JPS60175532A - Stable substituted anhydrous succinic acid/emulsifier composition and sizing method of paper using the same - 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 Background of the Invention The present invention relates to an improved method for imparting water repellency to surfaces containing reactive groups for stable hydrocarbi A/substituted anhydrides. Yet another 7m of the invention
relates to an improved method of sizing paper and paperboard. It is well known in the art that hydrocarbyl-substituted succinic anhydrides are excellent for treating paper, textiles, or other surfaces to impart water repellency. U.S. Patent No. 3,102,064, U.S. Patent No. 3,821,069
No. 5,968,005 and No. 4,040,
No. 900 (Reissue Patent No. 29,960), these compositions are used for paper sizing.
Useful for temples.

It is also known that these succinic anhydrides are best applied for these purposes in highly dispersed form, such as aqueous emulsions. Paper sizing emulsions prepared from mixtures of MW mono-dicarboxylic anhydrides and polyoxyalkylene alkyl or alkylaryl ethers or corresponding mono- or di-esters are described, for example in US Pat. No. 111I=: Fourth
, No. 090,900 (Reissue 4ewt% 29v960
Please refer to No.

Useful emulsifiers for d-converted succinic anhydrides include long-chain diester emulsifiers as well as monoester, alkylphenol ethoxylates and alcohol ethoxylates, as described in U.S. Pat. No. 960).

The major drawback of these prior art emulsifiers is that the succinic anhydride-emulsifier mixture is unstable once formed and must be used quickly. Accordingly, there is a need in the art for substituted succinic anhydride-emulsifier mixtures with improved aging or storage properties.

SUMMARY OF THE INVENTION The present invention provides a normally liquid hydrocarbyl-substituted anhydride having 6 to 50 carbon atoms in the N substituent.
5%; and (B) formula % [wherein R is a hydrophobic alkyl group, alkylaryl group, arylalkyl group or aryl group having 8 to 60 g atoms; W is is a water bathable polyethyleneoxy-containing group having from 6 to 80 ethylene oxynide units and is connected to R and Y individually by a bar, sulfur or type bond; Y is a group on W; , an acyl-capping group for a sulfur or nitrogen bond (provided that there are no more than 7 back atoms of methylene carbons, and in addition Y
Y is 2 if it does not include Yuma Cal 4 Gukishi Jv story
8 carbon atoms); n is "/3, l/2.1.2, or 6"; Stable hydrocarbyl-substituted succinic anhydride/emulsifier compositions are provided having a hydrophilic-lipophilic balance of between about 9 and 18% on the HLB scale.

According to the present invention, there is further provided a method for imparting water repellency to a surface having a reactive group on an anhydride, which comprises impregnating the surface with an aqueous emulsion of the substituted succinic anhydride/emulsifier composition of the present invention. provided.

The present invention also provides for the dispersion of an aqueous emulsion of the substituted anhydrous amber/emulsifier composition of the present invention into the wet papermaking pulp before its final conversion to dry quezo. Relating to a paper sizing method characterized by:

The present invention discloses the aging of substituted succinic anhydride with a polyethyleneoxy-containing (or "polyethylene glycol-based") germanium conductor emulsifier in which the free hydroxyl groups are capped with minority carbon functional groups. It is specifically based on the inventor's discovery that it is an extremely effective emulsifier for. These emulsifiers form stable mixtures with substituted succinic anhydrides and do not react with the succinic anhydrides under storage conditions.

The anhydrous amber-emulsifier mixture of the present invention is extremely effective in imparting water repellency to surfaces. These compositions are excellent paper sizing agents, especially for /Ij.

DETAILED DESCRIPTION OF THE INVENTION Hydrocarbyl-1a substituted succinic anhydride is a hydrophobic molecule useful for preparing the anhydride/emulsifier compositions of the present invention. this! V/J quality usually has one substituent at the 6-position, but may have substituents at both the 6- and 4-positions. The monovalent substituent in @ is generally an alkyl group, an alkenyl group or an aralkyl group. Other elements such as sulfur or ether linkages may also be present. 1)
The total number of carbon atoms in substituent 1i of No. 7I is between 6 and 50. The preferred size of the substituents is about 10 to 60 carbon atoms in total.
0, more preferably 12 to 25 ff1f
It is.

A preferred embodiment of the anticipated anhydride is an alkenyl succinic anhydride obtained by carrying out the well-known ene' reaction between an olefin and maleic anhydride. [Diels-Alder] products derived from .

