JPS60246893A - Preparation of size agent - 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 Alkenyl succinic anhydrides (ASA) useful in sizing cellulosic materials have met with considerable commercial success. These materials were first fully disclosed in US Pat. No. 3,102,064, which is incorporated herein by reference. This patent is based on the following structural formula: where R is a dimethylene or trimethylene group and R is a hydrophobic group having more than 5 carbon atoms selected from the group consisting of alkyl, alkenyl, aralkyl or aralkenyl groups. Disclosed are certain types of chemical materials having the following properties.

In describing the use of the ASA sizing agent disclosed in this document, the patentee indicates the following content. Thus, for their effective use, the sizing agent should be cationic in nature or used in conjunction with substances capable of ionizing or dissociating one or more cations or other positively charged groups. The cationic agents defined in this document are:
It is disclosed as "Aluminum sulfate, aluminum chloride, long chain fatty amines, sodium aluminate, I-lyacrylamide, chromium sulfate, animal glue, cationic thermosetting resins, and polyamide polymers."

The patentee discloses that as preferred cationic agents, the first, second,
Particular mention is made of tertiary or quaternary amine starch derivatives and other cationic nitrogen-substituted starch derivatives, as well as cationic sulfonium and phosphonium starch derivatives.

Such derivatives mentioned by the patentee can be made from all types of starch including corn, tapioca, potato, etc.

As the commercial use of sizes of the above type increases, significant problems remain in applying the size to a paper stock or sheet prior to forming it into a sheet or other useful form. . Some of the issues are as follows.

That is, the ASA sizing material is not water soluble and therefore must be uniformly dispersed in the /4' loop so that the sizing agent has sufficient contact with the cellulosic fibers and thus provides the desired effect on the final product.

Although the cationic agents disclosed in U.S. Pat. No. 3,103,061 have been successful, there are
A need arose to produce a "cationic agent" for the ASA size. In addition, such cationic agents will preferably assist in retaining the size on the fibers, and further enhance the wet and/or dry strength of the final sheet material if desired.

It is thus an object of the present invention to provide some additives which serve to emulsify or disperse the ASA size within the noclude and keep it retained on the fibers.

Another object of the invention is to use as an emulsifier for ASA sizing materials greater than io, ooo and preferably 1.000,
The use of water-soluble vinyl addition polymers having a molecular weight of less than 0,000.

Further objectives will be revealed below.

As briefly discussed above, the present invention utilizes cationic, water-soluble vinyl addition polymers having a molecular weight greater than 10,000 and preferably less than i,ooo,ooo as additives and emulsifiers for ASA sizing agents. Regarding things. The use of such cationic vinyl addition polymers serves as a useful emulsifier for the ASA size and further enhances the retention of the size on the cellulose sheet.

ASA sizing agents to which the present invention can be applied include U.S. Pat.
102,061.4,040,900.3,968,0
05, and 3,821,069 K,? ? All of the sizing agents mentioned above are included below for reference.

The sizing agents used in the subject matter of the present invention are generally represented by the following structural formula: 1 0 space below where R represents a dimethylene or trimethylene group and R1 is alkyl, alkenyl, or alkyl.

In a particularly useful embodiment of the invention, surfactants were also used to make the ASA sizes of the invention. Surfactants can be anionic, nonionic, or cationic. The surfactants used are generally water soluble and have a concentration of about 8 to about 30
or higher, preferably an HLB value of about 8-15. Surfactants are commonly used to make ASA sizes by simply mixing them with the raw ASA material.

Therefore, the ASA sizing agent used in the present invention and also in preferred embodiments of the present invention generally has an ASA size of 75 to 9
9.5 parts by weight plus 90 to 99 parts by weight of ASA and 0.5 to 25 parts by weight of surfactant, preferably 0.75 to 10 parts by weight
The content is most preferably 1.0 to 5 parts by weight.

The surfactant is preferably added to the ASA prior to aqueous medium pore formation. Surfactants can also be added to the aqueous medium prior to adding the ASA. Preferably the surfactant is AS
Added directly to A.

The surfactants used in the present invention are further disclosed in U.S. Pat. No. 4,040,900, which is incorporated herein by reference.

