JP2002529603A - Poly (vinyl alcohol) copolymer ionomer, its preparation, and its use in fabric size - Google Patents

Abstract

  (57) [Summary] Certain poly (vinyl alcohol) copolymer ionomers, as well as compositions that are mixtures of other sizing polymers with such ionomers, and fiber sizes based on such compositions are described. A method for preparing the ionomer is described. This composition is a poly (vinyl alcohol) copolymer having carboxylic acid ionomer comonomer units. Such ionomer-based sizes can be obtained from aqueous solutions of ionomers, or solutions of these and other poly (vinyl alcohol) s and their mixtures, or solutions / suspensions of various starches and ionomers, or both. is there. Desizing in water or in caustic solutions is generally far superior to similar polymer mixtures that do not contain a poly (vinyl alcohol) copolymer ionomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to compositions of certain poly (vinyl alcohol) copolymer ionomers, methods of preparing such compositions, and sizes of fabrics based on such compositions. The invention also relates to sizes based on mixtures of such ionomers with other poly (vinyl alcohol) copolymers or starch. This composition is:
It is a poly (vinyl alcohol) copolymer having a carboxylate ionomer comonomer unit. Desize of such ionomers or mixed sizes containing such ionomers in water or caustic solution is based on a copolymer or mixture of polymers that do not contain a poly (vinyl alcohol) copolymer ionomer. It is easier than desizing.

2. Discussion of the Related Art Poly (vinyl alcohol) homopolymers and certain poly (vinyl alcohol) copolymers with comonomers such as alkyl acrylates have been known for many years for use as fabric sizes. Have been. For convenience, both will hereinafter be referred to collectively as PVA polymers. If they need to be identified,
Homopolymers and PVA copolymers will be referred to. By convention, PVA homopolymers include only partially "hydrolyzed" or "saponified" homopolymers, PVA polymers derived from poly (vinyl acetate), and "completely (
> 98%) derived from "hydrolyzed" homopolymers. Where distinction is required, the terms "fully hydrolyzed PVA homopolymer" and "partially hydrolyzed PVA homopolymer" are used. It is also possible to include fully or partially hydrolyzed PVA copolymers. In fact, certain partially hydrolyzed copolymers have found particular use as sizes for hydrophobic fibers, as described below.

[0003] Different types of PVA polymers have very remarkable differences in the size properties of the fabrics and the possibility of desizing the fabrics glued therewith. This difference is mainly due to
It depends on the degree of saponification or hydrolysis, the type of comonomer and the comonomer content. Other factors, such as molecular weight and thermal history, can also be important for size characteristics.

[0004] PVA polymers are generally prepared by alcoholysis or hydrolysis of the corresponding poly (vinyl acetate) homopolymer or poly (vinyl acetate) copolymer. Strictly, alcoholysis carried out with a basic catalyst leads to the corresponding alkyl acetate and poly (vinyl alcohol) units and is carried out in alcohol as reaction medium. Hydrolysis in water generally uses higher amounts of metal caustic bases, and the corresponding metal acetate rather than alkyl acetate, and poly (vinyl alcohol)
Unit and bring. The formation of metal salts, such as acetates, has led to the use of the term "saponification" in this process, similar to the formation of metal salts of fatty acids by caustic in forming soap. When aqueous alcohol is used as the reaction medium, both hydrolysis and alcoholysis can occur. However, U.S. Pat. No. 2,940,948 discloses that under certain conditions, even with the use of aqueous alcohol, alcoholysis rather than hydrolysis occurs. Although this distinction is strictly dependent on the reaction product, the term has tended to be used less loosely. The product is commonly referred to as "hydrolyzed" or "saponified" product.

In cases where not all of the acetate groups are completely converted to alcohol groups, it is common to use the term “partially hydrolyzed” or “partially saponified”. It is a target. If the homopolymer poly (vinyl acetate) is only partially hydrolyzed, the resulting PVA is strictly a vinyl alcohol / vinyl acetate copolymer. However, as noted above, such polymers are generally PVA
Called a homopolymer. In this regard, the term copolymer usually refers to materials that result from the hydrolysis of the corresponding vinyl acetate copolymer, for example, polymers that also include units derived from monomers other than vinyl acetate, such as alkyl acrylates. Save for coalescing.

[0006] While fully hydrolyzed PVA homopolymer is very crystalline and strong,
Due to its high crystallinity, it dissolves only in hot water and does not dissolve in cold water. further,
Elevated temperatures can result in even higher levels of crystallinity than those prepared, resulting in a polymer that is more difficult to dissolve. Finishing mills using certain fabrics, especially blended fabrics, tend to use thermosetting conditions to relieve fiber stress. This treatment is usually carried out at a temperature that further promotes the crystallinity of the fully hydrolyzed PVA homopolymer, such that if such a polymer is used as the size of the fabric, this The treatment increases its crystallinity and subsequently reduces the ease of desizing.

[0007] PVA copolymers, and partially hydrolyzed PVA homopolymers, are less crystalline and dissolve at lower temperatures or more readily at a given temperature. As a result, they perform desizing more easily in water and are less susceptible to changes in crystallinity due to heat setting of the fabric and changes in the desizing function. However, for a given level of comonomer units, or residual non-hydrolyzed acetate units, the two types of PVAs are not identical in several respects. This is due in part to the distribution of comonomer units along the polymer chain (or units derived from the comonomer units by lactonization, as discussed below) along the chain after partial hydrolysis. This is because the distribution of the residual acetate units is not the same. For example, one of the differences
First, the acetate units tend to be blocky, and the blockiness of the partially hydrolyzed PVA, when used as a size, can further reduce the effect of surfactants and Causing more bubbling. In addition, differences in the conditions used for hydrolysis / saponification of a given copolymer,
In particular, it is disclosed that physical differences, such as the degree of agitation and kneading of the sedimented product, cause differences in the partially hydrolyzed product.

[0008] Various PVA copolymers have been disclosed as being useful for fabric size.
In 1972, U.S. Pat. No. 3,689,469 (Inskip et al.) Disclosed a PVA copolymer useful as a fabric size, containing 2 to 6.5 weight percent methyl methacrylate as a comonomer. These properties were compared to fully hydrolyzed and partially hydrolyzed PVA homopolymers. However, this disclosure has shown that copolymers in which methyl methacrylate is higher than about 6 weight percent are very soluble in water.

As a comonomer, methyl acrylate or methyl methacrylate may be used in the form of 1 to 1
A PVA copolymer containing 0 mole percent is disclosed in U.S. Pat. No. 4,990,335 (B
ateman et al.). (For methyl acrylate, this is
(Corresponding to about 2 to 16 weight percent of methyl acrylate in the polymer, calculated as a non-lactonized vinyl alcohol copolymer). The polymer was not disclosed as being useful for size.

However, recent US Pat. No. 5,362,515 (Hayes et al., 11/8/94)
In polymers having high acrylic ester comonomer levels or methacrylic ester comonomer levels (such as 7 to 15 weight percent methyl (meth) acrylate) above the Inskip comonomer level and within the highest range of Bateman comonomer levels. ) Was disclosed as being useful in a process for producing fabrics using such polymers for size. The polymer is disclosed to be very easily desizing, especially in caustic solutions.

