkali used for saponification is 0.8 to 1.2 times, preferably 0.9 to 1.1 times, the amount corresponding to the saponification value of the reaction product of the monoolefin with malefic ashy-drive. The foaming nature of the obtained sizing agent in-creases with the decrease of the amount of alkali, and when the amount is Less than 0.8 times the amount corresponding to the saponification value, the foaming increases rather substantially though the sizing effect is little influenced, The sizing agent related to this invention can be obtained by reacting a monoolefin or monoolefin mixture having 16 to 24 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more with malefic android and saponifying the resulting reaction product independently or saponifying 1~2~sg~
after mixing it with the other substance such as rosin or a reaction product of a monoolefin or monoolefin mixture having 15 or less carbon atoms with malefic android.
They can be mixed after saponification. The sizing agent can also be obtained by reacting the monoolefin or moo-olefin mixture used in this invention with malefic android after mixing with a monoolefin or monoolefin mixture having 15 or less carbon atoms and saponifying the obtained reaction product.
The water soluble salt (A of the malefic android adduce of the monoolefin or monoolefin mixture having 16 to 24 carbon atoms in this invention is desirably present in an amount of 10% by weight or more in the effective component of the sizing agent. The more the proportion occupied in the effective component of the sizing agent increases, the larger the restraining effect on foaming when it receives a fixing obstruction during use. However, even if the amount is less than 10% by weight, the restraining effect on foaming can be exhibited.
The sizing agent related to this invention can be added to a paper stock in the same manner as that of the conventional rosin type sizing agent. For example, it can be fixed on a pulp by adjusting the pi to about 4.0 to 5.5, preferably 4.2 to 5.0, by adding aluminum sulfate after adding the sizing agent related to this invention to 1~24598 a pulp slurry which is in or after the beating process.
The agent of this invention can be used together with other sizing agents such as a conventional rosin type sizing agent, a petroleum resin sizing agent and the like in any ratio, and may also be used for surface sizing.
In case of internal sizing, the amount (addition amount) of the sizing agent used in this invention is in the range of 0.01 to 5.0% by weight, preferably 0.05 to 3.0% by weight, based on the weight of the dry pulp. When surface sizing is carried out the sizing agent is coated in an amount of 0.005 to 0.5 g/m2 on a dry weigh basis.
As explained in the above, even a monoolefin or monoolefin mixture having 16 or more carbon atoms which was conventionally said not to afford a satisfactory sizing agent in the case of reacting it independently with malefic android can afford a paper sizing agent showing an excellent sizing efficiency and a low foaming nature. This good results are made possible by selecting a monoolefin or monoolefin mixture in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more.
The sizing agent of this invention is not only superior to the rosin type sizing agent over a wide range of addition amounts but it also remarkably restrains the foaming in receiving a fixing obstruction.
The characteristics of the sizing agent related . - 12 -1~4598 to this invention are explained above, and this invention is further specifically illustrated by the following Comparative Examples and Examples. However, the scope of the invention is not limited to these examples. The average ratio of the number of ethylene groups to that of methyl groups in the Comparative Examples and Examples are measured by the nuclear magnetic resonance spectral method.
COMPARATIVE EXAMPLE
A mixture of 250 parts by weight of propylene oligomers having 8 to 10 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups was 0.80 and 200 parts by weight of malefic android were heated to 215C in an autoclave under nitrogen atmosphere and reacted for 3 hours in the absence of catalyst. After the reaction was over, the reaction mixture was taken out and the unrequited oligomers and malefic android were removed by distillation under reduced pressure to afford 294 parts by weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 502.
The potassium hycLroxide corresponding to the specification value of the reaction product and water were added to the obtained reaction product, and the mixture was stirred at 90C for 2 hours and saponified to give a transparent sizing agent containing 40~ by weight of the solid component (Sizing agent A). The pi of this sizing agent was 10.1.
I
A mixture of 332 parts by weight of propylene oligomers having 16 to 21 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups was 0.87 and 166 parts by weight of malefic android were reacted in the same manner as described in Comparative Example 1 and the unrequited reactants were removed to afford 194 parts by weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 320.
This product was saponified in the same manner as described in Comparative Example 1 and adjusted so as to have 40 % by weight of the solid component. However, the product was in an emulsion state and could not afford a homogeneous trays-parent sizing agent. The pi of this emulsified sizing agent (Sizing agent B) was 10.1.
EXAMPLE
A mixture of 230 parts by weight of n-butylene oligomers having 16 to 20 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups was 0.93 and 100 parts by weight of malefic android were reacted in the same manner as described in Comparative Example 1. Unrequited reactants were removed to afford 159 parts by weigh-t of a reaction product. The saponification value of this reaction product was 350. This product was saponified in the same manner as described in Comparative 1~2459~
Example 1 to give a transparent sizing agent related to this invention containing OWE by weight of the solid component (Sizing agent C). The pi of this sizing agent was 10.1.
225 parts by weight of a straight chain inner olefin having 16 carbon atoms with the average ratio of the number of ethylene groups to that of methyl groups being 6.1 and 100 parts by weight of malefic android were reacted in the same manner as described in Comparative Example 1.
