JPS5948030B2 - Aqueous emulsion of rosin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous paper-size emulsion, and more particularly to an aqueous paper-size emulsion comprising a rosin material, a phosphoric acid ester emulsifier, and water, the purpose of which is to improve mechanical stability and dilution stability. An object of the present invention is to provide an aqueous emulsion that has excellent properties and exhibits excellent performance as a sizing agent for paper manufacturing.

Aqueous emulsions of rosin substances are already known.

For example, U.S. Pat. No. 3,565,755 discloses dissolving a rosin material in an organic solvent such as benzene and then mixing with an amount of aqueous alkaline solution to neutralize the rosin material;
It is described that a desired aqueous emulsion can be obtained by emulsifying the resulting heterogeneous mixture and further distilling off the organic solvent, and that the aqueous emulsion is used as a sizing agent for paper manufacturing. Also, JP-A-50-43
Publication No. 202 discloses that a rosin substance similar to the above and an aqueous solution of an alkali metal salt of an alkylbenzenesulfonic acid are mixed and emulsified in a heated molten state to obtain an aqueous emulsion of a rosin substance, and that the emulsion is useful as a sizing agent for paper manufacturing. Something is stated. Although these known aqueous emulsions have relatively good performance as paper sizing agents, the stability of the emulsion itself is not satisfactory.

Emulsions for various uses, not just sizing agents, are subjected to mechanical suring, often by pumps, in various steps from manufacture to use. Therefore, it is preferable that such an emulsion has mechanical stability, but the proposed aqueous emulsion is inferior to this stability, and for example, when subjected to mechanical suring, its particles become coarse or in severe cases. , there is a risk that the emulsion will be destroyed and agglomerates will be formed, and great care must be taken when handling them. Moreover, the pumps, transport lines, etc. for transporting Naoyuki emulsion must be frequently cleaned because the above-mentioned aggregates are deposited and adhered thereto. Furthermore, the water used for papermaking comes from rivers, taps, wells, etc., and is often highly hard water.

Therefore, it is preferable that the sizing agent for paper manufacturing has stability in hard water. In addition, it is usually concentrated at a high concentration due to transportation costs, and when used in papermaking, it is necessary to add a very small amount to the aqueous pulp dispersion, or to add it to the aqueous pulp dispersion. To facilitate the diffusion of the sizing agent,
It is usually diluted to a concentration of about 5% by weight. However, the aqueous emulsion of the proposed rosin material has poor dilution stability, especially in hard water. Therefore, it must be uniformly diluted and added to the pulp water-acid solution immediately before use and within a short period of time, and a special dilution device is required for this purpose. The present invention has significantly superior mechanical stability and dilution stability compared to the aqueous emulsions proposed above, and is extremely advantageous in handling when used as a sizing agent for paper manufacturing, and exhibits excellent stability even when diluted with hard water. The present invention provides a new paper-size aqueous emulsion of a rosin material that has high properties and can be used economically. That is, the present invention provides a paper-size aqueous emulsion comprising a rosin substance, an emulsifier, and water, wherein the emulsifier is
The present invention relates to an aqueous emulsion for paper manufacturing size, characterized in that it is a phosphoric acid ester emulsifier selected from phosphoric acid mono- or di-esters and their alkali salts represented by general formula [I] below.

The rosin substance in the present invention is preferably rosin 0-
95% by weight and 5-100% by weight of rosin adduct.

Here, as the rosin, gum rosin, oil rosin, tall oil rosin, modified products thereof, and mixtures thereof can be used. Examples of the above-mentioned modified products include hydrogenated rosin, disproportionated rosin, polymerized rosin, and aldehyde-modified rosin. Among these rosins, aldehyde-modified rosins are particularly preferred because their crystallization is suppressed. This is usually obtained by reacting rosin and 2 to 8% by weight of formaldehyde or acetaldehyde in the presence of an acidic catalyst such as sulfuric acid or para-toluenesulfonic acid at a temperature of about 140 to 200°C for 0.5 to 3 hours. The rosin adduct contains rosin (particularly preferably aldehyde-modified rosin) and 2 to 30% by weight, preferably 3 to 15% by weight of α.
, β-unsaturated carboxylic acid at a temperature of about 150 to 250°C. The α,β-unsaturated carboxylic acids used include acrylic acid, maleic acid, fumaric acid, itaconic acid, anhydrides thereof and mixtures thereof, with fumaric acid, maleic acid and maleic anhydride being particularly preferred. The aqueous emulsion of the present invention is produced by emulsifying the above rosin material in water using a specific phosphoric acid ester emulsifier. In the present invention, the above-mentioned phosphoric acid ester emulsifier has a general formula or a polyhydric alcohol fatty acid partial ester group, and R1 is an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group, a cycloalkyl group, and an alkylcyclo 6 to 24 carbon atoms selected from alkyl groups (
Preferably, R represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 50.