[0011] Poly (vinyl alcohol) copolymers, in which the comonomer provides the acid functionality directly, are known. The acid functionality can be derived from copolymerized monocarboxylic, dicarboxylic, or dicarboxylic acid half esters. However, acid functionality can result from hydrolysis of an ester comonomer unit, such as an alkyl acrylate or an alkyl methacrylate. Depending on the exact conditions such as the catalyst, catalyst concentration, and solvent used to hydrolyze / saponify the vinyl acetate ester units in the vinyl acetate copolymer, other ester units, such as comonomer ester units, may be hydrolyzed. It may or may not be the corresponding acid. In general, vinyl acetate ester units hydrolyze much more readily than alkyl ester units. The alkyl ester units are also hydrolyzed and, if sufficient base is present, the resulting acid units can also be neutralized to ionomer units.

[0012] Under some conditions, an internal transesterification reaction can take place between the vinyl alcohol unit resulting from the hydrolysis and the alkyl ester unit, resulting in an intrachain lactone unit. Both the vinyl acetate ester unit and the alkyl carboxylic ester unit undergo hydrolysis, and the hydrolyzed alkyl ester unit can be neutralized depending on the exact conditions, thus providing a number of potential hydrolysates. Decomposition products are possible.

[0013] As noted above, if a sufficient amount of base is present, the acid units present under some saponification conditions from the acid comonomer or as a result of hydrolysis of the ester comonomer. Can be neutralized to form carboxylate (ionomer) units. However, if the PVA polymer is removed from solution due to solvent conditions, the ionomer units may not be present in the isolated polymer. While it may seem that the reaction conditions allow for the formation of such units in view of the complexity of the situation, whether the isolated polymer contains ionomeric units depends on many references. It is not surprising that nothing is apparent in it, and certainly not mentioned.

[0014] Poly (vinyl alcohol) copolymer ionomers contain a certain level of acid / ionomer units, often with some degree of saponification / hydrolysis of vinyl acetate ester units, while It is stated to be used as a size for different materials such as textiles.

In particular, it is known to use certain poly (vinyl alcohol) copolymers containing ionomer units as sizes for hydrophobic fibers. Tokiko Sho 55-
44191 (11/11/80, JP 49-66988, 6/28/74) discloses a portion of vinyl acetate containing 0.1 to 10 mole percent monoalkyl maleate used as such size. Discloses copolymers which have been saponified. The level of saponification must be between 50 and 80 percent and it is disclosed that adhesion to hydrophobic fibers is inadequate and even flocculation is reduced. Alkali salts of monocarboxylic acid ester PVA copolymers are specifically disclosed as part of the invention. The comonomer units in the precursor polymer must be monoalkyl maleate. A polymer sizing solution is disclosed.

Japanese Patent Publication No. 60-14148 (4/11/85, JP-A-53-134990, 11
/ 25/78) is also a low saponified (65-90 mole percent) vinyl acetate copolymer (in this case, a vinyl acetate / monocarboxylic acid copolymer saponified with up to 3 mole percent acid) Sizing material). This product is also particularly useful for hydrophobic materials. If it exceeds 3 mole percent, when used as a size, excessive hygroscopicity occurs, lacks adhesion,
It is disclosed that the weaving efficiency is poor. The product may be prepared using alcohols, water, or alcohol, using either alcohol metal or metal hydroxide, under very specific conditions, especially without kneading or mixing, while the solid product is obtained. Produced by saponification at low temperature in aqueous alcohol. The example polymers contain up to 0.8 mole percent acid and an excess mole of base. However, nothing is shown about the metal hydroxide (ionomer) groups in the isolated saponified polymer.

JP-B-60-31844 (7/24/85, JP-A-53-91995, 8/1)
2/78) is from 0.1 to 50 dicarboxylic acid units from the dicarboxylic acid monomer.
The preparation of a PVA copolymer containing mole percent is described. This includes
It has been disclosed that polymers made by special methods are superior to prior art acid copolymers for applications such as paper reinforcement, fiber sizing, and adhesives. This particular method involves saponification using 2 moles of alkali per mole of dicarboxylic acid, plus 0.1 to 1.0 moles of alkali per mole of vinyl acetate, as well as controlling the concentration of dicarboxylic acid to control the polymerization. This is a solution method that maintains solubility throughout. Thus, while large amounts of base are present, this disclosure specifically mentions avoiding alkalis that remain in the saponified PVA polymer. Thus, the saponified product does not appear to contain metal carboxylate units.

US Pat. No. 4,747,976 (Yang et al.) Discloses use in washing laundry.
A water-soluble film pouch containing a surfactant is disclosed. The film is a PVA copolymer containing ionomer units derived from various comonomers, including methyl acrylate and methyl methacrylate. The concentration of comonomer in the polymer before saponification is between 2 and 6 mole percent. Of the comonomer units, it is believed that only 1 to 5 percent of the conomer units are converted to ionomer units. The disclosure vaguely states that "about 1 to 5 mole percent of the comonomer is converted to anionic comonomer." Perhaps this is because the final polymer has up to 5 percent of acrylate or methacrylate units converted to anionic units, or has a maximum of anionic units in the final polymer. It would mean having 0.3 mole percent.

Desizing usually requires water washing. However, desizing certain polymers with caustic solutions is also well known and has been described. Published Patent Publication 60-
No. 14148 uses, for example, a sodium carbonate solution as a desizing agent.

The solubility and dissolution time of various types of PVA polymers in water and caustic solutions are described in “Polyvinyl Alcohol”, Chapter 11, 1992, Jo.
hn Wiley & Sons Ltd. , P 365-368. Among them, partially hydrolyzed PVA homopolymers dissolve more slowly in caustic solutions than in water, whereas PVA copolymers having methyl methacrylate as a comonomer are more caustic than water. In particular, it is noted that it dissolves more rapidly. This indicates that caustic further hydrolyzes the partially hydrolyzed PVA to homopolymer, while the lactone ring, which can be derived from the comonomer, along with the copolymer, Decomposed, so that
This is explained by the fact that highly soluble ionic groups result. On the other hand, if free acids are present rather than lactone units, the free acids will be neutralized to form ionomer units.

Numerous other materials are known for use as fabric sizes. Unmodified starches are inexpensive, but generally do not have the properties as good as PVA polymers, and often strip the yarn when used as a size. Undenatured starch does not provide a stable solution and often requires the use of enzymes for desizing. A number of modified starches with various improvements over simple starches are known, but can be quite expensive. Polyacrylic sizes are also known and have excellent properties, but are extremely sensitive to water.

It is known and used to mix different gluing materials. It is well known that mixing can provide the properties of the size itself, as well as the intermediate economics of such components. As noted above, the polymer described in US Pat. No. 5,362,515 is disclosed in US Pat. No. 5,436,29.
No. 2 (Hayes et al., Issued Jul. 25, 95) and US Pat. No. 5,405,653 (Hayes et al., Issued Apr. 11, 95).
It is disclosed as being useful as a size mixed with the starch therein. The mixing of the readily desizing polymer of US Pat. No. 5,362,515 with starch and other PVA polymers was disclosed as a means of increasing desizing performance.
These three patents are incorporated herein by reference.