Unrequited reactants were removed to afford 156 parts by weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 352.
This product was saponified in the same manner as described in Comparative Example 1 to give a transparent sizing agent related to this invention containing 20% by weight of the solid component sizing agent D). The pi of this sizing agent was 10Ø
20 parts by weight of the reaction product obtained in Example 1 and 80 parts by weight of the reaction product obtained in Comparative Example 1 were mixed.
The saponification value of this mixture was 472. This was saponified in the same manner as described in Comparative Example 1 to afford a transparent sizing agent related to 1~24598 this invention containing 40% by weight of the solid component (Sizing agent E). The pi of this sizing agent was 10.1.
50 parts by weight of Sizing agent C obtained in Example 1 and 50 parts by weight of Sizing agent A obtained in Comparative Example 1 were mixed to give a transparent sizing agent related to this invention containing 40% by weight of the solid component (Sizing agent F). The pi of this sizing agent was 10.1.
40 parts by weight of Sizing agent D obtained in Example 2 and 80 parts by weight of Sizing agent A obtained in Comparative Example 1 were mixed and water was added thereto to afford a transparent sizing agent related to this invention containing 30% by weight of the solid component (Sizing agent G). The pi of this sizing agent was 10.1.
With respect to the sizing agents A and B obtained in the above-mentioned Comparative Examples 1 to 2 and the sizing agents C, D, E, F and G obtained in Examples 1 to 5, the sizing test was carried out. As a sizing agent for comparison, a commercial reinforced rosin sizing agent (RF Size 880 L-50 manufactured by Hymen Industry Co.) was 1~:24598 used. The testing method is as follows.
A 3% slurry of hardwood bleached raft pulp which was adjusted to the beating degree C.F.=400 cc was prepared and to this slurry was added Sizing agent A, Sizing agent s, Sizing agent C, Sizing agent D, Sizing agent E, Sizing agent F, Sizing agent G or the reinforced rosin sizing agent in an amount of 0.2% by weight, 0.5%
by weight or 1% by weight as solid component based on the weight of dry pulp and aluminum sulfate was added with stirring to make the pi of the slurry 4.5. The pulp slurry was diluted with water adjusted to pH-S.0 by aluminum sulfate to make the pulp concentration about 0.2~ by weight.
The pulp was made into paper by a TAIPEI standard sheet machine according to the general method and after pressing for dehydration (4 kg/cm2 x 1 mix), the wet paper was dried by a rotary dryer at 105~C for 3 minutes. The basis weight of this hand-made paper was 60 g/m2.
The obtained paper was allowed to stand in a room at 20~C and 65% humidity for 24 hours, and then the sizing degree was measured by JIS-P-8112 Stockigt sizing degree testing method. The results are summarized in Table 1.
Next, in order to examine the foaming under the conditions in which the pulp slurry concentration was low and the sizing agent could easily receive the fixing 12~459B
obstruction, a 0. owe by weight of slurry of hardwood bleached raft pulp which was adjusted to a beating degree C.F.=400 cc was added with Sizing agent A, Sizing agent B, Sizing agent C, Sizing agent D, Sizing agent E, Sizing agent F, Sizing agent G or the reinforced rosin sizing agent in an amount of 0.5~ by weight (as solid component) based on the weight of dry pulp, and aluminum sulfate was added to make the pi of the pulp slurry 4.5. Then 500 ml of this pulp slurry was put in lo a l of Erlenmeyer flask and sealed. It was attached to a horizontal reciprocating shaker (Shaking frequency 156 shaking/min, Amplitude 70 mm) and shook for l minute.
The volume of foam in the pulp slurry was then measured by the Broadway bubble measuring scale (Pulp and Paper Engineering, Vol. 2, No. 11, p. 22). The results are summarized in Table 1.
1~:24598 Table Stockigt Sizing Foam Content Sizing Agent Degree (sea) (I by volume) o _ 0.5* 1.0* 0.5 A (Coup. Example 1) 15.3 28.5 32.8 0.52 B ( " 2) 0 2.0 6.2 0.05 C (Example 1) 19.0 29.8 33.7 0.02 D ( " 2) 15.8 28.5 32.5 0.02 E ( " I 16.0 28.6 33.0 0.25 F ( " 4) 17.5 30.0 33.5 0.12 G ( " 5) 15.5 28.5 33.0 0.24 Reinforced Rosin 9.1 23.1 31.6 0.31 Sizing Agent Note: "*": Addition amount of sizing agent (% by weight) Sizing agent A in the examples obtained from the propylene oligomer mixture having 8 to 10 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 0.80 shows a sizing effect superior to the reinforced rosin sizing agent. However, the foaming amount in receiving a fixing obstruction is larger than that of the reinforced rosin sizing agent. In the emulsi-fled sizing agent B in this example obtained from the mixture of propylene oligomers having 16 to 21 carbon atoms in which the average ratio of the number of ethylene groups to that ~459~3 of methyl groups is 0.87, the amount of the foaming is less than that of the reinforced rosin sizing agent.