Pertinent portion of U.S. Pat. No. 4,040,900, column 4, 5
Starting from line 4, column 5 continues for 46 lines. However, other parts of this patent are also relevant.

Types of materials useful as surfactants in the present invention are: ethoxylated alkylphenols such as nonylphenoxypolyethoxyethanol and octylphenoxypolyethoxyethanol; polyethylene glycols e.g. EVA PEG 400 mono-oleate, and PEG 600 dilaurate: as well as other substances including several ethoxylated phospade esters.

The preferred surfactant used in the present invention is GAFA.
CRM510 and GAFAC'RE610, both complex organic phospade ester free acids manufactured by GAF Corporation.

Water-soluble yJ? which is a cationic agent useful in the present invention?
IJ moms include water-soluble vinyl addition homopolymers and colimers having molecular weights greater than 10,000, more preferably less than 1,000,000, where -'''CC
at least 10% by weight of the polymeromer content and 100%
00% by weight is cationic monomer or cationically modified monomer.

Preferably, at least 15 of the monomer units in the polymer
Furthermore, up to 95% by weight are cationic or cationically modified monomers. Most preferably, 20 to 75 monomer units in the polymer are cationic or cationically modified.

Polymers selected for use in the present invention generally have a molecular weight greater than 10,000 and less than 1,000,000. Polymers of this type should generally be water-soluble and more particularly preferred molecular weights are between 20,000 and 20,000.
It was found to be 7.50.000. Most preferably, the molecular weight range of the polymer used is 50,000
~150,000.

1. It has a molecular weight of 00,000 or more. ]? Rimers can be used as long as they are water soluble.

The following exemplary copolymers and homopolymers that can be used in the practice of the present invention include, but are not limited to, niacrylamide 9-dimethylamine ethyl acrylic V-)
, acrylamide-dimethylaminoethyl acrylate quaternary salt, acrylamide-diethylaminoethyl acrylate, acrylamide-diethylaminoethyl acrylate quaternary salt, acrylamide-dimethylaminoethyl methacrylate, acrylamide-dimethylaminoethyl methacrylate quaternary salt, acrylamide-diallyldimethylammonium chloride, Polydiallyl-dimethylammonium chloride, polydimethylaminoethyl methacrylate and its quaternary salts, polymethacrylamidopropyltrimethylammonium chloride; and acrylamide-methacrylamidopropyltrimethylammonium chloride.

Also useful are polymers and copolymers of acrylamide that have been subjected to the "Mannitzsch" reaction of lower alkyl secondary amines and formaldehyde. These polymers may be quaternized or non-quaternized.

Additionally, various condensation polymers are also useful in the practice of this invention, such as those obtained by condensation of dimethylamine and epichlorohydrin.

Conotype polymers are described in Reissue Patent Nos. 28,807 and 2B, SOS, which are incorporated herein by reference. Polymers of this type are typically the vinyl addition polymers described above with low molecular weights and even 0.15 to 1.5
It has an intrinsic viscosity within the range of . Other cationic water-soluble condensation polymers such as those obtained from ethylene dichloride and ammonia, which may or may not be quaternized with methylene chloride etc., can also be used. Although the sections refer to the polymers of the invention as vinyl addition polymers, this description is also applicable to such condensation polymers.

As will be appreciated, all polymers useful in the present invention are cationically charged and water soluble. Although many are prepared from vinyl addition monomers, condensation polymers are also useful. The number of cationically charged monomers imparted to the water-soluble polymer is essentially unlimited;
Although it is anticipated that any water-soluble cationically charged vinyl addition or condensation polymer having a molecular weight of ,000 or more and retaining total water solubility may be used.
The present inventors do not intend to limit themselves to those listed above.

As mentioned above, the polymers used are copolymers and terpolymers of various vinyl addition monomers. Although acrylamide is a preferred nonionic monomer useful in preparing the copolymers useful in the present invention,
Other ionic monomers such as methacrylamide, as well as certain anionically charged monomers such as acrylic acid and methacrylic acid, various sulfonated water-soluble vinyl addition monomers, etc. can also be used.

The polymers used in the present invention are water-in-oil emulsions (e.g., U.S. Repatents 28,474 and 28,576
(both of which are herein incorporated by reference), in the form of a dry powder, or a dilute aqueous solution. In order to use the polymers of the present invention in the emulsification of ASA sizing agents, an aqueous solution with the polymer must first be prepared.