It is clear that the mechanism of desizing using caustic solution can involve in-situ formation of ionomer species in PVA copolymer (as PVA copolymer by Hayes's reference). Consider using a highly hydrolyzed PVA copolymer ionomer with respect to vinyl acetate units in the precursor poly (vinyl acetate) copolymer, as the size itself or as a desizing enhancer in a mixed composition It doesn't seem to.

[0024] The ease of desizing can have a profound effect on the economics of textile products. Numerous sizing materials are known, each having its specific niche, while being much easier to desizing, having acceptable mechanical properties, and providing a stable size solution There is still a need for more advanced size materials. There is still a particular need for sizing materials that can be more highly desizing than known materials, because they are at a much lower level, even when added to these known sizing materials. This is because these known materials can be used to increase the desizing performance. In such elevated levels of use, the less desirable attributes of highly desirable materials, such as hygroscopicity, which can lead to stickiness, are that highly desirable materials are needed only at lower levels. Is minimized in the overall composition.

SUMMARY OF THE INVENTION The present invention is directed to a novel sizing composition that improves upon that described in the Hayes et al. Patent described above. The sizing composition is an aqueous solution of a polymer, or a polymer mixture containing the polymer, wherein the polymer has a controlled level of 0.1 to 10 mole percent of anionic carboxylate (ionomer) units. Is a PVA copolymer ionomer having Fabrics glued in such a size can be very effectively desizing compared to known size materials.

More specifically, the present invention provides a method wherein the copolymer ionomer is a precursor of a poly (vinyl alcohol) copolymer ionomer having from 0.1 to 10 mole percent of anionic carboxylate units, vinyl acetate A sizing solution comprising 1-2 weight percent of an aqueous polymer solution comprising a first polymer that is hydrolyzed to 90 to 100 percent, with respect to vinyl acetate ester units, remaining from the copolymer.

[0027] The sizing solution further comprises an amount of 10 to 90 weight percent of the second polymer relative to the total weight of the first and second polymers, wherein the second polymer comprises C1-C
Poly (vinyl alcohol) homopolymer or poly (vinyl alcohol) containing up to 15 weight percent of units derived from 8 alkyl (meth) acrylates or C1-C3 dialkyl fumarate or dialkyl maleate It is a non-ionomeric poly (vinyl alcohol) polymer which is a copolymer.

[0028] The size solution may further comprise, from the third polymer 10 to 90 weight percent with respect to the sum of the first and third polymers, in addition to the first polymer alone. The polymer of No. 3 is a natural starch, a synthetic starch, a physically modified starch, or a chemically modified starch.

A further aspect of the present invention is a method of preparing a poly (vinyl alcohol) copolymer ionomer, wherein the copolymer ionomer is obtained from the corresponding poly (vinyl alcohol) copolymer by means of 0.1 ionomer units. Having from 1 to 10 mole percent, the corresponding poly (vinyl alcohol) copolymer is a conomer derived from a C1-C8 alkyl (meth) acrylate, or a C1-C3 dialkyl fumarate or dialkyl maleate. Of 0.1 to 10 mole percent, which leaves the starting polymer of the poly (vinyl alcohol) copolymer, and the derived ionomer, insoluble as a slurry, In a reaction medium that can be isolated as a solid granular polymer, or in a solution for the derived ionomer This is done by completely or partially hydrolyzing such comonomer units with a base in a reaction medium which directly provides a solution which is both useful and sized.

DETAILED DESCRIPTION OF THE INVENTION In this disclosure, when reference is made to PVA copolymers, the use of the term comonomer as used herein, and conventionally used, is in addition. Alcohol decomposition /
It is to be understood that by hydrolysis / saponification, the poly (vinyl acetate) copolymer refers to a comonomer that is copolymerized in the poly (vinyl acetate) copolymer before it is converted to a PVA copolymer. .

The term hydrolysis, or saponification, refers to the conversion of vinyl acetate ester units into poly (vinyl alcohol) units in poly (vinyl acetate), even when the reaction is strictly alcoholysis. Used to siege. The term hydrolysis also refers to the conversion of an ester unit of an alkyl or dialkyl ester comonomer unit to a free acid unit, or a lactone unit (eg, an internal ester unit).
Also used for conversion to free acid units. Use the conventional term "neutralization" if the acid units are converted to ionomer units with a base, or use "partial neutralization" if not all of the acid is neutralized I do. Furthermore, when referring to polymers, the well-known term "ionomer" (usually used for ethylene copolymer ionomers) is used, as well as the term "ionomerization." The ionomer unit is an anionic carboquinate unit or a carboxylate unit,
All of these terms shall be used interchangeably.

A PVA copolymer is prepared by hydrolysis / saponification of a corresponding poly (vinyl acetate) copolymer containing the same comonomer. The poly (vinyl acetate) copolymer will be referred to as the "precursor" copolymer. PVA copolymer ionomers are prepared from PVA copolymers having comonomer units only by hydrolysis and / or neutralization (depending on whether the comonomer is an acid ester or an alkyl ester which must first be hydrolyzed). . The PVA copolymer before ionomerization is
To avoid confusion with the precursor acetate copolymer, it will be referred to as the "starting" copolymer.

The polymer of the present invention is used as a poly (vinyl alcohol) copolymer ionomer, PVA
Copolymer ionomers, or simply ionomers for convenience. When used alone the term PVA copolymer refers to a polymer without ionomer units. However, the term PVA copolymer ionomer can also include some residual non-hydrolyzed vinyl acetate units, and further, unhydrolyzed, residual lactone (internal ester) units and / or residual acrylic acid Includes polymers that can specifically contain methyl ester units or methacrylic acid methyl ester units.

It is well known that in PVA copolymers, ester comonomer units react with hydroxy groups from adjacent vinyl alcohols to form lactones and form free alcohols from ester units. Thus, the initial ester monomer units can no longer be present as the same entity as was present in the precursor poly (vinyl acetate) copolymer. The degree can vary with different comonomers and hydrolysis conditions, but almost complete lactonization can occur. The use of phrases such as PVA copolymers "with" or "containing" a given comonomer etc. should be understood within this context.

[0035] Starch is a macromolecule, and is referred to in this disclosure as a "polymer," which is, of course, a polymer of a significantly different type from strictly synthesized polymers such as PVA polymers. is there.

The PVA copolymer ionomer has been found to be uniquely useful in the preparation of textile sizing compositions. This is due to the exceptionally rapid desizing capability, both in water and in dilute caustic solutions. The PVA copolymer ionomer is a PVA having an equivalent comonomer content as described in previously referenced US Pat. No. 5,362,515.
It is much easier to desizing than a copolymer composition.

In addition, the size based on the mixing of either PVA polymers or starches of the prior art with PVA copolymer ionomers, both previously known for use as sizing materials, is PVA It can be desized more easily than many equivalent PVA polymer mixtures without the copolymer ionomer.
Because PVA copolymer ionomers are very easily desized, they can be used at relatively low levels in blends with other PVA polymers or starches, and may be attributable to PVA copolymer ionomers. It achieves a significant improvement in desizing performance without adding certain inherent disadvantages. Therefore, in the mixture, P
VA copolymer ionomers can be used in amounts as low as 10 percent, rather than the major admixture. Of course, in many cases, depending on the starch or PVA polymer to be mixed modified, high levels of PVA copolymer ionomer may be advantageous.