However, the sizing effect is apparently substantially inferior to the reinforced rosin sizing agent.
On the contrary, Sizing agent C obtained from the oligomer mixture of n-butylene in which the average ratio of the number of ethylene groups to that of methyl groups is 0.93 and Sizing agent D obtained from the straight chain inner olefin having of 16 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 6.1 which are related to this invention show not only a sizing effect superior to the reinforced rosin sizing agent over a wide range of addition amount but also substantially less foaming than that of the reinforced rosin sizing agent.
Sizing agent E of this invention obtained by mixing the reaction product obtained in Comparative Example 1 with the reaction product obtained in Example 1 followed by saponification, and Sizing agents F and G obtained by saponification followed by mixing show an excellent efficiency superior to the reinforced sizing agent over a wide range of addition amounts and at the same time the foaming when receiving a fixing obstruction is suppressed.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled ion the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
FIELD OF THE INVENTION
This invention relates to a paper sizing agent and, more particularly, it relates to a paper sizing agent which shows sizing efficiency superior to a rosin type sizing agent while hardly foaming during use.
BACKGROUND OF THE INVENTION
Hitherto, as an internal sizing agent, a so-called rosin type sizing agent which employs rosin as raw material has been generally used. However, rosin is a natural substance and has some problems such as fluctuation of price, instability of supply and the like. Therefore, as synthesized sizing agents which take the place of this, so-called petroleum resin sizing agents which employ, as raw material, petroleum resin obtained from a mixture of C5 and Cog fractions which can be obtained from naphtha cracked oil and other various synthesized sizing agents have been proposed.
However, until several years ago, such synthesized sizing agents, except the petroleum resin sizing agent, were hardly put to practical use due to problems related to efficiency an price, and the petroleum resin sizing agent practically used was also limited in use due to problems related to efficiency.
1~:24598 However, recently substantial use has been made of synthesized sizing agents superior in efficiency and price to the rosin type sizing agents. Such agents are water-soluble salts of alkenyl succinic acids which are made from highly branched olefins and malefic android.
The paper sizing process using water-soluble salts of alkenyl succinic acids as internal sizing agents has been well-known as described in Japanese Patent Publication No. 565/65 (corresponding to US. Patent 3,139,373).
In this Publication, it is described that water soluble salts of alkenyl succinic acids have an alkenyl group having 8 to 15 carbon atoms and those having an alkenyl group having 16 or more carbon atoms cannot afford a satisfactory sizing efficiency. Presently, there is no known sizing agent which is the water soluble salt of alkenyl succinic acid which has an alkenyl group having 16 or more carbon atoms or-a sizing agent containing this salt and which shows a sizing efficiency superior to the rosin type sizing agent.
Water-soluble salts of alkenyl succinic acids have been said to have a problem in practical use due to foaming as described in Japanese Patent Publication (unexamined) No. 27003/79. The present inventors have found that the foam is formed only when the sizing agent is obstructed from fixing on pulp during sizing and the us-fixed water-soluble salt of alkenyl succinic acid or a reaction product of alkenyl succinic acid with aluminum sulfate remains in a pulp slurry. Thus, the present inventors found that when fixing proceeds normally, there is no problem in practical use since there is almost no foaming. The undesirable obstruction to fixing of the sizing agent on pulp is herein referred to as "fixing obstruction".
However, though the obstruction to fixing of the sizing agent in the paper making process is a rare phenomenon, the foaming phenomenon caused by the unfixed sizing agent consisting of the water-soluble salt of alkenyl succinic acid causes serious damage to the process and the quality of the produced paper.
In this way, conventionally, when the water soluble salt of the reaction product of the monoolefin with malefic android was used as a sizing agent, the principal object was only the sizing efficiency.
Accordingly, this resulted in attention only being given to the relationship of the number of carbon atoms in the monoolefin used as raw material with the sizing efficiency.
However, the relationship of its structure with the sizing efficiency andthefoaming nature was not investigated.
Therefore, foaming problems were often caused during actual use as a sizing agent. Further, there were caused problems that satisfactory results could not be obtained when a ~224598 l monoolefin having 16 or more carbon atoms was used as raw material.
SUMMARY OF THE INVENTION
The present inventors carried out studies related to the relationship between the molecular structure of manliness used as raw materials and the sizing efficiency and foaming nature. These studies were carried out in order to develop a synthesized sizing agent which shows a sizing efficiency superior to the rosin type sizing agent and hardly foams even if it receives a fixing obstruction during use. As a result the present inventors have found that the sizing efficiency and foaming nature of the water soluble salt of alkenyl succinic acid remarkably depend on the macular structure of the olefin used as raw material, particularly, the condition of branching which is represented by a value of an average ratio of the number of ethylene groups to that of methyl groups According to the present invention there is provided a paper composition including a sizing agent comprising a water soluble salt obtained by a process comprising the steps of carrying out a thermal addition reaction of malefic android with a monoolefin having 16 to 24 carbon atoms and a ratio of the number of ~$~
1;~24598 - pa -1 ethylene groups (-SHEA-) to methyl groups (-SHEA of 0.9 or more or a mixture of monoolefins having 16 to 24 carbon atoms and an average ratio of the number of ethylene groups to methyl groups of O r or more;
and subjecting the reaction product to alkali saponification to obtain the water soluble salt.