The emulsifier of the composition of the invention has six essential properties. First, the emulsifier dissolves in the ASA at ambient temperature.

Second, it is storage stable when dissolved in ASA. Thirdly, there is a surfactant that emulsifies ASA in water. In order to satisfy these requirements, the emulsifier of the present invention contains A
It contains no free H, -OH or -NH4 that could react with SA and has a hydrophilic-lipophilic balance (HLB) of between about 9 and 18.

To achieve the desired HLB, the emulsifier is generally about 6
It has an average number of moles of ethylene oxide between .about.80. More generally, the preferred range for the number of moles of ethylene oxide used is about 5-40.

The emulsifier of the present invention is derived from commercially available polyethylene glycol containing free hydroxyl groups.
L emulsifier can be manufactured. These commercially available emulsifiers themselves are dissolved in ASA and are effective in emulsifying aqueous substances in water. An example of this German hydroxyl-containing compound is described in U.S. Pat. These compounds include Nagayorinaga alcohol, alkyl phenol, and polyethylene glycol 1 compounds commonly used to prepare hydrogen atom. These compounds generally contain one free hydroxyl group; It is expressed by the following formula.

1 0X, E(iC-(OCR2C)12)-0r(CXH
... Ding (OCH2CH2), -OH% (where χ is a 8 to 24 princess ridge, and 2 is an indigo number from 5 to 20). These hydroxyl group-containing compounds (Igepal) CO-630 (manufactured by GAJ'),
Triton X-100 (manufactured by Rohm and Haas), Tergit
ol) TMN-6 and Tergitol 15-s-
9 (Union Carbide & Co.) and PgG 400 mono- and dilaurate (Stepan Co.).

In addition to the monohydroxy-functionalized surfactants described in MiJ, suitable surfactants may be functionalized with a variety of hydrophilic moieties that are familiar in the art. In addition to polyethyleneoxy groups, they may contain certain basic glyceryl, polyglyceryl, anhydride rubityl or pentaerythrityl groups. These compounds in which there are 11+61 or more hydroxyl groups that must be blocked are used to form the surfactants of the present invention. Small amounts of propyleneoxy compounds may also be present.

Surfactants having four or more hydroxyl groups are undesirable because they require a large amount of sealant.

It is also contemplated to use surfactants having a valence of yellow or yellow, either between the hydrophilic groups or on the hydrophobic or blocking groups. For example, ethoxylated mercaptans or ethoxylated IJb' fatty amides can also be used. Ethoxylated sulfonamides can also be used.

The hydrophobic moiety may be linear, branched or monkey-like.

This can be alkyl, alkylaryl or arylalkyl. This also refers to acyl adjuncts.

The above-mentioned compounds can be converted into the present emulsifier by blocking the hydroxyl groups or reacting the free hydroxyl groups with a small number of loose carbon collapse holes. This blocking group (
Capping group) generally have a tendency to slightly lower the hydrophilic-lipophilic balance (HLB) of the emulsifier due to the capping group adding a small number of monohydric moieties to the molecule. The surfactant and the capping group must be separated so that the capped emulsifier is within the desired HLB. The reactivity in the surfactant used is 8H, -OH.
and - Use enough encapsulant to cover all of the NH&.

The side neck punishment in 1iiJ is generally performed using an emulsifier of 10H, -8
H or -Nm4 derivatives are formed and the derivatives are AS
Any sequestering agent that will give a stable emulsion when dissolved in A may be used. Unfortunately, the inventors have discovered that certain common derivatives do not provide stable emulsions. For example, t[silyl ethers and sulfonate esters do not form stable emulsions upon ripening.

However, carboxylic acid esters, carbamate esters and keto esters have been found to form stable emulsions in ASA. Therefore, the capping agent used for producing the composition of the present invention is preferably one that adds an acyl capping agent to the starting emulsifier.

Capping agents contemplated for use are those that form carboxy derivative bonds, such as esters, amides, carbamates, ureas, etc., with the hydrophilic moieties described above. Suitable agents are carboxylic acid anhydrides, acid) 1lides, incyanates, ketene dimers, and the like. Examples of suitable agents include acetic anhydride, ketene, diketene, acetyl chloride, acetyl zolomite, zolobioic anhydride, butyryl chloride, pivaloyl chloride, hexaroyl chloride, benzoyl chloride, tolyl chloride, ethyl isocyanate, Ethyl isothiocyanate, hexyl isocyanate, etc. are used.