[0038] The size of the present invention may be a PVA copolymer ionomer alone, a PVA copolymer ionomer and a non-ionomer PVA polymer, a PVA copolymer ionomer and a starch, or a PVA copolymer ionomer and a non-ionomer PVA polymer and a starch. And can be in solution. The PVA copolymer ionomer of the present invention can be, to a limited extent, a mixture of PVA copolymer ionomers, each having a different composition. Similarly, non-ionomeric PVA polymers are, to a limited extent,
It may include a mixture of non-ionomeric PVA polymers. Starch can also include a mixture of starches. It is to be understood that the terms PVA copolymer ionomer, non-ionomer PVA polymer, and starch used in the claims include mixtures in the aforesaid sense.

The PVA copolymer ionomer of the present invention is derived from a poly (vinyl acetate) copolymer having comonomer units that can be converted to ionomer units.
The vinyl acetate units in the precursor polymer are highly saponified / hydrolyzed, but at least 90% hydrolyzed, preferably 95% hydrolyzed, but can be "fully" hydrolyzed. The ionomerization reaction (using a base) on the alkyl ester units during preparation of the ionomer from the starting PVA copolymer also acts to hydrolyze the remaining vinyl acetate units. It is believed that the vinyl acetate ester units are actually hydrolyzed preferentially over the alkyl ester units and that little vinyl acetate will remain. However, in the ionomer, only a low molar percentage of the ionomer units is desired, so that if the amount of base used in the ionomerization reaction is small, it appears that some vinyl acetate units remain. For the entire ionomer, the mole percent of vinyl acetate remaining was 10%.
Less than percent, consistent with precursor vinyl acetate units that are hydrolyzed by more than 90 percent. In ionomers containing greater than 2 mole percent ionomer units, it is believed that at least 95 percent of the vinyl acetate units are hydrolyzed to vinyl alcohol units, and perhaps more than 98 percent. However, no attempt was made to accurately measure the level of residual vinyl acetate units. These low levels of residual vinyl acetate are prominent in contrast to the ionomers prepared from the precursor poly (vinyl acetate) carboxylic acid or monoalkyl maleate copolymer discussed in the background section. In such polymers, the ionomer units are formed by neutralization of the acid units, and the vinyl acetate units clearly remain, indeed requiring the disclosed utility. Therefore, in such polymers, the hydrolysis of vinyl acetate is relatively low.

The ionomers of the invention are generally very suitable for hydrophilic fibers. But,
Since the level of ionomer units can be as low as 0.1 mole percent,
It is also suitable for hydrophobic fibers. The ionomer can be used in admixture with other PVA-based sizes, or starch sizes, and in the mixture:
The utility of the ionomer for different fibers can vary depending on the other components in the mixture, and the ionomer level. The level of ionomer units can vary from 0.1 to 10 mole percent, but is preferably 2 to 8 mole percent. In a mixture, the actual amount of ionomer units generally varies, both by varying the number of ionomer units in the PVA copolymer ionomer in the mixture and by varying the amount of PVA copolymer ionomer in the mixture. can do. Thus, for a given hydrophobic or hydrophilic fiber, the most suitable composition is determined by varying the percent ionomer units in the PVA copolymer ionomer, as well as the proportion of the PVA copolymer ionomer, in the mixture. Obtainable. Thus, within the scope of the invention, there are a large number of variables that can be changed, and thus there is great diversity in achieving maximum fit. Despite considerable trial and error, it is still within the skill of the ordinary artisan to determine the optimal composition that most closely approximates the desired sizing characteristics and the desired desizing performance.

Yet another variable that can be manipulated independently of the number in the PVA copolymer ionomer is the mole percent ionomer units. Therefore, the number of methylalkyl (meth) acrylate comonomer units (or twice as many in the case of alkyl maleate / alkyl fumarate units) in the precursor PVA copolymer is dependent on the derived PVA copolymer. It can be greater than the number of ionomer units in the polymer ionomer, since complete hydrolysis of such ester units ("ionomerization") is not essential. As noted, unconverted alkyl esters, or derived lactone units, may remain. Thus, there are numerous variables within the inventive composition that can be adjusted to suit a given fiber.

In the mixed compositions tested, the ease of desizing can, in a very rough sense, desize the mixture rather than being ng limited by the most difficult components to desize. It was found to be a weighted average of the ability. This is because in sizing materials that are difficult to desizing, if a particular property of the sizing material is desired, e.g., specific properties, or low cost, a mixture with the PVA copolymer ionomer will have a desizing property. This means that an ideal compromise between desizing capabilities can be provided. Of course, the simplest way to change the ionomer content in a mixed size composition is to change the PVA in the composition rather than to change the properties of the PVA copolymer ionomer.
The only change is the amount of A copolymer ionomer. The higher the amount of ionomer functionality in the PVA copolymer ionomer, the lower the amount required to introduce a particular amount of ionomer functionality into the mixture. This allows the advantageous sizing properties of the non-ionomer components of the mixture to be more dominant.

The PVA copolymer ionomer of the present invention can be made from a PVA copolymer that contains a comonomer that can be converted to an ionomer. Thus, the comonomer units can be free carboxylic acid units, or dicarboxylic acid units, and are simply neutralized to form the corresponding ionomer. However, it is preferred to avoid the presence of free acid comonomers and free acids. This is preferred because the free acid comonomer consumes the alcoholysis / saponification catalyst. A more preferred method of preparing copolymer ionomers is to prepare from PVA copolymers containing alkyl acrylates or dialkyl dicarboxylates, so that no free acid remains in the polymer . In addition, some ester units (external as acrylic esters or internal as lactones) can remain, adding diversity to the composition. P containing such a monomer
VA copolymers are made from the corresponding poly (vinyl acetate) copolymers.

The preparation of further PVA copolymer ionomers from such monomers involves a series of methods, some of which are well known in the prior art, but for clarity, , Are listed here and the quantities are given.

1. Preparation of poly (vinyl acetate) copolymers containing C1-C8 alkyl (meth) acrylates or C1-C3 dialkyl maleates or fumarate dialkyls. Preferably, the comonomer is an alkyl (meth) acrylate,
Most preferably, it is methyl acrylate. The molar amount of comonomer in the vinyl acetate copolymer will obviously be at least the molar amount of ionomer units required in the final PVA copolymer ionomer if an alkyl ester of a monocarboxylic acid comonomer is used. It must be as large as possible (or as much as one-half if dialkyl esters of dicarboxylic acids are used, since potentially two ionomer units can be derived from each comonomer unit). However, the molar amount in the poly (vinyl acetate) polymer can be higher. In the finally derived PVA copolymer ionomer, the molar amount of a suitable ionomer unit, when used in a size composition, is from about 0.1 to about 10%. When used as a size, levels higher than 2 percent are preferred. Above 10 percent, it is clear that excessive water sensitivity may begin. If an ionomer having 10 mole percent ionomer units is required, the precursor vinyl acetate copolymer contains 10 mole percent of this conomer relative to a monocarboxylic acid alkyl ester comonomer such as methyl acrylate, or Contains 5 mole percent dialkyl fumarate or dialkyl maleate.