R is R3O-, SR3COO+CHCH, O hand.

, polyhydric alcohol fatty acid partial ester residue or M2O
-, R3 is a hydrocarbon having 1 to 24 carbon atoms (preferably 6 to 22) selected from alkyl groups, alkenyl groups, aryl groups, alkylaryl groups, arylalkyl groups, cycloalkyl groups, and alkylcycloalkyl groups. The group R4 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 50. or M1 and M2 are the same or different and are hydrogen atoms, alkali metals such as lithium, sodium, potassium, etc., ammonia, primary organic amines,
An ammonium group derived from a secondary organic amine or a tertiary organic amine] is used. - Typical phosphoric acid ester emulsifiers to be used include, for example, monoesters represented by the above general formula [1] such as monooctyl phosphate, monononyl phosphate, monodecyl phosphate, monododecyl phosphate, mono- myristyl phosphate,
Monoalkyl phosphates such as monocetyl phosphate, monostearyl phosphate, monoeicosyl phosphate, and monodocosyl phosphate; monoalkenyl phosphates such as monooleyl phosphate; monoaryl phosphates such as monophenyl phosphate; Ester; mono(octylphenyl) phosphate, mono(dodecylphenynol) phosphate, mono(
Mono(alkyl aryl) phosphates such as myristyl phenyl phosphate; mono(arylalkyl) phosphates such as mono(phenylhexyl) phosphate; mono(alkylcyclohexyl) phosphates such as mono(nonylcyclohexyl) phosphate; Examples include phosphoric acid monoesters having only a hydrocarbon group such as (alkyl) phosphate esters, and monothiophosphoric acid monoesters represented by the general formula [1] corresponding to these.

Similarly, as monoesters, mono(polyoxyethylene octyl ether) phosphate ester, mono(polyoxyethylene dodecyl ether) phosphate ester, mono(polyoxyethylene stearyl ether) phosphate ester, mono(polyoxyethylene Mono(polyoxyalkylene alkyl ether) phosphate ester such as oxypropylene cetyl ether) phosphate ester;
Polyoxyethylene octyl phenyl ether) phosphate ester, mono(polyoxyethylene nonylphenyl ether) phosphate ester, mono(polyoxyethylene dodecyl phenyl ether) phosphate ester, mono(polyoxyethylene polyoxy Mono(polyoxyalkylene/alkylaryl ether) phosphate ester such as propylene cetyl phenyl ether) phosphate ester; mono(polyoxyethylene stearyl sulfide)
Mono(polyoxyalkylene alkyl sulfide) phosphoric acid ester such as phosphoric acid ester; Mono(polyion alkylene/alkylaryl sulfide) phosphoric acid such as mono(polyoxyethylene/nonyl phenyl sulfide) phosphoric acid ester Ester; mono(polyoxyalkylene alkyl ester) such as mono(polyoxyethylene dodecyl ester) phosphate ester; mono(polyoxyalkylene alkenyl ester) such as mono(polyoxyethylene polyoxypropylene oleyl ester) phosphate ester; ) Phosphoric acid ester; Phosphoric acid having a polyoxyalkylene chain with a degree of polymerization of 1 to 50, such as mono(polyoxyalkylene alkylaryl ester) phosphoric ester such as mono(polyoxyethylene/decyl phenyl ester) phosphoric ester Monoesters or monothiophosphoric acid monoesters represented by the general formula [1] corresponding to these and the like can be mentioned. Furthermore, monoesters are
For example, phosphoric acid monoesters of polyhydric alcohol fatty acid partial esters such as phosphoric acid monoesters of stearic acid diglyceride are included. In addition, the diesters represented by the above general formula [I] include diesters corresponding to the monoesters exemplified above, as well as monodecyl monohexyl phosphate, monobutyl monododecyl phosphate, monoethyl monomyristyl Phosphate ester, monobutyl mono(octyl phenyl) phosphate ester, mononyl mono(polyoxyethylene decyl ether) phosphate ester, monodecyl mono(polyoxyethylene octyl phenyl ether) phosphate ester, monooctyl mono(polyoxyethylene nonyl) phenyl ester) phosphate ester, mono(polyoxyethylene stearyl ether) mono(polyoxyethylene phenyl ether)
Mention may be made of phosphoric diesters with two different alcohol residues such as phosphoric acid esters or dithiophosphoric diesters corresponding to these diesters. Further, as emulsifiers of the present invention, alkali metal salts of the above-mentioned phosphoric acid mono- or di-esters, such as lithium salts, sodium salts, potassium salts, etc., and ammonia, monoethanolamine, ethylamine, diethanolamine, dimethylamine, pyridine, triethanol, etc. Organic amine salts such as amines can be used as well. Among these salts, sodium salts or potassium salts are particularly suitable. Further, the above-mentioned phosphoric acid ester having a polyoxyalkylene chain can be preferably used in either the form of a free acid or the above-mentioned salt.
．． However, in the case of phosphoric esters having only hydrocarbon groups, it is preferable to use them in the form of salts. The amount of the phosphoric acid ester emulsifier (hereinafter sometimes simply referred to as emulsifier) used is usually 0.2 to 5% of the rosin substance to be emulsified.
Weight % preferably 0.5. The use of emulsifier in an amount of more than 5% by weight may improve the mechanical stability of the resulting aqueous emulsion, but on the other hand, the performance as a papermaking sizing agent, i.e. tends to reduce size effects.