In the case of water-in-oil emulsions of vinyl addition polymers, we have determined that the water-soluble surfactant used to convert the water-in-oil emulsion is related to the action of the polymer used to emulsify the ASA size. It was found that it did not exhibit any harmful effects. In preparing polymer solutions from water-in-oil emulsion polymers, a useful method or apparatus for forming the solution is disclosed in US Pat. No. 4.4, which discloses a mixed block.
057,223.

Final sizing emulsion 0.0 to be added to the /4 loop composition depending on the molecular weight and cationic charge of the polymer.
From 1 to 25 parts by weight, especially from 0.01 to 10 parts by weight, may be a polymer.

z? according to the present invention? The ASA Emulsigon supplied to the Lupus slurry contains the following ingredients: 50-99.9 parts by weight water 0.0 bone width 50 part A-bone width 0001-25.0 parts by weight water-soluble polymer.

Preferably, these emulsions contain the following ingredients: 50 to 99.9 parts water 0.01 to 40 parts ASA 0.010 to 10 parts polymer Most preferably the ASA emulsions contain 001 to 75 parts of polymer, more typically 1 to 5.0 parts of OO.

Therefore, the 1 +7 mer is used in the preparation of dispersions or emulsions of ASA Zyziking materials.

The polymers of the present invention can be used to emulsify ASA'i or can be added to preformed ASA emulsions. In both cases, the polymer has a
It will increase the efficacy of the emulsion. When adding polymer to an already formed ASA emulsion, the usual emulsifier is yj? IJ mom - should be used in addition. No other additives are required if added or used during making the ASA emulsion.

To test the invention, the following experiment was conducted. The polymers listed below were either commercially available or prepared as described.

Examples 1-10 Type DMAEM-MsCl quaternary salt, acrylamide copolymer solution of MAPTAC and 10,000-400
．． 000 molecular weight polyDADMAC, as well as several condensed 4-limer i ASA emulsification and retention aids. These novel sizing compositions are based on ASA particle size,
A description of these polymers compared by physical emulsion stability and sizing performance against conventional ASA emulsions in water or cationic starch is given in Table 1.

1) ASA emulsion was prepared by combining 95 parts distilled water and 5 parts ASA in a Niepelbach semi-micro emulsion cup. The mixture was dispersed at high speed for 3 minutes. The resulting emulsicon was diluted with distilled water to O,!10% AHA solid base and then incorporated in Example 1.An ASA emulsion of cationic starch was prepared using 5 parts of cationic starch in 95 parts of water. Pre-glued cationic potato starch was prepared by first hydrating and stirring for 30 minutes.The size emulsion was then combined with 75 parts starch liquid in a 25 parts ASA i emulsion cup and then mixed for 20 seconds. To disperse K
It was prepared from This emulsion? ASA of 0.501
Diluted to solid base and used in Example 2. Finally, add vinyl addition polymer ASA Emulsi N/A8 to the primer solution.
It was prepared by dispersing A't in a 5:1 ratio of dry solid base. These emulsicones were diluted into 0.50% ASA solid base by the method previously described. Example 3~
8 describes a novel use of these addition polymers.

Recirculate the ASA emulsion with 50 m/y, yr,
Other Nuralino flatmeters tested separately in a base slurry of 504 recycled newsprint composition were 0.51 consistency, 400 Canadian Standard Freeness (Fr.
eeene8m), pi(7,5), and 12.5 parts added per million aluminum sulfate hydrate25
Degree Celsins.

A handsheet with a basis weight of 950 pounds per 3300 square feet was prepared according to the TAPPI T-205 procedure. Add the above-mentioned sizing agent to the oxide gold immediately before forming the wet paper.
- Gloss - 0.10 and 0.15% of the solids content was added to the base 74-slurry (added) to the solid base of Examples 11-18 in a rotating drum immediately. Copolymers of MeC1 quaternary salt or MAPTAC with acrylamide and vinyl addition polymers such as polyDADMAC were further evaluated as ASA emulsification and retention aids. These new Saijisui/G compositions were
Comparisons were made regarding emulsion particle size, physical processing stability with aging, and aging efficacy against conventional ASA emulsions of water or cationic starch. The molecular weight of these polymers is io,ooo~400,000
It was within the range of Descriptions regarding these /IJ moms can be found in Table ①.