More surprisingly the present inventors have .
found that even a monoolefin containing 16 or more carbon atoms (which was conventionally considered to be unsuitable as raw material for a sizing agent as it could not afford a satisfactory sizing efficiency) could be used as raw material for a sizing agent when the average ratio of the number of ethylene groups to that of methyl groups is OWE
or more. The present inventors found that such a monoolefin can afford a homogeneous transparent sizing agent by alkali saponification of a reaction product which is obtained by the thermal addition reaction with malefic android. Such a sizing agent causes substantially no foaming even when receiving a fixing obstruction and has a sizing efficiency superior to the rosin type sizing agent over a wide range of addition amounts.
In addition to this, as a result of further-studies based on the knowledge obtained from these results, the present inventors have found that a water soluble salt (A) which is obtained by alkali saponification of a reaction product obtained by reacting a monoolefin (having 16 to 24 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more) or a mixture thereof with malefic android reduces foaming without reducing the sizing efficiency when it is mixed with a conventional paper sizing agent which readily causes foaming when it receives a fixing obstruction.
1~:24598 The sizing agent containing the water soluble salt (A) related to this invention was developed as a result of clarifying the relationship of the foaming nature and sizing efficiency in using a sizing agent with the molecular structure of the olefin used as raw material.
This relationship was not previously known. The present invention is a paper sizing agent containing the water soluble salt (A) which is obtained by alkali saponification of a reaction product obtained by thermal addition reaction of a monoolefin having 16 to 24 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more, or the mixture thereof.
The monoolefins having 16 or more carbon atoms were previously considered to be unsuitable as raw material for a paper sizing agent consisting of a water soluble salt of alkenyl succinic acid. The sizing agent of the present invention not only shows a sizing efficiency superior to the rosin type sizing agent over a wide range of addition amounts but also causes substantially no foaming when receiving a fixing obstruction.
DETAILED DESCRIPTION OF THE INVENTION
The oligomer having 16 or more carbon atoms (which is obtained by polymerization of a monoolefin such as propylene, battalion and the like or a mixture thereof in the presence of an acid catalyst such as phosphoric acid, . - 6 -i2~4598 and the like or a Friedel-Crafts catalyst such as aluminum chloride and the Lucas generally known to have a highly branched structure, and the average ratio of the number of ethylene groups to that of methyl groups is generally less than 0.9 The sizing agent obtained from a malefic android adduce of such a highly branched oligomer having 16 or more carbon atoms is not preferable for purposes of this invention because the sizing efficiency is insufficient.
Contrary to this, the oligomer having 16 or more carbon atoms which is obtained by polymerization of a monoolefin such as propylene, battalion, Helene, octane and the like or a mixture thereof in the presence of, for example, an organic aluminum type catalyst has a structure less branched than that of the oligomers obtained by the acid catalyst mentioned above, and the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more.
As already mentioned above, the monoolefin or monoolefin mixture in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more and the number of carbon atoms is 16 to I preferably 16 to 20, can be suitably used for the purposes of this invention as paper sizing agent for all types of paper.
A monoolefin having 25 or more carbon atoms or the mixture thereof is not preferable because the reaction 1 product obtained from reacting it with malefic android does not easily afford a homogeneous aqueous solution by alkali saponification and the obtained sizing agent cannot afford a satisfactory sizing effect though it shows a low foaming nature.
Examples of the monoolefin or monoolefin mixture used in this invention in which the number of carbon atoms is 16 to 24 and the average ratio of the number of ethylene groups to methyl groups is 0.9 or more include oligomers obtained by polymerization of a monoolefin having 3 to 8 carbon atoms such as propylene, battalion, Helene, octane and the Lowe or a plurality thereof, straight chain inner olef.ins obtained by dehydrogenation of n-paraffin and the like - and straight chain ~-olefins obtained by polymerization of ethylene and the like/ and mixtures thereof ~11 of the sizing agents obtained from these monoo:Lefin$
or monoolefin mixtures causes little foaming when receiving a fixing obstruction. The oligomers of n-butylene or straight chain inner olefins are preferably used due to the particularly excellent sizing efficiency.
It is also possible to use a monoolefin mixtures prepared by mixing the monoolefins having 16 to 24 carbon atoms which has the average ratio of the number of ethylene groups to that of methyl groups of 0.9 or more with those having the average ratio of 0.9 or less. In this case, the thus prepared monoolefin mixture must be adjusted so that 1~245g8 the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more.
On the other hand, a monoolefin or monoolefin mix-lure in which the average ratio of the number of ethylene groups to that of methyl groups is 22 or more is not suit-able for the purposes of this invention because they are composed of a monoolefins having 25 or more carbon atoms.
Therefore, the average ratio of number of ethylene groups to that of methyl groups is preferably 0.9 or more and less than 22.