In the present invention, it is also possible to use up to the same amount of a nonionic surfactant or other known anionic surfactant together with the phosphoric acid ester emulsifier.

In particular, when a nonionic surfactant is used in combination, the mechanical stability of the aqueous emulsion and the dilution stability against hard water are further improved. Examples of such nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene Glycol fatty acid esters, polyoxyethylene alkylamines, fatty acid monoglycerides, sorbitan fatty acid esters, pentaerythritol fatty acid esters, propylene glycol fatty acid esters, sucrose fatty acid esters, polyglycerol fatty acid esters, fatty acid alkanolamides, and amine oxides, etc. Generally non-ionic Examples include those known as surfactants. Examples of anionic surfactants include fatty acid salts, alkylbenzene sulfonates, alkyl sulfates, α, olefin sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkyl phenyl ethers. Examples include sulfate, sodium N-lauroylsarcosine, and sulfonate of naphthalene-formalin condensate. Conventionally known methods can be used to emulsify the rosin substance using the emulsifier.

For example, first, a rosin substance is dissolved in a water-insoluble organic solvent to form a solution having a solution viscosity (at 25° C.) of 1000 cps or less, preferably 500 cps or less. In this case, the solution concentration is usually about 20 to 70% by weight, preferably about 40 to 60% by weight. In the above, the water-insoluble organic solvent is preferably one that can azeotrope with water, such as benzene, toluene, cyclohexane, carbon tetrachloride, etc., with benzene being particularly preferred. Next, water and an emulsifier or an aqueous emulsifier solution are added to the organic solvent solution obtained above to pre-emulsify it, and then emulsification is carried out at a temperature of about 10 to 80°C, preferably about 30 to 60°C. Here, the amount of water used is preferably adjusted so that the mixture of the rosin material, organic solvent and water before emulsification contains 10 to 40% by weight of the rosin material. Since the emulsion thus obtained contains an organic solvent, in this method, the organic solvent is then distilled off, preferably under reduced pressure at about 30 DEG to 90 DEG C., to obtain the desired aqueous emulsion. When the organic solvent is distilled off, a portion of the water is usually also distilled off, so that the concentration of the resulting aqueous emulsion is somewhat increased. The aqueous emulsion of the present invention can also be produced by the following method.

That is, first, the rosin material is heated and melted, and water and an emulsifier or an aqueous solution of an emulsifier are added thereto, or the three are heated simultaneously, and then the molten mixture is emulsified. The temperature during melting and emulsification of the rosin material must be within a range that imparts fluidity to the rosin material but does not cause its decomposition, and is generally about 140 to 200 °C, preferably about 160 to 19 °C.
A temperature of 0°C is adopted. The viscosity of the rosin material melted in this temperature range is 300 cps or less, preferably 100 cps.
It is preferable to set it to less than ps. As is clear from the above description, emulsification by this method must be carried out in a closed container, and the internal pressure may be approximately 10 kg. Further, the amount of water used is appropriately determined depending on the desired concentration of the aqueous emulsion to be obtained. In any of the above methods, a homogenizer, a piston-type high-pressure emulsifier, an ultrasonic emulsifier, etc. can be used as the emulsifier.