ASA in water emulsion with 95 parts distilled water and 5 parts A
The SA was prepared by combining in a laboratory 8 oz off-teriday cup. The mixture was dispersed at high speed for 3 minutes. Dilute the obtained emulsion with distilled water.
．． 501 ASA solid base and used in Example 11. A cationic starch solution, ASA emulsion, was prepared by first hydrating 5 parts of pre-stratified cationic potato starch in 95 parts of water and stirring for 30 minutes. A sizing emulsion was then prepared by combining 95 parts starch and 5 parts ASA in an Osterizer cup and dispersing the sizing agent for 25 seconds. The emulsion was diluted to 50% ASA solid base and then used in Example 12. ASA emulsions of vinyl addition polymers were prepared by dispersing the ASA in an I remer solution for 5 to 30 seconds at a ratio of ASAI:1 to polymer solids in Osteriderideka. These emulsions are then prepared as described above.
．． Diluted to 50% ASA solids. Examples 13-18 illustrate novel uses of these vinyl addition polymers.

Each ASA emulsion was tested separately in a base slurry of composition 50% bleach softener kraft and 504 bleach hard water kraft bulb. Other slurry parameters are 0.51 consistency, 330 Canadian standard freeness, p) 17.3 and 27 degree celsius.

A handset with a basis weight of 3300 ft.) was prepared according to the TAPPIT-205 procedure. The easing composition listed above was added to the paper slurry at a dosage of 0.201 ASA solids to 1,000 solids of paper just prior to wet paper formation. Immediately, the dried sheet was pressurized to about 50% residual moisture and dried in a rotating drum dryer to a 98% solids base. CONCLUSIONS 19-27 The following examples further illustrate the use of molecular weight 1.0 as emulsifiers and retention aids for alkenylconophosphate sizing compositions.
00,000 or more acrylamide copolymer type D
MAErvi-MeSQ, DMAEA-MeSQ
.

A novel use of DEAEA-Me SQ and DADMAC is described. The resulting ASA emulsions were compared with respect to particle size and sizing performance with respect to conventional emulsions obtained from ASA water emulsions and cationic starches.

For comparison, ASA emulsion in water and Niepelbach semi-micro emulsion are 7' in 95'! 117) Prepared by combining distilled water and 5 parts of ASA and dispersing the size for 60 seconds. The resulting emulsion was diluted to 0.504 ASA solid base with water and used in Example 19. ASA of cationic starch
Emulsion, '! -t” 97 m of stirred cold water 3
Preliminary gluing cationic pa? Prepared by hydrating tetostarch for 30 minutes, then dispersing the emulsion in a semi-micro emulsion cup using 30 parts of ASA in 70 parts of 3 parts cationic starch or 9 parts of ASA in 91 parts of 3 parts cationic starch, respectively. The ratio of two types of ASA to the starch solid content is 10
:1 and 3:1. The resulting emulsion was diluted with water to 0.5% ASA solid base and then Example 2
1 and Example 22.

Each of the copolymers listed below was prepared by hydrating 0.6 parts (as polymer solids) of each of the following copolymers of acrylamide in 99.4 parts of water and mixing for sufficient time to ensure complete hydration. . Add AS to 94 parts of a 0.61 polymer solids solution using a semi-micro emulsion cup.
By dispersing 1.8 parts of ASA in 6 parts of A or 98.2 parts of a 0.6% polymer solids solution, the emulsion was prepared in a 10:1 ratio of the two ASAs to polymer solids.
and 3:l.

Further dilution was performed to 0.5% ASA solids. The following examples illustrate the advantages provided by the present invention: AS of these cationic water-soluble acrylamide copolymers
A. Emulsion initiation ability and ability to use ASA emulsion particles as a cellulose substitute.