The reaction product of a monoolefin or mixture thereof with malefic android used in this invention can be obtained by thermal addition reaction of the monoolefin with malefic android in the absence of catalyst. The no-action is preferably carried out in an inert atmosphere swishes nitrogen under atmospheric or some increased pressure, at 180 to 250C, more preferably at 200 to 230C, followed by reacting at the same temperature for 1 to 30 hours, preferably for 3 to 20 hours. The mow ratio of the moo-olefin to the malefic android is not necessarily limited but is preferably used in an amount of 0.5 to 3 mow per mow of monoolefin. After the reaction is over, the us-reacted monoolefin and the malefic android are removed by distillation to afford a liquid reaction product having rather low viscosity. The saponification value (JIG K 5902) of the reaction product is about 250 to 350. Depending on the reaction conditions, a small amount of by-products may _ g _ i224598 be formed. The by-products can be removed as distillation residue by distillation under reduced pressure, but the amount of by-product is small and its removal is not alleges required, The reaction product thus obtained is saponified by alkali and made a transparent solution to afford the sizing agent of this invention, Examples of the alkali used for saponification in this invention include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like, ammonia, or water soluble amine such as trimethylamine, diethylamine and the lice, but the use of sodium hydroxide or potassium hydroxide is desirable. The amount of alkali used for saponification is 0.8 to 1.2 times, preferably 0.9 to 1.1 times, the amount corresponding to the saponification value of the reaction product of the monoolefin with malefic ashy-drive. The foaming nature of the obtained sizing agent in-creases with the decrease of the amount of alkali, and when the amount is Less than 0.8 times the amount corresponding to the saponification value, the foaming increases rather substantially though the sizing effect is little influenced, The sizing agent related to this invention can be obtained by reacting a monoolefin or monoolefin mixture having 16 to 24 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more with malefic android and saponifying the resulting reaction product independently or saponifying 1~2~sg~
after mixing it with the other substance such as rosin or a reaction product of a monoolefin or monoolefin mixture having 15 or less carbon atoms with malefic android.
They can be mixed after saponification. The sizing agent can also be obtained by reacting the monoolefin or moo-olefin mixture used in this invention with malefic android after mixing with a monoolefin or monoolefin mixture having 15 or less carbon atoms and saponifying the obtained reaction product.
The water soluble salt (A of the malefic android adduce of the monoolefin or monoolefin mixture having 16 to 24 carbon atoms in this invention is desirably present in an amount of 10% by weight or more in the effective component of the sizing agent. The more the proportion occupied in the effective component of the sizing agent increases, the larger the restraining effect on foaming when it receives a fixing obstruction during use. However, even if the amount is less than 10% by weight, the restraining effect on foaming can be exhibited.
The sizing agent related to this invention can be added to a paper stock in the same manner as that of the conventional rosin type sizing agent. For example, it can be fixed on a pulp by adjusting the pi to about 4.0 to 5.5, preferably 4.2 to 5.0, by adding aluminum sulfate after adding the sizing agent related to this invention to 1~24598 a pulp slurry which is in or after the beating process.
The agent of this invention can be used together with other sizing agents such as a conventional rosin type sizing agent, a petroleum resin sizing agent and the like in any ratio, and may also be used for surface sizing.
In case of internal sizing, the amount (addition amount) of the sizing agent used in this invention is in the range of 0.01 to 5.0% by weight, preferably 0.05 to 3.0% by weight, based on the weight of the dry pulp. When surface sizing is carried out the sizing agent is coated in an amount of 0.005 to 0.5 g/m2 on a dry weigh basis.
As explained in the above, even a monoolefin or monoolefin mixture having 16 or more carbon atoms which was conventionally said not to afford a satisfactory sizing agent in the case of reacting it independently with malefic android can afford a paper sizing agent showing an excellent sizing efficiency and a low foaming nature. This good results are made possible by selecting a monoolefin or monoolefin mixture in which the average ratio of the number of ethylene groups to that of methyl groups is 0.9 or more.
The sizing agent of this invention is not only superior to the rosin type sizing agent over a wide range of addition amounts but it also remarkably restrains the foaming in receiving a fixing obstruction.
The characteristics of the sizing agent related . - 12 -1~4598 to this invention are explained above, and this invention is further specifically illustrated by the following Comparative Examples and Examples. However, the scope of the invention is not limited to these examples. The average ratio of the number of ethylene groups to that of methyl groups in the Comparative Examples and Examples are measured by the nuclear magnetic resonance spectral method.
COMPARATIVE EXAMPLE
A mixture of 250 parts by weight of propylene oligomers having 8 to 10 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups was 0.80 and 200 parts by weight of malefic android were heated to 215C in an autoclave under nitrogen atmosphere and reacted for 3 hours in the absence of catalyst. After the reaction was over, the reaction mixture was taken out and the unrequited oligomers and malefic android were removed by distillation under reduced pressure to afford 294 parts by weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 502.
