JPS61266699A - Self-emulsifiable size composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application J] The present invention relates to a sizing composition for paper manufacturing. More specifically, the present invention relates to an internally added size agent composition that is suitable for neutral papermaking and has excellent self-emulsifying properties.

[Prior Art] As a sizing agent for paper manufacturing, a sizing agent manufactured from natural rosin or modified rosin, particularly a so-called reinforced rosin sizing agent obtained by saponifying the maleic acid-added proboscis of ronone, has been widely used. These sizing agents are employed in the acid sizing method, which is fixed by sulfuric acid bands.

However, the use of sulfuric acid, which is an essential component, lowers the pH of the papermaking system, resulting in corrosion of papermaking equipment and disadvantages in that the strength and durability of the resulting paper is reduced. Furthermore, because it is difficult to use inexpensive alkaline fillers such as calcium carbonate, it has not been possible to expect a significant reduction in paper production costs.

In order to solve the drawbacks of the acidic sizing method, research has been conducted on a neutral papermaking method that does not use sulfuric acid, and a so-called neutral sizing agent that provides excellent sizing effects to paper under papermaking conditions in the neutral region has been developed. Proposed. For example,
A sizing agent containing a cyclic dicarboxylic acid anhydride described in Japanese Patent Publication No. 05, a sizing agent consisting of a maleic anhydride adduct of an internal olefin described in Japanese Patent Publication No. 53-28526,
Examples include a sizing agent comprising a substituted dicarboxylic anhydride, a polyoxyfulkylene compound, and water described in Japanese Patent Publication No. 53-36044.

However, as is clear from the description in Japanese Patent Publication No. 53-38044, the sizing agents described in Japanese Patent Publication No. 39-2305 and Japanese Patent Publication No. 53-28528 contain the dicarboxylic anhydride in water. There are many restrictions for dispersion. That is, protective colloids, which are suspending agents such as cationized starch, gelatin, and polyvinyl alcohol, must be included as essential ingredients.
Moreover, it can only be dispersed in water by using a specific strong stirring device such as a high-speed shaker, mechanical homogenizer, or ultrasonic homogenizer.

On the other hand, Japanese Patent Publication No. 53-36044 discloses that by using a polyoxyalkylene compound as a surfactant in the substituted dicarboxylic anhydride, the turbidity step using the strong stirring device can be omitted. ing.

That is, using the surfactants described in the same publication, such as polyoxyalkylene alkyl ether and polyopylene dialkylene furkylaryl ether, the dicarbonyl Il
! When suspending the anhydride, it is sufficient to simply pass it through an aspirator or a 17th chamber without high-speed stirring.

However, when a substituted dicarboxylic acid anhydride and the furkyl or 717-lether type surfactant are mixed and left to stand, the dispersibility of the mixture in water decreases over time, and the size effect also decreases accordingly. Tend.

On the other hand, when the polyoxyalkylene furkyl diester described in the same publication is used, the decrease in the size effect over time due to leaving is not observed when the above-mentioned furkyl or aryl ether type surfactants are used. However, since the alkyl group originally has a large number of carbon atoms and is highly hydrophobic, it has the disadvantage that it is difficult to easily disperse in water by simple mixing and agitation.

As mentioned above, none of the dispersants described in this publication can be suitably used.

[Problem to be solved by the invention 1 Conventionally known neutral sizing agents such as Ekigami have poor performance such as dispersibility in water, oral dispersion stability, Cy-X effect, and low foaming properties. However, acidic papermaking methods using the above-mentioned reinforced ronone sizing agent are still the mainstream.

In view of the current situation, the present inventors have conducted intensive studies to develop a neutral sizing agent that is comparable to the reinforced non-sizing agent and can be applied to actual equipment. We have discovered that a neutral sizing agent that can simultaneously satisfy the above-mentioned properties can only be achieved by using a sizing agent.
This led to the completion of the present invention.

[Means for solving the problem] That is, the present invention has (^) general formula (I): +1 (wherein R1 has 9 to 23 carbon atoms, preferably 13 to 19 carbon atoms)
linear or branched substituted succinic anhydride represented by an alkyl group or an alkenyl group) and general (
(2): (wherein, R2 is a straight-chain or branched alkyl group having 1 to 27 carbon atoms, and R' is a straight-chain or branched furkyl group or alkenyl group having 2 to 28 carbon atoms. and R2
and R3 have a total number of carbon atoms of 9 to 29, preferably 13 to 2.
At least one substituted succinic anhydride selected from the group consisting of branched substituted succinic anhydrides represented by 3), and [white space below] (B) General formula (■): i [wherein, A is R 0 + ClICH2O9 or R4COOf C) ICH20+I (where R4
represents an aryl group or a furkyl group having 2 to 6 benzene rings, R4 is a hydrogen atom * or a methyl group, and the upper part represents an integer from 1 to 50), and B and D are the same or different. or H2O- (where %R' is a 7-aryl group having 2 to 6 benzene rings or a fururaryl group, Rγ is a hydrogen atom or a methyl group, n is a!! number from 1 to 50, Ml and 1M2 are the same or different and represent a hydrogen atom, an alkali metal, ± or a 7 ammonium group derived from ammonia or an organic amine)] or a salt thereof as a main component. The present invention relates to a self-emulsifying sizing composition characterized by:

[Example 1] Residues of homopolymer of ethylene oxide, residues of homopolymer of propylene oxide, residues of ethylene oxide and propylene oxide in the general formula (I) described in the claims of the present application The concept includes any residues of copolymers (including random copolymers, block copolymers, etc.).

In the present invention, the substituted succinic acid hydroxide represented by the general formula (1) is prepared by an addition reaction between an a-olefin having a double bond at the terminal or an oligomer thereof and maleic anhydride.

Specific examples of the substituted succinic anhydride include inoctadecenyl succinic anhydride, n-hexadecenyl succinic anhydride, and n-hexadecenyl succinic anhydride. Examples include anhydrides, dodecenylsuccinic anhydride, triisobutenylsuccinic anhydride, etc., and the corresponding saturated substituted succinic anhydrides can be obtained by subjecting these unsaturated substituted succinic anhydrides to a hydrogenation reaction.

The branched substituted succinic anhydride represented by the general formula (Illr) is prepared by an addition reaction between an internal olefin and maleic anhydride.

Specific examples of the substituted succinic anhydride include adducts of internal olefins such as decene-5, dodecene-6, tetofudecene-7, hexadecene-7, octadecene-9, and eifsen-11 and maleic anhydride; Further, by subjecting these unsaturated substituted succinic anhydrides to a hydrogenation reaction, corresponding saturated substituted succinic anhydrides can be obtained.

The reaction between the a-olefin insect or internal olefin and maleic anhydride is carried out in the presence or absence of a catalyst, preferably under an inert atmosphere, at normal pressure or under pressure.The reaction temperature is 180 to 250°C. , preferably 190-220
℃, and the reaction time is 1 to 50 hours, preferably 10 to 3 hours.
It is better to set it to 6 hours.

The molar ratio of olefins to maleic anhydride is not particularly limited, but it is usually appropriate that the ratio is 0.4 to 2 moles, preferably 0.8 to 1.3 moles, of maleic anhydride per mole of olefins. .

After the reaction is completed, unreacted olefins and maleic anhydride are removed by distillation, thereby allowing the substituted succinic anhydride to be extracted.

The specific dispersant essential to the present invention has the general formula (I
[Limited to phosphoric acid esters or salts thereof shown in parentheses. Such a dispersant can be produced, for example, as follows. That is, it can be handled by addition-polymerizing at least one of ethylene oxide or propylene oxide to aryl 7 ether or furkylarylphenol having 2 to 6 benzene rings, and then adding phosphorus oxychloride to perform esterification. It is possible to obtain a phosphoric ester salt by adding various neutralizing agents to this material to form a salt.

Examples of phenols that serve as starting materials for the dispersant include:
The following types are listed.

a) Ortho, meta, para phenylphenol; α, β-
b) Benzylated products of phenol and alkylphenol, more specifically c) styrylated products of phenol and alkyl 7-enol, more specifically d) benzylated products of phenyl-7enol, more specifically He) is an arylphenol such as s7thole or a styryl compound of phenylphenol, or an alkyl7lylphenol.

It is necessary that the dispersant does not contain alcoholic hydroxyl groups and has appropriate hydrophilicity.

That is, substituted amber I of the general formula CI) and (or) (■)! ! ! Even if the anhydride and the dispersant are mixed and left for a long time, the anhydride ring of the substituted succinic acid does not open and is chemically stable, so the dispersibility of the mixture in water does not change over time. *This dispersant has moderate hydrophilicity, so it has excellent self-emulsifying properties, and it can be used in a smaller amount than conventionally known dispersants such as polyoxyalkylene alkyl ether or polyoxyalkylene furkyl 7-aryl ether. , it is possible to improve defects such as foaming, which were problems when applied to conventional actual equipment.

An anionic metal salt type emulsifier comprising dodecylbenzenesulfonic acid or lauryl sulfate and at least one metal selected from potassium, sodium, and calcium can also be used in combination with the dispersant of the present invention.