Further, the water used during emulsification and which is a constituent component of the aqueous emulsion of the present invention does not need to be purified water, but it is preferable to use so-called soft water. The aqueous emulsion of the invention thus obtained has a concentration of 1 to 60% by weight of rosin material, preferably 30 to 45% by weight, and 0.2 to 5% by weight relative to the rosin material, preferably 0.5 to 3.0% by weight. % of the phosphoric acid ester emulsifier, and the rosin material can usually be dispersed in the emulsion as particles of about 0.03 to 4 microns.

The aqueous emulsion has a white to milky appearance and a pH value of 2 to 6. It is stable at room temperature for at least 6 months, does not form precipitates, and has excellent mechanical stability and dilution stability as shown in the Examples below. When the aqueous emulsion of the present invention is used as a sizing agent for paper manufacturing, it is added to an aqueous dispersion of pulp together with a fixing agent such as sulfuric acid at a pH of 4 to 6.
Alternatively, as described in Japanese Patent Publication No. 49-30201, it is added to an aqueous dispersion of pulp together with a small amount of a fixing agent such as sulfuric acid and a very small amount of a cationic fixing aid at a pH of 5 to 7. Paper making method can be adopted.

In this case, the aqueous emulsion of the invention is used in an amount of 0.1 to 2% by weight (dry weight basis) based on the pulp. As mentioned above, the aqueous emulsion of the present invention has excellent dilution stability, so it can be sufficiently diluted with water from rivers, taps, wells, etc., and is well dispersed in the aqueous pulp dispersion. Moreover, the diluted solution is stable for a long time. Therefore, special equipment and space for dilution are not required, unlike when using the proposed known aqueous emulsion. The aqueous emulsion of the present invention can also be used as a surface sizing agent, and is applied to preformed wet paper by conventional methods such as spraying, dipping, coating, etc.

The aqueous emulsion of the present invention will be explained in more detail with reference to Examples below.

Note that the reference example shows one example of a method for producing the rosin substance used in the present invention. Examples Middle and % are based on weight unless otherwise specified. Reference Example 1,800 parts of tall oil rosin was heated and melted, and 2.7 parts of p-toluenesulfonic acid monohydrate was added as a catalyst while stirring at 165°C.

Then, 165 parts of a 37% formaldehyde aqueous solution was added to 160 parts.
Addition takes 90 minutes at ~170°C. 15 at the same temperature
After stirring for a minute, 1.2 parts of sodium hydroxide dissolved in 12 parts of water was added to neutralize only the catalyst, and the mixture was further stirred for 1 hour to obtain a formaldehyde-modified rosin. Further, 1200 parts of gum rosin was added to this modified rosin, and the mixture was stirred and mixed at 175°C for 1 hour. 2950 parts of the above mixture and 177 parts of fumaric acid were heated and melted, and reacted at 200° C. for 3 hours. The obtained rosin material has an acid value of 208 and a softening point (ring and ball method) of 103.5°C. Example 1 100 parts of the rosin material obtained in Reference Example is dissolved in 100 parts of benzene, and then an aqueous solution prepared by dissolving a predetermined amount of various phosphoric acid ester emulsifiers in 200 parts of soft water is added.

This mixed solution is heated to 40° C. and pre-emulsified in a homomixer, and then passed twice through a piston-type emulsifier adjusted to a discharge pressure of 300 k9/d to emulsify. Benzene is distilled off from the obtained emulsion at 40° C. under reduced pressure to obtain the aqueous emulsion of the present invention. Table 1 shows the type and amount of emulsifier used in each emulsion, and Table 2 shows the properties of each emulsion obtained. In addition, for comparison, the cases in which a predetermined amount of sodium salt of dodecylbenzenesulfonic acid was similarly used as the emulsifier in the above are shown as comparative emulsions AM, N, and o, respectively, and the cases in which a predetermined amount of sodium salt of dodecylbenzenesulfonic acid was similarly used as the emulsifier were used as comparative emulsions AM, N, and o. The case where potassium hydroxide was used in an amount corresponding to 4 equivalent % of the emulsion value is also listed as comparative emulsion P. 100 parts of the rosin material obtained in the reference example, 200 parts of soft water, and 2 parts of sodium salt of monododecyl phosphate were charged into an autoclave connected to the emulsifying machine described in Example 1, heated to 180°C, and heated to 180°C. Stir for some time to pre-emulsify.