The potassium hycLroxide corresponding to the specification value of the reaction product and water were added to the obtained reaction product, and the mixture was stirred at 90C for 2 hours and saponified to give a transparent sizing agent containing 40~ by weight of the solid component (Sizing agent A). The pi of this sizing agent was 10.1.
I
A mixture of 332 parts by weight of propylene oligomers having 16 to 21 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups was 0.87 and 166 parts by weight of malefic android were reacted in the same manner as described in Comparative Example 1 and the unrequited reactants were removed to afford 194 parts by weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 320.
This product was saponified in the same manner as described in Comparative Example 1 and adjusted so as to have 40 % by weight of the solid component. However, the product was in an emulsion state and could not afford a homogeneous trays-parent sizing agent. The pi of this emulsified sizing agent (Sizing agent B) was 10.1.
EXAMPLE
A mixture of 230 parts by weight of n-butylene oligomers having 16 to 20 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups was 0.93 and 100 parts by weight of malefic android were reacted in the same manner as described in Comparative Example 1. Unrequited reactants were removed to afford 159 parts by weigh-t of a reaction product. The saponification value of this reaction product was 350. This product was saponified in the same manner as described in Comparative 1~2459~
Example 1 to give a transparent sizing agent related to this invention containing OWE by weight of the solid component (Sizing agent C). The pi of this sizing agent was 10.1.
225 parts by weight of a straight chain inner olefin having 16 carbon atoms with the average ratio of the number of ethylene groups to that of methyl groups being 6.1 and 100 parts by weight of malefic android were reacted in the same manner as described in Comparative Example 1.
Unrequited reactants were removed to afford 156 parts by weight of a yellowish brown oily reaction product.
The saponification value of this reaction product was 352.
This product was saponified in the same manner as described in Comparative Example 1 to give a transparent sizing agent related to this invention containing 20% by weight of the solid component sizing agent D). The pi of this sizing agent was 10Ø
20 parts by weight of the reaction product obtained in Example 1 and 80 parts by weight of the reaction product obtained in Comparative Example 1 were mixed.
The saponification value of this mixture was 472. This was saponified in the same manner as described in Comparative Example 1 to afford a transparent sizing agent related to 1~24598 this invention containing 40% by weight of the solid component (Sizing agent E). The pi of this sizing agent was 10.1.
50 parts by weight of Sizing agent C obtained in Example 1 and 50 parts by weight of Sizing agent A obtained in Comparative Example 1 were mixed to give a transparent sizing agent related to this invention containing 40% by weight of the solid component (Sizing agent F). The pi of this sizing agent was 10.1.
40 parts by weight of Sizing agent D obtained in Example 2 and 80 parts by weight of Sizing agent A obtained in Comparative Example 1 were mixed and water was added thereto to afford a transparent sizing agent related to this invention containing 30% by weight of the solid component (Sizing agent G). The pi of this sizing agent was 10.1.
With respect to the sizing agents A and B obtained in the above-mentioned Comparative Examples 1 to 2 and the sizing agents C, D, E, F and G obtained in Examples 1 to 5, the sizing test was carried out. As a sizing agent for comparison, a commercial reinforced rosin sizing agent (RF Size 880 L-50 manufactured by Hymen Industry Co.) was 1~:24598 used. The testing method is as follows.
A 3% slurry of hardwood bleached raft pulp which was adjusted to the beating degree C.F.=400 cc was prepared and to this slurry was added Sizing agent A, Sizing agent s, Sizing agent C, Sizing agent D, Sizing agent E, Sizing agent F, Sizing agent G or the reinforced rosin sizing agent in an amount of 0.2% by weight, 0.5%
by weight or 1% by weight as solid component based on the weight of dry pulp and aluminum sulfate was added with stirring to make the pi of the slurry 4.5. The pulp slurry was diluted with water adjusted to pH-S.0 by aluminum sulfate to make the pulp concentration about 0.2~ by weight.
The pulp was made into paper by a TAIPEI standard sheet machine according to the general method and after pressing for dehydration (4 kg/cm2 x 1 mix), the wet paper was dried by a rotary dryer at 105~C for 3 minutes. The basis weight of this hand-made paper was 60 g/m2.
The obtained paper was allowed to stand in a room at 20~C and 65% humidity for 24 hours, and then the sizing degree was measured by JIS-P-8112 Stockigt sizing degree testing method. The results are summarized in Table 1.
Next, in order to examine the foaming under the conditions in which the pulp slurry concentration was low and the sizing agent could easily receive the fixing 12~459B
obstruction, a 0. owe by weight of slurry of hardwood bleached raft pulp which was adjusted to a beating degree C.F.=400 cc was added with Sizing agent A, Sizing agent B, Sizing agent C, Sizing agent D, Sizing agent E, Sizing agent F, Sizing agent G or the reinforced rosin sizing agent in an amount of 0.5~ by weight (as solid component) based on the weight of dry pulp, and aluminum sulfate was added to make the pi of the pulp slurry 4.5. Then 500 ml of this pulp slurry was put in lo a l of Erlenmeyer flask and sealed. It was attached to a horizontal reciprocating shaker (Shaking frequency 156 shaking/min, Amplitude 70 mm) and shook for l minute.