The above-mentioned functional groups are usually -'1 functional, but may be difunctional or trifunctional as long as the functional groups are proportionately matched to each functional group. Examples of difunctional cross-agents include succinyl chloride, maleyl chloride, adipoyl chloride, decanedicarbone, toluene diincyanate, diphenylmethane-4,4'-diisocyanate, and the like.

The following describes a range of suitable carbon-containing groups and reactive functionalities that can be attached to form suitable agents.

Carbon-miya groups include methyl, ethyl, propyl, ethyl, pentyl, hexyl, heptyl (branched or straight chain), cyclopentyl, cyclohexyl, phenyl,
Includes benzyl and tolyl groups. Reactive functionalities include anhydrides, acid nitrides, incyanates, and inthiocyanates.

Sequestering agents that do not require catalysts or co-reactants and do not form by-products and therefore do not require additional processing steps are preferred. Examples of suitable agents include ethyl isocyanate,
Toluene diisocyanate, ketene and ketene dimer are produced.

The acyl capping group on the emulsifier, designated Y in the formula OiJ, generally contains 2 to 8 carbon atoms when the methylene carbons are no more than 7 carbon atoms.

This capping group Y must also not contain free carboxyl groups. The inventor uses the term "methylene" to mean any carbon atom that has at least three bonds attached to hydrogen or other carbon atoms. Therefore, methyl groups and some methine groups are also included within this thorn. A relatively small number of methylene carbon atoms 'Ff L , a lipophilic group, will not change the hydrophilic-lipophilic balance (LB) of the emulsifier too much. Also taking into account the carbon atoms involved in carbon-JA hydrogen depletion, these are equal to 2/3 of the methylene return water. Preferably, Y has 2 to 6 carbon atoms. In the case of difunctional capping agents, these numbers of carbon atoms are doubled. Inert groups such as ether or thio bonds may also be present. In addition to this, inert amide bonds can also be present, such as in carbamates removed from isocyanates.

In the case of capping agents containing reactive functionality, such as the double bond in maleyl diesters, this compound is a product compatible with the present invention, it can be reacted with this functionality by reactions known in the art. For example, suitable emulsifiers are obtained by isomerizing maleyl diesters to fumaryl diesters.

Examples of suitable capping groups on the emulsifiers of the compositions of the invention include: where R' is an n-alkyl group, an inalkyl group, a cycloalkyl group or an aryl group having 1 to 7 carbon atoms. ); (wherein R" is hydrogen, methyl group or ethyl group)
: (wherein R"' is n- having 2 to 14 carbon atoms
alkylene, alkylene, cycloalkylene or arylene groups).

For the specific example of the enclosed @group we are expecting: CH2-C-1 1 is said.

Examples of 'M'kA' emulsifiers that are compatible with the compositions of the present invention include emulsifiers sequestered with molten anhydride, such as succinic anhydride, at temperatures of 1 to 500°C at 150° to 230°C. There are products made by heating for hours. Such anhydride sequestration is described in the inventor's co-pending Application No. M4546,764, filed October 28, 1983, the disclosure of which is incorporated herein by reference. For heat treatment to remove carboxyl side groups to make a capped emulsifier with the compositions of the invention, 19
Inventor's US Patent Application No. 5 filed on June 29, 1983
No. 09,270, the disclosure of which is incorporated herein by reference.

The hydrophilic/hydrophobic balance of the sequestered emulsifier is in the same range as in conventional emulsifier-detergents.

One way to assess this balance is the HLB scale (a, aqueous-lipophilic balance).
1967), edited by M. J. Schick.
See Chapter 18 of "Nonionic Surfactants" by Beaker. Hydrophilicity-
Lipophilic balance is a measure of the hydrophilicity (prevalence of water) in a surfactant. Using this scale, Hr = B of the inventor's oil-in-water type sequestered emulsifier is approximately 9 to 18.
, preferably between 11 and 16.

HI, B is N? by comparing the properties of each building such as HLB known emulsifier and water clarity. can be valued.

Alternatively, HLIB can be calculated by several methods known in the art. For example, J, T.

426 Tei (1957
Please refer to 2013). A simple method when using polyethylene oxy-containing nonionic compounds is to divide the % of polyethylene oxy P by 5. In this way, the inventors have determined that the HLB of some emulsifiers of the compositions of the invention
was estimated. When this approximate HLB is 11 to 16, a very good ASA emulsion in water is obtained.