In the art, comonomer levels are generally expressed as weight percent. In this regard, the preferred monomer, methyl acrylate, is 10 mole percent methyl acrylate because methyl acrylate and vinyl acetate have the same molecular weight relative to the vinyl acetate / methyl acrylate precursor copolymer. , 1
Equivalent to 0 weight percent. For methyl methacrylate, the weight percentage is even closer to 11 weight percent, and for higher alkyl (meth) acrylates, the weight percentage will, of course, be higher. However, for a given mole percent of the comonomer, the weight percent of that comonomer in the resulting PVA copolymer (rather than the weight based on the derived lactone,
Is calculated as its comonomer), because the molecular weight of the vinyl alcohol unit is low,
Note that it is much larger than in the poly (vinyl acetate) precursor copolymer. Examples include poly (vinyl acetate / methyl acrylate) copolymer, 90/10 weight percent or mole percent to poly (vinyl alcohol / methyl acrylate) copolymer, 90/10 mole percent, or about 80/100 mole percent. 20 weight percent is obtained.

Regardless of the value of the initial mole percent of alkyl acrylate units in the precursor poly (vinyl acetate) copolymer, only 0.1 mole percent in the finally derived PVA copolymer ionomer Need to be present.
For size compositions, at least 2 mole percent ionomer units are preferred. Whether an excess (eg, non-ionomerized) alkyl ester unit in a PVA copolymer ionomer is better or not, standard measurements to determine a given utility are useful. You can do trial and error.

[0048] 2. Partial or complete hydrolysis / saponification of poly (vinyl acetate) copolymer to the corresponding polyvinyl alcohol copolymer, for example, from poly (vinyl acetate) / methyl acrylate to poly (vinyl alcohol) Methyl acrylate is preferred. The degree of hydrolysis should be higher than 90 percent and can approach 100 percent to the extent that hydrolysis can be achieved. Typically, 99 to 99.8 percent is an achievable degree. The degree of hydrolysis is 95
Preferably it is higher than the percent. In many cases, depending on the exact conditions, the ionomer is prepared by hydrolysis of an alkyl ester comonomer in a PVA / alkyl ester copolymer, and the copolymer is prepared using the precursor poly (vinyl acetate)
(With respect to the vinyl acetate units in the copolymer precursor), if only partially hydrolyzed / saponified, the desired hydrolysis of the alkyl ester units and, together with the ionomerization, further hydrolysis of the vinyl ester units Also happens.

Poly (vinyl acetate) polymers, and poly (vinyl acetate) copolymers have their original utility in these rights and, thus, while isolated as such, And a significant portion of the copolymers are used, in particular, for the production of PVA. Preparation of poly (vinyl acetate) without isolation of poly (vinyl acetate) polymer,
And it is possible to perform saponification. Therefore, U.S. Pat. No. 2,940,948
No. 4 describes a process in which a slurry of a poly (vinyl acetate) homopolymer is directly hydrolyzed as prepared to a PVA polymer. This method is similarly applied to poly (vinyl acetate) copolymers. In other words, the two steps 1 and 2 are combined without isolating the polymer between the steps. In principle, in step 3 below, the conversion to the ionomer can be performed without isolating the PVA polymer, so that both the poly (vinyl acetate) copolymer and the PVA copolymer can be isolated. Instead, it is possible to use a combination method that combines the preparation, hydrolysis, and ionomerization of a poly (vinyl acetate) copolymer. The resulting PVA copolymer ionomer can even be made directly into a size solution without isolation as a polymer. However, this method, which is part of the present invention, involves only the step of converting the granular PVA copolymer into a PVA copolymer ionomer. This is called Step 3.

[0050] 3. Partially or fully ionomerized PVA of PVA copolymer
Conversion to copolymer ionomer (hydrolysis and neutralization in the same step). This step is described in detail below.

Conventional Preparation of Such Poly (vinyl acetate) Copolymer (eg Step 1)
And their hydrolysis describe a laboratory-scale preparation for copolymers containing up to 10 mole percent of alkyl (meth) acrylates, US Pat.
No. 9,469, and U.S. Pat. No. 4,900,335, which describes a continuous process for such polymerizations. During preparation, the amount of monomer in the feed is adjusted to different levels and different reactivity required in the polymer. These two patents are incorporated herein by reference.

[0052] Methacrylates are more reactive than acrylates, but both are more reactive than vinyl acetate, so that while they react completely, vinyl acetate, which is less reactive, Must be removed and reused in an industrial continuous process. Dialkyl maleates are considerably less reactive.

The saponification / hydrolysis of poly (vinyl acetate) polymers and poly (vinyl acetate) copolymers and isolation of PVA copolymers produced as powders are standard procedures well known in the art. Procedure. The PVA copolymer is usually isolated as a granular powder.

A preferred method of the present invention for preparing PVA copolymer ionomers comprises
Granular P containing from 0.1 to 10 moles of 1 to C8 alkyl (meth) acrylates or 0.1 to 10 moles of C1 to C3 alkyl dimaleates or dialkyl difumarate
A process for converting VA copolymers into PVA copolymer ionomers containing 0.1 to 10 mole percent anionic carboxylate units. The method itself can be performed in different ways. Further, after preparation, the polymer can be isolated as a solid material or converted directly into a size solution. While the limits of ionomer and comonomer in the starting PVA copolymer are the same, the amount of ionomerization need not be complete and is usually not complete. The number of ionomer units can be as small as a small percentage of the initial comonomer units in the starting copolymer. For example, P with 10 percent comonomer
If only one percent of the comonomer is converted to the ionomer in the VA copolymer, there will still be 0.1 percent of the ionomer unit, which is the size of the ionomer used in the size of the invention. It is the lowest ionomer unit. Typically, the conditions used convert an estimated 20 to 70 percent of the comonomer units to ionomer units, as described in the Examples below. However, no accurate analysis of any ionomer has been performed.

The PVA copolymer is mixed with a liquid reaction medium for a suitable time and at a suitable temperature, and is reacted with a suitable base which should be partially soluble in the reaction medium. The reaction medium is P
The VA copolymer as well as the resulting PVA copolymer ionomer can be selected on the one hand to ensure that it remains largely undissolved, so that the ionomer can be easily isolated. On the other hand, the reaction medium can also be chosen such that the PVA copolymer ionomer can be easily dissolved and form a size solution directly from the reaction mixture. With such a reaction medium, it is believed that the starting PVA copolymer can also be dissolved to some extent in the medium.

The former method uses a reaction medium that is close to a non-solvent for the PVA copolymer and even a poor solvent for the PVA copolymer ioomer formed. This method is referred to herein as the slurry method. Specifically, the reaction medium should not dissolve more than 5 percent of either the starting PVA copolymer or the resulting PVA copolymer ionomer. However, the reaction medium contains at least 0.1 base material.
001 weight percent must be dissolved. The reaction medium of the slurry method includes C1-C3 aliphatic alcohols such as methanol, ethanol and propanol, lower alkyl ketones such as acetone and methyl ethyl ketone, and mixtures thereof with water to such an extent that the solubility limit is not exceeded. and so on. Methanol and ethanol are preferred, optionally with water. The slurry can be a solid from 1 to 9
It may contain as little as 0 percent, but is preferably 5 to 40 percent, most preferably 10 to 30 percent.