The volume of foam in the pulp slurry was then measured by the Broadway bubble measuring scale (Pulp and Paper Engineering, Vol. 2, No. 11, p. 22). The results are summarized in Table 1.
1~:24598 Table Stockigt Sizing Foam Content Sizing Agent Degree (sea) (I by volume) o _ 0.5* 1.0* 0.5 A (Coup. Example 1) 15.3 28.5 32.8 0.52 B ( " 2) 0 2.0 6.2 0.05 C (Example 1) 19.0 29.8 33.7 0.02 D ( " 2) 15.8 28.5 32.5 0.02 E ( " I 16.0 28.6 33.0 0.25 F ( " 4) 17.5 30.0 33.5 0.12 G ( " 5) 15.5 28.5 33.0 0.24 Reinforced Rosin 9.1 23.1 31.6 0.31 Sizing Agent Note: "*": Addition amount of sizing agent (% by weight) Sizing agent A in the examples obtained from the propylene oligomer mixture having 8 to 10 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 0.80 shows a sizing effect superior to the reinforced rosin sizing agent. However, the foaming amount in receiving a fixing obstruction is larger than that of the reinforced rosin sizing agent. In the emulsi-fled sizing agent B in this example obtained from the mixture of propylene oligomers having 16 to 21 carbon atoms in which the average ratio of the number of ethylene groups to that ~459~3 of methyl groups is 0.87, the amount of the foaming is less than that of the reinforced rosin sizing agent.
However, the sizing effect is apparently substantially inferior to the reinforced rosin sizing agent.
On the contrary, Sizing agent C obtained from the oligomer mixture of n-butylene in which the average ratio of the number of ethylene groups to that of methyl groups is 0.93 and Sizing agent D obtained from the straight chain inner olefin having of 16 carbon atoms in which the average ratio of the number of ethylene groups to that of methyl groups is 6.1 which are related to this invention show not only a sizing effect superior to the reinforced rosin sizing agent over a wide range of addition amount but also substantially less foaming than that of the reinforced rosin sizing agent.
Sizing agent E of this invention obtained by mixing the reaction product obtained in Comparative Example 1 with the reaction product obtained in Example 1 followed by saponification, and Sizing agents F and G obtained by saponification followed by mixing show an excellent efficiency superior to the reinforced sizing agent over a wide range of addition amounts and at the same time the foaming when receiving a fixing obstruction is suppressed.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled ion the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (14)
1. A paper composition including a sizing agent comprising a water soluble salt obtained by a process comprising the steps of carrying out a thermal addition reaction of maleic anhydride with a monoolefin having 16 to 24 carbon atoms and a ratio of the number of methylene groups (-CH2-) to methyl groups (-CH3) of 0.9 or more or a mixture of monoolefins having 16 to 24 carbon atoms and an average ratio of the number of methylene groups to methyl groups of 0.9 or more;
and subjecting the reaction product to alkali saponi-fication to obtain the water soluble salt.
and subjecting the reaction product to alkali saponi-fication to obtain the water soluble salt.
2. A paper composition including a sizing agent as claimed in claim 1, wherein the water soluble salt comprises 10% by weight or more of the effective component of the sizing agent.
3. A paper composition including a sizing agent as claimed in Claim 1 or 2, wherein the monoolefin or mixture thereof is an oligomer obtained from a monoolefin having 3 to 8 carbon atoms or a plurality of said monoolefins.
4. A paper composition including a sizing agent as claimed in Claim 1 or 2, wherein the monoolefin or mixture thereof is a straight chain inner olefin.
5. A paper composition including a sizing agent as claimed in Claim 1 or 2, wherein the monoolefin or mixture thereof is an oligomer of n-butylene.
6. A paper composition including a sizing agent as claimed in Claim 1 or 2, wherein the monoolefin or mixture thereof contains 16 to 20 carbon atoms.
7. A paper composition including a sizing agent as claimed in Claim 1, wherein the monoolefin mixture is a mixture of monoolefins having 16 to 24 carbon atoms consisting of monoolefins having an average ratio of the number of methylene groups to methyl groups of 0.9 or more and monoolefins having an average ratio of the number of methylene groups to methyl groups of 0.9 or less, the monoolefins being present in a mixture such that the average ratio of the number of methylene groups to methyl groups is 0.9 or more.
8. A paper composition including a sizing agent as claimed in Claim 1 or 2, wherein the average ratio of the number of methylene groups to methyl groups is in the range of 0.9 or more and less than 22.
9. A paper composition including a sizing agent as claimed in Claim 1 or 2, wherein the addition reaction is carried out at a temperature in the range of 180°C to 250°C for a period of time of 1 to 30 hours.
10. A paper composition including a sizing agent as claimed in Claim 1 or 2, wherein the addition reaction is carried out in an atmosphere of inert gas.
11. A paper composition including a sizing agent as claimed in Claim 1 or 2, wherein the amount of maleic anhydride is 0.5 - 3 mole per mole of monoolefin.