The emulsifier of the composition of the present invention is produced by reacting the unstable water W4-containing emulsifier described above with the sealant until the hydroxyl groups thereof are reacted. This reaction generally takes several minutes to several hours at temperatures of about 80° to 200°C. The use of catalysts allows the use of relatively low temperatures and relatively short times. Ester derivatives, commonly prepared from carboxylic acid anhydrides or halide drugs, can alternatively be prepared by other esterification reactions well known in the art, such as acid-catalyzed esterification or base-catalyzed transesterification. Can be made from carboxylic acids or esters.

Before making the ASA/emulsifier composition of the invention, water,
It is preferred to remove any abrasives that may be formed, such as acetic acid or hydrogen chloride. The sequestered emulsifier is then incorporated into the ASA to form the ASA/emulsifier emulsifier composition of the present invention.

Alternatively, if the capping agent is sufficiently active, the hydroxyl-containing emulsifier can be first dissolved in the ASA and then reacted with the capping agent.

The AHA/emulsifier composition of the present invention contains 70 to 99.5
substituted succinic anhydride, preferably 80 to 98 parts by weight, and 0.5 to 60 parts by weight, preferably 2 to 20 parts by weight.
A sized portion of sequestered emulsifier is included.

These ASA/emulsifier combinations are central iMP)
The ASA emulsion can be easily manufactured at the factory and stored and transported to the location where the ASA emulsion is prepared. Both components are miscible and the mixture is liquid at chest temperature.

The ASA/emulsifier composition can be made into a glaze by 1 to 8 minutes of mixing, even without the use of shear forces! tit
It emulsifies easily in water at both pH and pH. Adverse droplets are formed and the emulsion is stable until it is used to treat surfaces containing anhydride-reactive groups.

The time between formation and use can range from a few seconds to a few hours; relatively long times are unfavorable since the anhydride groups are gradually hydrolyzed by the water present.

The water used can be relatively pure or contain impurities that are common in household water. The pf4 of this water is 1 (or higher) than 7, but is generally within the range of 6 to 11. Calcium and magnesium hardness ions are also
It may be a%.

The amount of ASA suspended in water can vary widely from a few ppm to 10% or more depending on the use and method of application. For wood or textile applications, concentrations around 1% are used, while for paper internal sizes, the concentration in the bond slurry is usually about lQ01)])m. Therefore, the final absorption into the paper is about 0.1-1% AHA.

The surface treated with the ASA/emulsifier composition of the present invention to impart water repellency should contain a primary group reactive with the ASA anhydride group. This usually includes hydroxyl groups,
It is highly reactive with groups such as amino or mercapto groups. A preferred class of materials that can be treated with emulsions of the compositions of the invention are materials that are depleted of carbohydrate molecules, such as cellulose or starch, on the surface of the material. These silicas contain a large number of hydroxyl groups that can react with ASA. As noted above, the ASA/emulsifier compositions of the present invention can be used to impart water repellency to cellulosic materials. Preferably, the water-breaking composition described above is applied to the substance in an aqueous emulsion. This emulsion is
To distribute the derivative uniformly throughout the material, it is sprayed onto the material or immersed in the emulsion. After soaking, remove from the solution and air dry. After air drying, the material is preferably heated to a YI! Heating with LL hardens the drug impregnated within the material. It has been found convenient for this to be carried out for 15 to 20 minutes at a temperature of approximately 125°C. A relatively short time contributes to a relatively long time in the curing process. Lower temperatures and shorter times can be used when an acylated medium is present. When carried out pre-incubation, the incubation time should be as short as possible, typically 1 hour without vortexing. At relatively moderate temperatures, heat curing takes place in a relatively short time. The upper temperature limit at which thermal curing can be carried out is the silver layer at which the cellulosic material begins to decompose. When using the compositions of the invention, about 0.5-6% of the weight of the material is ASA.
/ It is preferable to use an emulsifier composition.

The ASA/emulsifying compound of the present invention can also be used as a paper sizing agent. These new sizes have all the characteristics and advantages of prior art sizes. Additionally, the novel sizing agents of the present invention provide particularly superior resistance to acidic liquids such as acidic inks, citric acid, lactic acid, etc. compared to papers sized with prior art sizing agents. Grants resistance. In addition to the properties described above, these sizes can also be used in combination with alum and any additives, fillers and other acids that can be added to the paper. The sizing agents of the present invention can also be used in combination with other sizing agents to obtain additional sizing effects. Still another advantage is that this sizing agent does not reduce paper stiffness and actually increases the strength of the finished sheet when used with certain yuzu additives. Only mild drying or curing conditions are required to fully develop the size values.