Each of the ASA emulsions listed below was prepared with a composition of 40 parts of bleach hard water sulfate, 40 parts of bleach softener sulfate), 20 parts of 300 Canadian standard freeness (u(8,2) calcium carbonate). 0,5 with
were added separately to the Chico/Cystinchyi pulp slurry. A 3300 square foot basis weight 50 bond handsheet was prepared according to the TAPPIT-205 procedure. Dry the ASA emulsion immediately before forming the wet paper iJ? The sheets were dried in a rotating drum dryer to a 98% solids base (2% residual moisture). The results are shown in Table ■.

This example clearly illustrates the use of cationic vinyl addition polymers as ASA emulsification aids and emulsion retention aids. Improvements in water resistance have been realized over conventional AS8 in water or cationic starch emulsions. Secondly,
Improved water resistance (・soil,
These same cationic polymers cannot simply contribute to improved paper machine retention, as demonstrated by adding them separately to the paper composition.

However, use of polymers in this molecular weight range resulted in the formation of sticky deposits and unstable emulsions.

As a result of further research as demonstrated by the present invention, the following contents were found. That is, polymers having molecular weights greater than or equal to io, ooo and less than 1,000,000, more preferably from 20,000 to 750,000, had performance comparable to polymers having substantially higher molecular weights. In addition, 50,
It is believed that the use of polymers having molecular weights in the preferred range of 0.000150.000 eliminates the formation of deposits described above and further increases the safety of the ASA emulsion so prepared.611 ° Margin Examples 28-39 Below The effects of various other polymers on the emulsification of ASA sizing materials as well as the results obtained using such polymers were reviewed. In this type of experiment, three different classes of polymers were used (see below). All these materials were prepared as polymeric water-in-oil emulsions. Poly! to obtain a product base of about 2 tIb or a polymer solution of about 0.6 tIb width. An aqueous solution of - was prepared. The polymer solution was diluted with 288.9% deionized water (and an ethoxylated (9) nonylphenol surfactant) in a double bone width solution of 6.
Om/i mixed together, then water-in-oil emulsion approx.
cc was prepared by adding cc to the stirred mixture.

The aqueous solution was then adjusted to obtain a double-width polymer product. The ASA selected for this series of studies was a substituted (alkenyl) cyclic dicargenic acid anhydride, in which the alkenyl group contained 14 to 22 Derived from a mixture of carbon atoms.

The ASA sizing agent comparison used in these tests was
It was prepared by mixing Polymer Solution 19611 with 4.0 liters of conventional paper-grade alkenyl succinic anhydride sizing agent available from Tiburon Chemical Co., Ltd.;
Contains 1.0 wt. fac RM-510 surfactant. The resulting mixture was then mixed in an Epelpach semi-micro emulsion cup for 30 seconds and then received at a final dilution of 0.51 ASA solids.

Add ASA emulsion to 40% of dry sample solids.
A dose of 259 g was added to a commercially available calcium carbonate filled bleaching kraft composition.

The neutral ink penetration test is concerned with the resistance of paper to the penetration of aqueous liquids and is further tested to a predetermined degree (80
It is a measurement of the time (in seconds) required for the ink to penetrate the paper relative to the end point (% reflectance). The more time, the more resistant the paper will be to ink penetration.

Those skilled in the art will readily recognize this test as the commonly performed Herkie Lama size penetration test. See the results
Shown in the table.

Q Acrylamide-MAPTAC97,5: 2.5
--R95:5 13.7 S 85:15 11. OT Acrylamide-DMAEA-Q 97.5:
2.5 --U 95:5 14.3 V # 85:15 12.6 W Acrylamide)"-DMAEM-Q 97.5:
2.5 --X 95:5 14. I Y 85:15 12.3 Z 92.3 Near, 7 -- Below margin

Claims (1)