The pre-emulsion is then passed through an emulsifier and the resulting aqueous emulsion is cooled in a water-cooled condenser. The obtained aqueous emulsion is white, has a pH of 4.8, a concentration of 34.2 (F6, and a particle size of 1 to 3 μm). This is referred to as emulsion 1 of the present invention Q. In addition, in the above, the sodium salt of monododecyl phosphate is Instead, use 2 parts of sodium salt of dodecylbenzenesulfonic acid and repeat the same operation to obtain a white,
PH4. An aqueous emulsion with a concentration of 33.9% and a particle size of 1 to 3 μm is obtained. This is designated as comparative emulsion R. Ku. Stability test of emulsion> For the emulsion/F6A-R obtained in each of the above examples,
Measure the mechanical stability and dilution stability of each.

(1) Mechanical stability Each emulsion 509 was weighed into a container of a Marlon stability tester (manufactured by Shinsei Sangyo Co., Ltd.), and the temperature was 25°C and the load was 10.
After applying mechanical suture for 5 minutes at a rotational speed of 1000 rpm, the resulting aggregates were filtered out using a 100-mesh stainless steel net, and the mechanical stability was calculated according to the following formula.

The results are shown in Table 3.

(2) Dilution stability Each emulsion has a hardness of 5J0 or 20MaDH at 25℃.
dilute each with dilution water to a 5% concentration.

After dilution, the time required for the emulsion to coagulate and form flocs is measured with the naked eye. The results are shown in Table 3. Practical test> The degree of sizing of paper (
seconds) is measured by the Stekicht method (JISP8l22).

In other words, SR pulp (LBKP) with a freeness of 30 is mixed with tap water (
Make a 1% slurry of approximately 4.5% DH) and add to it the following a)
Or, after adding chemicals in the order of (b) and uniformly dispersing them, paper is made using a TAPP standard sheet machine to have a basis weight of 60±19/Trl.

This paper stock was dried at 80℃ for 5 minutes and then heated to 65℃ at 20℃.
The size effect is measured after 24 hours of humidity control in an atmosphere of constant temperature and humidity within % range. (a) Emulsion (0.2 or 0
．． 5%) → Sulfate band (2.5%) (l Emulsion (0.2 or 0.5%) → Sulfate band (0.5%) →
Cationic fixing aid (0.05%) The amount of each chemical added above represents the non-volatile content % of each chemical added based on the dry weight of the pulp.As a cationic fixing aid, "Araphix 200" (manufactured by Arakawa Forestry Chemical Industry Co., Ltd.) was used.

Claims (1)

[Claims] 1. In a paper-size aqueous emulsion consisting of a rosin substance, an emulsifier, and water, the emulsifier has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ [wherein A is R_1O-, R_1S, ▲ mathematical formula, There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼ or indicates a polyhydric alcohol fatty acid partial ester residue, R_1 is an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group, a cycloalkyl group, and an alkylcycloalkyl group. The selected hydrocarbon group having 6 to 24 carbon atoms, R_2 is a hydrogen atom or a methyl group, and m is an integer of 1 to 50. B is R_3O-, R_3S-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Polyhydric alcohol fatty acid partial ester residue or M_2O -, R_3 is a hydrocarbon group having 1 to 24 carbon atoms selected from an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, an arylalkyl group, a cycloalkyl group, and an alkylcycloalkyl group, and R_4 is a hydrogen atom or Methyl group and n are 1-5
Indicates an integer of 0. In addition, 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, a primary organic amine, a secondary organic amine, or a tertiary organic amine. An aqueous emulsion of a rosin material for papermaking size, characterized in that the emulsifier is a phosphoric ester emulsifier selected from - or di-esters and their alkali salts. 2. The aqueous emulsion according to claim 1, wherein the phosphoric acid ester emulsifier is a phosphoric acid monoester or an alkali salt thereof. 3. The aqueous emulsion according to claim 1, wherein the phosphoric acid ester emulsifier is a phosphoric acid diester or an alkali salt thereof. 4. The aqueous emulsion according to any one of claims 1 to 3, in which the rosin substance is used in a concentration of 1 to 60% by weight and the phosphoric acid ester emulsifier is used in 0.2 to 5% by weight based on the rosin substance. .