The actual use of these sizes in papermaking involves a number of technical variations, any of which may be further modified by the particular ammonia of the skilled worker. In any case, in all of these methods, it is best to uniformly disperse these sizes throughout the fiber slurry in the form of tiny droplets that allow intimate contact with the frozen fiber surface.
It is important to emphasize that electrical equipment is also essential. Uniform dispersion can be obtained by adding the size to the pulp as a fully dispersed emulsion or by adding a preformed fully dispersed emulsion. Chemical dispersants can also be added to the fiber slurry.

Other important factors for utilizing the sizing agents of the present invention for M efficacy include cationic or in a manner that produces one or more cations or other positively encapsulated moieties. It is used in combination with substances that can be ionized or dissociated.

These cationic agents (Kikiri; hereafter referred to as ``Kikiri'') help the sizing agent to be retained in the pulp fiber circle, as well as serve as a means of bringing the pulp fibers and the sizing agent into close proximity. It has been found that Among the substances that can be used as cationic agents in the sizing process are alum, aluminum chloride, aliphatic amines, sodium aluminate, substituted polyacrylamide, nichrome sulfate, animal glue, cationic thermosetting resins,
and polyamide polymers. Of particular interest for use as cationic agents are primary, secondary, tertiary or quaternary amine denone derivatives and various other cationic, substituted starch conductors, including cationic sulfonium and phosphonium conductors. It is a cationic starch attractant. Such derivatives can be made from all types of starch including corn, tapioca, potato, waxy corn, wheat, and rice.

Additionally, they may be in their original particle form or pregelatinized,
It can also be modified to cold water soluble products.

Any of the cationic agents described above may be added to the stock, ie, the pulsing agent, before, along with, or after the addition of the sizing agent. However, for maximum distribution it is preferred to add the cationic agent after the sizing agent or in direct combination with the sizing agent. The actual nitric addition of any of the cationic or sizing agents to the stock can be added at any point in the papermaking process before the wet pulp is finally converted to wire or sheet. These sizes N
o can be agitated to the pulp while it is in the headbox, beater, hydropulper or stock chest, for example.

The water resistance of paper made using the new size is further improved by curing the sized web, sheet or molded article. This curing process requires 80
A step of heating the paper for 1 to 60 minutes at a temperature in the range of 150°C to 150°C is provided. However, it should again be noted that this post-curing treatment is not required for successful implementation of the method of the invention.

The sizing agents of the present invention can, of course, be successfully used for sizing papers made from all types of paper, both cellulose and combinations of cellulose and non-cellulosic fibres. Cellulose fibers that can be used include bleached and unbleached sulfate (kraft), bleached and unbleached sulfide,
Includes bleached and unbleached soda, neutral sulfides, semi-chemicals, chemical wood pulps, groundwood pulps and any combinations of these fibers. These names apply to wood pulp fibers produced by proprietary methods used in the pulp and paper industry. In addition, synthetic or regenerated cellulose versions of viscose rayon can also be used.

Papers sized with the novel sizing agents of this invention can be loaded with all kinds of pigments and fillers. Such materials include clay, tar, silica, titanium dioxide, calcium sand, calcium sulfate, and diatomaceous earth. Other additives can also be used with these sizes, including alum as well as other sizes.

In terms of proportions used, this sizing agent accounts for about 0.05 to about 6.0 of the dry coulage of the pulp of the finished sheet or web ψ.
It can be used in amounts within %. Amounts in excess of 6% can be used, but the benefits of increased sizing are usually not economically justified. The exact extent of the sizing agent to be used within the foregoing ranges depends in large part on the specific milling conditions of the pulp used and the maximum length of use for which the paper is intended.

For example, papers requiring good +ij (aqueous or ink retention) may require the use of a sizing agent that is even thicker than papers that do not.

The following actual measurement examples are presented to clarify the present invention based on the principles of the present invention. 'I'pr with /+≦
EXAMPLE 1 The alkenyl anhydride (AS
A) was a 4 mg liquid C1s~20 ASA produced by a "dyne" reaction of anhydrous maleic 1 wing and a C'15~2o olefin. This olefin consists of a 50150 mixture of a straight olefin and a branched propylene oligomer, both of which contain ClI
It belonged to 5-02oi criminal 4.