[Claims] 1. An improved method for preparing an emulsified alkenyl succinic anhydride sizing agent useful in the production of sized paper products, the emulsion comprising water, alkenyl succinic anhydride, W, and a cationic agent; At least io, oo as a cationic agent
The method comprises using a water-soluble cationic vinyl addition polymer having a molecular weight of 0. 2. The cationic vinyl addition polymer is io or oo. Polymer monomers selected from water-soluble vinyl addition polymers having a molecular weight greater than and less than 1,000,000, the polymers being prepared from cationically or cationically modified vinyl addition monomers. Claim 1 having a content of at least 10 A and a weight factor of 100
The method described in section. 3. The cation or cation-modified vinyl addition monomer is a, diallyldimethylammonium chloride: b, methacrylamide propyltrimethylammonium chloride; C1 dimethylaminoethyl methacrylate; d, dimethylaminoethyl methacrylate quaternary salt; e, dimethylaminoethyl Acrylate; f, dimethylaminoethyl acrylate quaternary salt; g, diethylaminoethyl acrylate; h, diethylaminoethyl acrylate quaternary salt: 16 reaction product of acrylamide, formamide, and lower secondary amine by Mannich reaction; and j, Mannich reaction 3. The method according to claim 2, wherein the acrylamide quaternary salt is selected from the group consisting of acrylamide quaternary salts. 4. The polymer has a polymer solid content of 0.01 to 10.
2. The method of claim 1, wherein the alkenylconophosphate sizing agent is present in the emulsion at a level of 0% by weight. 5. The polymer has a polymer solid content of 0.01 to 5.0
The method of claim 1, wherein the alkenylconophosphate sizing agent is present in the emulsion at a range of levels by weight. 6. A paper sizing method in which an emulsion of alkenyl succinic anhydride is applied to a paper material and an alkenyl cono-phosphate sizing agent is used as an emulsifier for the alkenyl cono-phosphate sizing agent. 1
The method comprises using a water-soluble cationic vinyl addition polymer having a molecular weight of less than ,000,000. 7. The following monomer containing one or more cationic water-soluble vinyl addition polymers: a, diallyldimethylammonium chloride; b, methacrylamide propyltrimethylammonium chloride; c, N-methylaminoethyl methacrylate; d, dimethylaminoethyl methacrylate; class salt; e, J methylaminoethyl acrylate; f, dimethylaminoethyl acrylate quaternary salt; g, diethylaminoethyl acrylate; h, diethylaminoethyl acrylate quaternary salt;
1. A reaction product of acrylamide, formamide, and a lower secondary amine obtained by a Mannich reaction; and j. Homo- and copolymers of acrylamide quaternary salts subjected to a Mannich reaction, according to claim 6. the method of. 8. The method according to claim 6, wherein an emulsion containing a water-soluble polymer is added to the paper stock. 9. The following a-c: 8.50-99.9 weight range of water, o, 01-40 weight range of alkenyl succinic anhydride e, 0.001-10.0 weight range of io, over ooo An emulsion of a water-soluble cationic vinyl addition polymer colored alkenyl succinic anhydride having a molecular weight of . 10. The water-soluble cationic vinyl addition polymer comprises a,
diallyldimethylammonium chloride; b, methacrylamide propyltrimethylammonium chloride; C, dimethylaminoethyl methacrylate; d, dimethylaminoethyl methacrylate quaternary salt; e, dimethylaminoethyl acrylate; f, dimethylaminoethyl acrylate quaternary salt: g, Diethylaminoethyl acrylate: h, Diethylaminoethyl acrylate quaternary salt:
i. A reaction product of acrylamide P, formaldehyde, and a lower secondary amine by a Mannich reaction; and j. A homopolymer and a copolymer of an acrylamide quaternary salt subjected to a Mannich reaction.Claim No. 9 Emulsion as described in Section. 11. An improved method for producing an emulsified alkenyl succinic anhydride sizing agent useful for producing sized paper products, wherein the emulsion comprises water, an alkenyl succinic anhydride, a sizing agent, and a cationic agent. using a water-soluble cationic condensation polymer having an intrinsic viscosity of at least 0.15. 12. The method according to claim 11, wherein the cationic condensation polymer is a polymer of epichlorohydrin and dimethylamine. 13. Add the above polymer to an alkenyl cono-phosphate anhydride-sized emulsilane, and add 0.01 to 10 to each part of alkenyl cono-phosphate anhydride contained in the emulsion silane.
．． 12. Process according to claim 11, characterized in that 0 parts by weight of polymer are obtained. 14. The following aNe: a, 50-99.9% by weight of water, 0.01-50% by weight of alkenylconollic anhydride, c, O,OO of 1-5.0% by weight, more than 0.15 An emulsion of alkenylconolic anhydride comprising a water-soluble cationic condensation polymer having an intrinsic viscosity of