The paper making method using the self-emulsifying sizing agent of the present invention as described above usually involves dispersing the SaiX agent in water in advance or injecting the sizing agent and water in proportion at the time of use. This can be done by adding a predetermined amount to the pulp slurry. In addition, various cationic compounds such as polyethyleneimine resin, cationic polyacryl 7mide resin, cationic polyamide polyamine tMm, cationic starch derivatives, etc. can be used to further improve the fixability to pulp.

Next, the present invention will be explained in more detail by referring to Reference Examples and V Examples, but the present invention is not limited to these Examples.

Reference Example 1 Addition reaction of maleic anhydride to a branched a-olefin having 14 carbon atoms! Alkenyl succinic anhydride was obtained by s.

Reference Example 2 An alkenylsuccinic anhydride was obtained by subjecting a branched a-olefin having 20 carbon atoms to an addition reaction with maleic anhydride.

Reference Example 3 Alkenylsuccinic anhydride was obtained by addition reaction of maleic anhydride to tetradecene-7.

Reference Example 4 Alkenylsuccinic anhydride was obtained by addition-reacting maleic anhydride to Eifsen-11.

Reference Example 5 Flukenylfuhaku Wl anhydride was obtained by subjecting octadecene-9 to an addition reaction with maleic anhydride.

Example 1 Alkenylsuccinic anhydride i obtained in Reference Example 1.

Phosphate ester dispersant 1 shown in Table 1 below for i
(After mixing, add 1g of the mixture to 100z
The sample was collected in a sample bottle, 881F water was added thereto, and the mixture was lightly shaken by hand to form an emulsifier to obtain a sizing agent.

Examples 2 to 14 Various sizing agents were obtained by dimarque conversion in the same manner as in Example 1, except that the substituted succinic anhydride and dispersant used were changed to those shown in Table 1.

The self-emulsifying properties of the CyX agents obtained in Examples 1 to 14 above were examined immediately after Sta and 7 days later, and the results are shown in Table 1.

The size effect of the infested sizing agent was determined by the above test method, and the results are shown in Table 1.

(Size performance test) The valve (L-BKP) was
The slurry was beaten to a 1% aqueous slurry with a 7-thickness of 450 il. A polyamide polyamine resin (Arafix 100, manufactured by Arayo Kagaku Kogyo Co., Ltd.) was added to the slurry as a fixing agent.
Add 0.3% (in terms of solid content) to the bulb, and further add 0.2 or 0.5% (in terms of solid content) of the sizing agent obtained in this example to the bulb to uniformly Dispersed.

The resulting slurry was made into paper using a Tappi Standard Sheet Machine to a paper size of 1,609±1,171 tsubo. The resulting wet paper was then compressed and dehydrated, dried at 100°C for 1 minute, and then conditioned at a relative humidity of 65% for 24 hours.
Then, each size degree (seconds) is calculated using the Stekicht method.
was measured.

(Foaming property test) The various emulsion polishes prepared in this example were mixed with deionized water.
JIS K 33 for the diluted solution obtained by diluting to %
The height (mm) of the bubbles produced was measured in accordance with 82.

[Effects of the Invention] As described above, the self-emulsifying sizing agent composition of the present invention has excellent dispersibility in water, dispersion stability over time, size effect,
It has the effect of having various performances such as low foaming property.

Claims (1)

[Claims] 1(A) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 represents an alkyl group or an alkenyl group having 9 to 23 carbon atoms. ) Linear or branched substituted succinic anhydride and general formula (II): ▲Mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^2 is a carbon number of 1 to 27 A straight chain or branched alkyl group, R^3 represents a straight chain or branched alkyl group or alkenyl group having 2 to 28 carbon atoms, and the total number of carbon atoms of R^2 and R^3 is 9. -29) at least one substituted succinic anhydride selected from the group consisting of branched substituted succinic anhydrides represented by: ▼(III) [In the formula, A is ▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲There are mathematical formulas, chemical formulas, tables, etc.▼(Here, R^4 is an aryl group having 2 to 6 benzene rings or an alkylaryl group, R^5 is a hydrogen atom or a methyl group, n is 1
(represents an integer from ~50), B and D are the same or different, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, M^1O- or M^2O- where R^5 is the benzene ring from 2 to 6
Aryl group or alkylaryl group, R^7
is a hydrogen atom or a methyl group, n is an integer from 1 to 50, M^
1 and M^2 are the same or different and represent a hydrogen atom, an alkali metal, or an ammonium group derived from ammonia or an organic amine)] or a salt thereof as a main component. A self-emulsifying sizing agent composition.