The latter method uses a reaction medium that can be a solvent for the PVA copolymer ionomer formed and a partial solvent for the starting PVA copolymer. The reaction medium must be a solvent for the ionomer, but the reaction product may need to be heated to form a solution and must remain in solution upon cooling. This method is referred to herein as the solution method. In this case, the preferred reaction medium is water, but small amounts of lower alcohols are acceptable provided that the PVA copolymer ionomer remains soluble. The solution thus formed may have a concentration of 0.1 to 90 weight percent of the PVA copolymer ionomer formed in the liquid medium, preferably 5 to 40 weight percent, preferably 5 to 20 weight percent. Weight percent is most preferred.

The order of adding both the solution method and the slurry method can be changed. Thus, the polymer can be added to a base that is already in solution in the reaction medium, or a solid base or a solution of the base in a suitable solvent can be added to the PVA copolymer / reaction medium mixture.

Suitable bases include alkali metal hydroxides, alkaline earth metal hydroxides, quaternary ammonium hydroxides, and the like. Preferred bases are sodium hydroxide,
And potassium hydroxide. The amount of basic material required will depend on the basic material, the amount and proportion converted to the desired ionomer. Usually, stoichiometric amounts are sufficient, while excess amounts result in a more rapid reaction, based on the amount of alkyl ester units that are desired to be converted to ionomers. The amount of base is from 0.1 to 20 moles per 100 moles of monomer-derived units in the starting polymer, but the number of moles of comonomer-derived units (or lactone units derived therefrom) in the starting polymer is It can be only twice. For example, a starting polymer having 5 mole percent comonomer should use as little as 10 moles of base, based on the amount of polymer "containing" (eg, polymerized therein) 5 moles of comonomer. is there. For polymers having a maximum allowable amount of 10 moles of comonomer, the maximum amount is 20 moles of base, based on 100 moles of monomer and therefore the amount of polymer containing 10 moles of comonomer.

The rate of conversion of the PVA copolymer to the PVA copolymer ionomer is determined by the exact chemistry of the PVA copolymer, the amount of PVA copolymer in the reaction mixture, the reaction medium, and the amount of base used. And a complex function of the exact properties, reaction temperature, and reaction time. By analyzing the ionomer units formed, for example by IR, it is possible to determine the appropriate conditions. Typical conditions such as the time at certain temperatures and the media used for the different starting PVA copolymers and conditions are given in the Examples section. This provides guidance for other polymers and conditions.

As indicated above, it is desirable to isolate the ionomer PVA copolymer as a solid after the ionomerization step because it is convenient to market the dry granular PVA copolymer ionomer. This is because there is a good possibility. With respect to size, fabric producers will produce their own size solutions of PVA copolymer ionomers or PVA copolymer ionomers mixed with other PVA copolymers and starch. However, there are an infinite number of possibilities. The PVA copolymer ionomer is isolated as a dry granular material, mixed with other polymeric sizing materials,
The dry product mixture can be transported to the textile producer. On the other hand, the PVA copolymer ionomer can be produced in a mixed size solution together with other PVA polymers and starch without isolating the PVA copolymer ionomer. Granular PVA
High temperatures are usually required to prepare aqueous size solutions from copolymer ionomers or mixtures with other PVA polymers and starch. The time and temperature required to form a solution will depend on the actual composition, but can be readily determined by trial and error.

[0062] The total concentration of polymer in the size solution should be from 1 to 20 weight percent, with 4 to 12 weight percent being preferred. The sizing solution can incorporate other ingredients commonly found in sizing compositions. Such materials include wax-type lubricants, defoaming surfactants, other surfactants, and the like. One of ordinary skill in the art can determine what concentration of sizing solution to use to achieve the desired sizing level, and what additives are most suitable for my job. There will be.

The free carboxylic acid should preferably not be present in the poly (vinyl acetate) copolymer, poly (vinyl alcohol) copolymer or derived PVA ionomer, but the free acid Not as long. Small amounts of acid can remain or be present in any of these.

The rate of dissolution or ease of dissolution of a PVA copolymer ionomer in water (which is related to desizing sensitivity) depends on the degree of crystallinity due to the increased number of comonomer units. Decline, a net decrease in polarity with increasing levels of relatively non-polar comonomer units (usually as lactone units) that are not converted to ionomer units, and increased water to rise due to the presence of polar ionomer units. It depends on the dissolution rate. Any PVA copolymer ionomer can be expected to have water solubility or sensitivity as a result of the balance due to the interaction of these factors. All ester comonomer and lactone rings that such factors can form are less polar and therefore less sensitive to water than vinyl alcohol units, while ionomer units are generally more sensitive. Within the scope of the invention, the most water-sensitive PVA copolymer ionomers are generally the most easily desizing polymers. In some sizing situations, such polymers are of a suitable size, but in other situations they are too sensitive to water. However, such highly desizing compositions are not suitable for obtaining a given level of desizing power.
Because lower amounts may be required, it may be the best composition to use in the mixture.

In general, PVA copolymers have great diversity in that they can be designed to have a variable and controllable degree of water sensitivity and desizing capability based on the above factors. are doing. It would be within the skill of a person of ordinary skill in the art to explore, based on trial and error, a large number of mixed-size aesthetics that, based on trial and error, make the best use of a particular desired attribute. .

In particular, PVA homopolymers having relatively low levels of comonomer, such as less than about 6 weight percent, and many non-ionomer PVA copolymers, are less descalable or have the same amount. Higher temperatures are required to desizing or to facilitate desizing. As noted, caustic desizing can assist in desizing the copolymer. Generally, the PVA copolymer ionomer is
Desizing in water is much faster than in the original PVA copolymer because it contains very soluble ionomer groups. It is believed that caustic desizing also aids in desizing the PVA copolymer ionomer. This is especially true if non-ionomer alkyl ester groups remain in the copolymer since the copolymer is then further ionomerized. However, one of the advantages of PVA copolymer ionomers is that PVA copolymers with comparable levels of comonomer do not rely on caustic desizing.
This means that desizing can be performed more quickly than A copolymer. If caustic desizing is used, especially when slightly elevated temperatures are used for desizing, the concentration of the caustic solution can be as high as about 10 percent, but not as high as about 10 percent.
. It can be very diluted, such as 001 weight percent.

For blends containing non-ionomer PVA copolymers, the idea of mixing such copolymers with PVA copolymer ionomers, in principle, offers the advantage of immediate desizing in water. Although it must be done, caustic desizing may be advantageous. However, in mixtures containing partially hydrolyzed PVA homopolymer, increased saponification due to caustic increases crystallinity due to the increased percentage of vinyl alcohol units, and therefore reduces desizing performance. So water may be preferred.