12. A paper composition including a sizing agent as claimed in Claim 1, wherein the alkali saponification is carried out utilizing an alkali in an amount in the range of 0.8 to 1.2 times the amount of alkali estimated as necessary from the saponification value of the reaction product.
13. A paper composition including a sizing agent as claimed in Claim 12, wherein the alkali saponification is carried out utilizing alkali in an amount in the range of 0.9 to 1.1 times the amount estimated as necessary from the saponification value of the reaction product.
14. A method of sizing paper comprising incorporating a sizing agent comprising a water soluble salt obtained
14. A method of sizing paper comprising incorporating a sizing agent comprising a water soluble salt obtained
Claim 14 continued...
by a process comprising the steps of carrying out a thermal addition reaction of maleic anhydride with a monoolefin having 16 to 24 carbon atoms and a ratio of the number of methylene gropus (-CH2-) to methyl groups (-CH3) of 009 or more or a mixture of monoolefins having 16 to 24 carbon atoms and an average ratio of the number of methylene groups to methyl groups of 0.9 or more; and subjecting the reaction product to alkali saponification to obtain the water soluble salt into the paper composition during the paper making process.
by a process comprising the steps of carrying out a thermal addition reaction of maleic anhydride with a monoolefin having 16 to 24 carbon atoms and a ratio of the number of methylene gropus (-CH2-) to methyl groups (-CH3) of 009 or more or a mixture of monoolefins having 16 to 24 carbon atoms and an average ratio of the number of methylene groups to methyl groups of 0.9 or more; and subjecting the reaction product to alkali saponification to obtain the water soluble salt into the paper composition during the paper making process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17513/83 | 1983-02-07 | ||
| JP1751383A JPS59144695A (en) | 1983-02-07 | 1983-02-07 | Papermaking size agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1224598A true CA1224598A (en) | 1987-07-21 |
Family
ID=11946045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000446416A Expired CA1224598A (en) | 1983-02-07 | 1984-01-31 | Paper sizing agent |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS59144695A (en) |
| CA (1) | CA1224598A (en) |
| DE (1) | DE3404068A1 (en) |
| FR (1) | FR2540507B1 (en) |
| GB (1) | GB2137614B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4489120A (en) * | 1983-08-12 | 1984-12-18 | Hollinger Jr William K | Archival container construction material |
| CA2114816A1 (en) * | 1993-02-03 | 1994-08-04 | Shigeto Hatanaka | Sizing agent for papermaking |
| DE102005055541A1 (en) * | 2005-11-18 | 2007-05-24 | Basf Ag | Alkenylsuccinic anhydrides from oligomers of C4 to C8 olefins and maleic anhydride, process for their preparation and their use |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB954901A (en) * | 1960-11-22 | 1964-04-08 | Shell Res Ltd | A process for the production of substituted carboxylic acids |
| US3139373A (en) * | 1962-06-08 | 1964-06-30 | Allied Chem | Process for the internal sizing of paper with a salt of a substituted succinic acid |
| DK130417A (en) * | 1968-08-08 | |||
| BE791320A (en) * | 1971-11-18 | 1973-05-14 | Unilever Nv | TENSIO-ACTIVE COMPOUNDS |
| JPS5281111A (en) * | 1975-12-26 | 1977-07-07 | Mitsubishi Oil Co | Sizing method of paper surface |
| JPS5328526A (en) * | 1976-08-30 | 1978-03-16 | Nippon Kokan Kk | Process and apparatus for producing steel pipe having zenccplated outer surface |
| JPS5427003A (en) * | 1977-08-03 | 1979-03-01 | Nippon Oil Co Ltd | Sizing agent for paper making |
| US4302283A (en) * | 1978-01-16 | 1981-11-24 | Ethyl Corporation | Sizing process and composition |
| DE2804202A1 (en) * | 1978-02-01 | 1979-08-02 | Basf Ag | METHOD OF SIZING PAPER |
| FI803358L (en) * | 1979-11-23 | 1981-05-24 | Basf Ag | FOERFARANDE FOER MASSALIMNING AV PAPPER |
| JPS57154495A (en) * | 1981-03-19 | 1982-09-24 | Mitsubishi Petrochemical Co | Papermaking size agent |
-
1983
- 1983-02-07 JP JP1751383A patent/JPS59144695A/en active Pending
-
1984
- 1984-01-31 CA CA000446416A patent/CA1224598A/en not_active Expired
- 1984-02-06 DE DE19843404068 patent/DE3404068A1/en not_active Withdrawn
- 1984-02-06 GB GB08403085A patent/GB2137614B/en not_active Expired
- 1984-02-07 FR FR8401853A patent/FR2540507B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59144695A (en) | 1984-08-18 |
| GB8403085D0 (en) | 1984-03-07 |
| FR2540507B1 (en) | 1988-04-15 |
| DE3404068A1 (en) | 1984-08-09 |
| GB2137614A (en) | 1984-10-10 |
| FR2540507A1 (en) | 1984-08-10 |
| GB2137614B (en) | 1986-12-03 |
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