A nonionic oil-in-water emulsifier for the painting industry.
Igepal) Co-650 10% bath for one night.
-+11 ij Prepared in my own ASA. This solution was a homogeneous Wfa solution that was transparent at room temperature. 1 drop of this mixture (0,
026g) was shaken with 25d of water for 15 seconds in a graduated container with a stopper. A stable white emulsion was formed. H.L.B.
13.0, this emulsifier is an excellent emulsifier for ASA when freshly mixed.

[A mixture of 10% emulsifier in ASA of the Book of Ju.
d. After one week it no longer formed a stable emulsion. Similarly, this mixture did not form a stable emulsion when aging was accelerated for 6 hours at 80°C.

6 other commercial emulsifiers (i.e. soda) -y
TMN-75, Soda Toru 15-s-12, Triton x-114, Triton X-100, if”ha #
Co-620 Oyohii'f Bar Co-72
Similar results were obtained with 0. When heated at 80° C. for 6 hours, the 10% mixtures in ASA lost their self-emulsifying power. The HLB of these emulsifiers is 1 i,
In this actual measurement example, the ASA
The results show that although the mixture forms an excellent emulsion when freshly mixed, it no longer forms a stable emulsion after the mixture is aged.

Example 2 Ibupar co-660 was added to anhydrous i! at a 1/1 molar ratio. I
i: [ and heated at 80° C. for 16 hours. Infrared analysis of this mixture showed that acetic anhydride was consumed as the ester was formed and that a by-product was present.

The strong absorption of the ester carbonyl at 17.35 cm-”
was replaced by the anhydrous honey peak. The absorption of the water sales group at 3480 m-1 of the alkylphenol ethoxylate disappeared. The calcic acid in the biomass was removed by heating at 80° C. overnight in a vacuum oven.

Assuming that Ike9par Co-630 is an ethoxylated nonylphenol containing 9.6 ethylene oxide groups, the HLB of this sequestered emulsifier is 1.
2.2 and approximately >4.

EXAMPLE 6 The capped emulsifier of Example 2 was mixed into the ASA of Example 1 at the 10% level. A homogeneous bath solution was obtained at room temperature.

When the emulsifying power of this mixture was tested in the manner described in Example 1, it formed a good emulsion in water. In this case the mixture was storage stable. After accelerated aging at 80° C. for 6 hours, the mixture was still a nice emulsion.

Indeed, this storage-stable ASA/emulsifier composition exemplifies the present invention.

LaughMa Example 4 Ibupar Co-630 was mixed with ethyl isocyanate in a 1/1 molar ratio and heated at 80°C for 16 hours. Infrared examination of the product revealed 3480 crtt-'
The absorption of the hydroxy group disappears, and the N-H band becomes 555
0C11L-'' and a large carbamate carbonyl band was present at 1725cIIL-1.

The HLB of this sequestered emulsifier is estimated to be 11.7. The ethyl isocyanate sample is advantageous because no by-products are formed in the capping process.Example 5 Example 1 Example 1 Example 1 Example 1 Example 1
A homogeneous 14d solution was obtained at 0 room temperature mixed in ASA.

When the emulsifying power of this mixture was tested by the method described in Example 1, it formed a good emulsion in water. In this case the mixture was storage stable. Even after accelerated aging at 80° C. for 6 hours, the mixture became a good emulsion.

This storage stable ASA/emulsifier composition therefore exemplifies the present invention.

Example 6 Ibupar Co-660 was used as the starting material and was tested in a similar manner to Examples 2 and 6, blocked in some cases with methanesulfonyl chloride and in other cases blocked with chlorotrimethylsilane. In both cases the sequestered emulsifier was dissolved in ASA.

A good to excellent emulsion in water was formed when freshly mixed. In this example, no stable emulsion was formed after aging at 80°C for 6 hours.
It is shown that some common hydroxyl agents are not satisfactory capping agents for use in the present invention.
Similar negative results were obtained for o-720.

EXAMPLE A test was carried out in the same manner as in Examples 2 and 6, using Fiber/L/Co-630 as a starting material and blocking it with 1 equivalent (l/2 mol) of succinyl chloride.

In this case, the final ASA/emulsifier mixture was also stable on storage and produced a good emulsion in water even after heating at 80°C for 3:11j.