In general, excess caustic must subsequently be washed away to avoid higher than appropriate concentrations of caustic. For any particular PVA copolymer ionomer, or mixture, determine how quickly and how thoroughly desizing is required, and determine the level of addition, heat treatment of the fabric, and concentration suitable for the desizing caustic solution, And the temperature suitable for desizing can be easily determined. Thus, for economic reasons, the emphasis can be placed on quick desizing. Alternatively, since the material is temperature sensitive to some extent, emphasis can be placed on desizing at the lowest possible temperature.
Usually, almost complete desizing is required. There are various alternative conditions, as well as only one suitable desizing condition. If caustic desizing is used, suitable caustic materials include, for example, hydroxides or carbonates of alkali metals such as sodium, potassium, lithium, etc., with sodium hydroxide being preferred. But,
In some mills, weak desizing conditions may be required. In this case, desizing with water or desizing with carbonate can be used, and the concentration, time and temperature of desizing are adjusted.

The yarns in which the sizes of the invention can be used to advantage are textile fibers or monofilaments,
Or any conventional yarn from other knitable structures, either hydrophilic, such as cotton, or hydrophobic, such as nylon or polyester, or from a hydrophilic / hydrophobic combination be able to. Some final operations on (woven) fabrics can also advantageously use the size of the present invention.

[0070] The PVA copolymer ionomer of the present invention can have a viscosity of 1 to 60 centipoise in a 4% solution. It should preferably have a viscosity between 3 and 25 centipoise. It is within the skill of the art to determine the optimum polymer viscosity, polymer size concentration, and addition level for the particular yarn, fabric, and knitting conditions used.

The prior art PVA polymer in the PVA copolymer ionomer / PVA polymer mixture of the present invention may be any PVA polymer previously known for use as size.
It can be an A homopolymer, or a PVA copolymer, or a mixture of such a prior art polymer with a PVA copolymer ionomer. This includes both fully and partially hydrolyzed homopolymers and alkyl groups,
Examples include PVA copolymers having comonomers selected from the group consisting of alkyl methacrylates, alkyl acrylates, dialkyl fumarate, and dialkyl maleate containing from 1 to 8 carbon atoms. The partially hydrolyzed non-ionomeric PVA in the mixture can be 50-98% hydrolyzed, but preferably is more than 80% hydrolyzed.

Starches that can be advantageously mixed with the PVA copolymer ionomer to improve the desizing performance of the PVA copolymer ionomer (and generally increase its size effect) include natural starch, There are synthetic starches and some chemically modified starches. As a result of the very modification, the properties and the ability to desizing are largely removed and are not particularly advantageously mixed with the PVA copolymer ionomer.
There are some starch-derived materials. For example, some modified starches already have properties that are fairly easily desized and / or far removed from native starch. In fact, such materials may already be very modified, so that these modifications alone can serve the similar purpose of improving the sizing action and the desizing performance, and the inventive PVA Mixing with the copolymer ionomer offers only a few additional advantages. However, in general, PVA ionomers are easier to desizing than the majority of available starches.

The starch which is advantageously mixed with the PVA copolymer ionomer of the present invention is preferably a natural starch which is unmodified or modified only to a small extent, or a synthetic starch.

[0074] Natural starch is a carbohydrate originating in natural vegetables that is generally considered to be composed primarily of amylose and / or amylopectin. Specific examples of naturally occurring starches include starches such as corn, wheat, potatoes, sorghum, rice, beans, cassava, sago, tapioca, bracken, water lily, and watershed berries. In these, the level of the function to be desized is substantially raised, and in general,
Starch is a preferred sizing material of the invention because these properties as size are inferior to modified starch. The main advantage of these is that they are relatively cheap.

Examples of synthetic starch and chemically or physically modified starch include alpha starch, fractionated amylose, wet-heat treated starch, hydrolyzed dextrin, produced by enzymatic degradation. Dextrin, amylose, etc., enzymatically modified starch, acid-treated starch, starch oxidized with hypochlorous acid, chemically degraded starch such as dialdehyde starch, esterified starch, etc. Examples include chemically modified starch derivatives.
Specific examples of chemically modified starch derivatives include starch acetate, starch succinate, starch nitrate, starch paste, starch paste urea, starch xanthate, starch Esterified starch such as acetoacetate, allyletherified starch, methyletherified starch, carboxymethyletherified starch, hydroxyethyletherified starch, hydroxypropyletherified starch, etc. Starch, reaction products from starch and 2-diethylaminoethyl chloride, cationized starch such as reaction products from starch and 2,3-epoxypropritrimethylammonium chloride, formaldehyde, etc. Crosslinked starch, epichlorohydrin crosslinked starch, crosslinked starch such as phosphoric acid crosslinked starch, and the like any of the above or mixtures of the same starch.

The mixture used to prepare the size solution was PVA copolymer ionomer 1
It can contain 0 to 90 weight percent, and 90 to 10 weight percent of another PVA polymer or starch. The lowest levels are very effective in increasing the desizing power, due to the extremely easy desizing of ionomers containing high levels of ionomer units.

The PVA copolymer ionomers used in the sizes and blend sizes of the present invention may also be adaptable for use in certain film applications. Such films include agricultural multi-films, biodegradable packaging films, water-soluble films, and the like. They may also be adaptable for use as hot melt adhesives, binders and the like.

EXAMPLES The PVA copolymer ionomer, designated as C9AI in Table I, is an example of a “slurry” method for preparing a PVA copolymer ionomer from a PVA copolymer.
It was prepared as follows. To a solution prepared by dissolving 0.64 g of sodium hydroxide in 30 g of water and 120 g of methanol, 50 g of the PVA copolymer C9A was added with stirring to form a slurry. The slurry was stirred at room temperature of about 22 ° C. for 1 hour and then vacuum filtered through a fritted glass filter. The wet filtrate was dried in a vacuum oven at room temperature under nitrogen and then at 80 ° C. overnight for about 4 hours. A white granular product (about 49.6 g) was obtained. The amount of sodium hydroxide used is sufficient to ionomerize about 1/3 of the comonomer units. The polymer had 9 weight percent comonomer, or 6 mole percent. Thus, the product has about 2 mole percent ionomer units.

To produce a size solution from this product, it is merely dissolved in water for a suitable amount of time and at a temperature sufficient to dissolve it. Generally, 2 hours at about 90 ° C. is more than sufficient. A mixed size containing the slurry PVA copolymer ionomer was prepared by dissolving a 50/50 mixture of the polymer and other mixed components together in water at 90 ° C. for 2 hours. This polymer was used extensively in a desizing test and only the slurry polymer was tested. PVA copolymer ionomers for other slurry methods were prepared using the same method, but with different starting polymers and different base amounts. As a control, the same procedure was performed on polymers that could not form ionomers, thus allowing the polymers to be compared. The polymer used, the amount of base used, and certain properties of the copolymer are listed in Table IV. The above example of slurry ionomerization is set forth in the table (64 g NaOH and C9A polymer). Its properties are designed to indicate the degree of ionomerization based on IR testing and its effect on solubility and solubility rate for different starting polymers.

The “solution” method for making the PVA copolymer ionomer, for example, where the reaction medium is essentially water so that the polymer can be dissolved in the reaction medium, is illustrated by the following examples. . 0.13 g of sodium hydroxide was dissolved in 45 g of water, 5 g of polymer C9A was added, and the mixture was stirred at room temperature for 5 minutes. The mixture is then added to 9
Heated to 0 ° C. and held at this temperature for 1 hour. The resulting solution was clear. Table IV shows the IR analysis and film dissolution times of several PVA copolymer ionomers prepared in this manner, as well as polymers that could not form ionomers but were treated in the same manner.