This method of sequestration with bifunctional agents yields compositions that exemplify the invention. The HLB of this blocked emulsifier is
The JR calculation is 12.2.

Example 8 An experiment similar to Example 7 was conducted using succinyl chloride as the difunctional drug and Ibupar Co-720 as the starting material. In this case, excellent emulsions were produced before and after accelerated ripening. Assuming that Ibupar Co-720 is a sulfethoxylated nonylphenol rich in 12 ethylene oxides, its HLB is estimated to be 16.4.

Example 9 A procedure similar to Examples 2 and 3 was carried out using Ibupar Co-630 as the starting material and blocking it separately with diketene and toluene diisocyanate. In each case,
The formed ASA/sequestered emulsifier formed a stable emulsion in water after accelerated aging.

These reeds are advantageous because no by-products are produced in the M-chain process. The HLB of the emulsifier chained with diketene is 11.
．． The HLB of the emulsifier capped with toluene diisocyanate was estimated to be 11.4.

Example 10 Ibupar Co-720 was used as the starting material and was carried out in a similar manner to Examples 2 and 6 by blocking separately with diketene and 1.10 decanedicarbone, benzoic acid, pivalin and n-hexanoic acid. . In each case, the ASA/sequestered emulsifier formed formed a stable emulsion in water after accelerated aging.

The HLB of the sequestered emulsifier was estimated to range from 12.4 to 12.7.

Agent Akira Asamura

Claims (1)

[Scope of Claims] (1) 1 is a substitute for a normally liquid hydrocarbyl-substituted succinic anhydride having 6 to 50 carbon atoms 70 to 9
9.5%, and (B) formula [wherein R is a hydrophobic alkyl group having 8 to 60 carbon atoms, W represents 6 to 80 ethylene oxide groups,
4 to R and Y individually by acid system, fanhuang or nitrogen bond
is a water-soluble 4 raw polyethyleneoxy-i'' radical that is combined; Y is IRg, illi on W, which is not bonded to R
: Huang Kinare Shigun Gen, ・An acyl group for the punishment axis for N (provided that methylene carbons are not more than 7 carbon water atoms, and further that Y does not contain free carboxyl groups) and Y contains 2 to 8 carbons); n is l/3, V2, 1, 2, or 6, and its hydrophilic-lipophilic path is about 9 on the HLB scale. -18% of an emulsifier]. The composition according to claim 1, wherein the group is selected from the group consisting of an alkyl group, an alkenyl group, and an acylkyl group. (3) The hydrocarbyl substituent of component (A) is an alkenyl group. (4) The composition according to claim 2, wherein the hydrocarbyl compound of component (A) contains 10 to 60 carbon atoms. The composition according to claim 4. (5) The composition according to claim 4, wherein the hydrocarbyl substituent of component (A) contains 12 to 25 carbon atoms. (6) W has 5 to 40 ethylene oxide units. +7) W is connected to R and Y by acid group plugging. Compositions as described. (8) Claim 1 in which Y contains 2 to 6 carbon atoms. ! The composition described in JI. (9) R-W- is 1 c, H,;7 c-(ocH2Cn,)-os %CX
H2,,, (OCR20H2) "OH% (wherein, X is 8
The composition as claimed in claim 1, which is derived from a hydroxyl-poor compound different from the group consisting of: (wherein R' is an n-alkyl group, inalkyl group, cycloalkyl group or ary-, /I/ group having 1 to 7 carbon atoms), R'' (wherein f is water-based, methyl group or ethyl group)
and (wherein R'' is an n-alkylene group, an isoalkylene group, a cycloalkylene group, or an arylene group having 2 to 14 carbon atoms). The composition according to Ql) Y is selected from the group consisting of 114Fl\fClaim 1
I Seichi 〇α4 described in 01j4 The emulsifier of the component (B) has an HLB shakuja of about 1
A composition according to claim 1 having a hydrophilic-lipophilic balance of between 1 and 16. 4. The composition according to claim 1, wherein the composition is in the form of an aqueous emulsion. A method for imparting water repellency to a surface containing a group reactive with anhydride, the method comprising impregnating the surface with the aqueous emulsion according to claim 1. (1ω) The method according to claim 14, wherein the surface of the front a-pi is a cellulosic material. Paper sizing method 0 characterized by the step of closely dispersing the aqueous emulsion composition according to item 1.