The analytical tests were as follows:

Heated water soluble. With sufficient heating of the water, all PVA copolymers can be dissolved.
Solubility was measured under a selected set of intermediate temperature conditions to distinguish the solubility of the different materials in water. The condition is 35 ° C. for 1 hour. This test was used only for slurry polymers, as the slurry method produces a solid granular polymer, while the solution method results in a polymer solution.

Slurry 10 grams of polymer with 190 grams of water at 35 ° C. for 1 hour with gentle mixing. After cooling, the remaining solids were filtered off, an aliquot of the clear filtrate was dried in an aluminum dish in a desiccator box and the polymer weight in the aliquot was determined. Next, the percent of solubility could be calculated. The results are shown in Table IV.

An infrared analysis of the cast film was performed. For the slurry polymer, a 10 percent solution was prepared by dissolving at 80 ° C. for 1 hour. The polymer prepared by the solution method was used directly for casting. The film was cast at 52 ° C. using a 15 mm knife gap, dried for 30 minutes, dried under vacuum at room temperature overnight under nitrogen, and further dried at 80 ° C. for 4 hours. The elongated film was stored in a desiccator box.

[0085] Infrared analysis of the films was performed using a Nicolet 710 FT-IR spectrometer. According to known techniques, the IR peak at 1725 to 1750 cm ^-1 is due to the lactone group as a result of the internal lactonization of a methyl acrylate or methyl methacrylate comonomer at the hydroxyl group of vinyl alcohol, for example. It is. The presence of the lactone group indicates that the condition could not be ionomerized (eg, controlled conditions without a base) or that incomplete conversion of the lactone to the ionomer unit occurred, resulting in a non-ionomerized unit. (Presence of). No attempt was made to quantify the amount of residual lactone units. The results are displayed qualitatively. Based on the art, the IR peak at 1550-1575 cm ^-1 is due to carboxylic ionomer units. However, the presence of a small amount of sodium acetate ash also causes a peak at this wavenumber, so that all samples show a small peak in this region, even in the absence of ionomer units. The results are shown in Table IV.

Film dissolution time. An advanced test of solubility in water was performed, in this example testing the dissolution time at ambient temperature rather than the amount soluble under specific temperature / time conditions. The film prepared as above was suspended in water with gentle stirring,
The time for complete dissolution was measured. The results are shown in Table IV.

All three tests provide an indication of the amount of ionomerization of the three copolymers tested. For C3M, the solubility at 35 ° C. was determined to be 6.7 percent for the nonionomerized copolymer by ionomerizing with 0.84 grams of base in 200 grams of reaction medium, compared to 6.7 percent for the ionomer. After the conversion, it can be seen to increase dramatically to 34.4%. Dissolution time decreased to 25.3 minutes 8.5 minutes, IR peak of the ionomer in 1550～1570Cm ^-1 increases with the consumption of the lactone of the IR peak at 1725~1750cm ^-1. C3
As the amount of base relative to M decreased, the solubility at 35 ° C. decreased, indicating that less alkyl methacrylate was ionomerized. A similar trend is observed for polymers C5M and C9A, but the solubility at 35 ° C. of ionomerized C9A using slurry polymerization, for example,
Occasionally, the results appear to deviate from the trend, as it appears that 2.56 g of base is smaller than 1.28 g of base. However, both values are very high compared to the non-ionomerized C9A control. In general, the C9A nonionomerized copolymer is more soluble in these tests than C3M and C5M,
Ionomers derived from A are relatively more soluble than similarly ionomers derived from C3M and C5M copolymers. A similar trend is seen with solution polymers.

All PVA copolymer ionomers used in the desizing test were prepared by a solution method except for C9AI. The solution method was used because this method gives a solution that can be used immediately in size. While this method is essentially always the same, whether the base is added to the polymer / liquid medium mixture as a solid or as an aqueous solution (loose slurry, but the final polymer is always Do not confuse with the slurry method, which is the shape of the slurry), or make small differences in terms of whether the polymer is added to the base solution. In Table II,
Used for the polymers used, and those for which small differences were noted above,
Show details of solution method. When preparing the mixed size, the mixed components which cannot be ionomerized are mixed with the reaction medium (methanol /
It is different from a water mixture at room temperature in water) at room temperature to mix with a polymer that can be ionomerized, mainly to complete the dissolution.
Both polymers were then heated to 90 ° C. for further ionomerization.

The size solution was generally clear and slightly viscous if only a PVA polymer was used. If the starch was part of the mixture, there was sometimes some haze and the starch was suspended rather than completely dissolved.

When the mix size was tested, the mixture contained 50 weight percent of each component. The sizes tested are shown in Table II divided into three. Column 1, Table I
IA indicates size based on homopolymerization. Column 2, Table IIB shows PVA
It relates to a size based on a mixture of copolymer, several controls and several ionomer mixtures. Column 3, Table IIC shows the starch / PVA copolymer,
Or an ionomer mixture.

A sample of the glued fabric was prepared as follows. Test Fabr
ics Inc. 7 oz (198 g), all cotton, bleached canvas fabric type 464, approximately 2 inches (5 cm) x 2 inches (5 cm)
The four sides were immersed in the size solution at about 35 ° C. for about 2 minutes with first weighing and then gentle mixing. The weight of the fabric was generally between 0.4 and 0.7 grams and the amount of size added was between about 0.13 and 0.4 grams. The sample was then placed on aluminum foil and dried and treated with Teflon® lubricant at 50 ° C. for 17 +/− 1 hours in a convection oven to prevent sticking. These were then cooled in a box dried over calcium sulfate and reweighed to determine the amount of added size. In some cases, the samples were heat treated by placing them in a convection oven at 140 ° C. for 10 minutes.

The desizing test was performed by immersing a sample of the sized fabric in 100 grams of test desizing medium (water or caustic) for 10 minutes with gentle mixing.
If water was used, in some cases the sample was further desizing by immersion in another 100 grams of water for 10 minutes. If caustic was used, in all cases the samples were then soaked in 100 grams of water for 10 minutes. This subsequent water treatment not only provides a slightly advanced desizing but also removes caustic. Next, the desizing sample or the partially desizing sample is dried in a convection air oven at 140 ° C. for 1 hour, and then cooled in a box dried with calcium sulfate. Details are shown in Table III, divided into three parts. Column 1, Table IIIA, relates to the homopolymer composition (ionomer and control); Column 2, Table IIIB relates to the mixed PVA polymer composition (ionomer and non-ionomer mixture);
Table IIIC relates to mixed PVA copolymer / starch compositions (copolymers that are ionomers or non-ionomers). The desizing test of each Table III uses the size indicated in the corresponding Table II (eg, Table IIIB and Table IIB).

When examples of the PVA copolymer ionomers or mixed sizes of the present invention are shown in the table, they are numbered without the prefix C. When referring to size examples outside the inventive composition, the inventive PVA polymer, whether from a homopolymerized non-ionomer PVA polymer, is indicated.
A prefix C, whether from a mixture without the A copolymer ionomer, is indicated to indicate for comparison.

While complete desizing is generally considered necessary, the desizing percentages in the examples are considered indicative of the ease of complete desizing. If the value shown is less than 100%, longer desizing times, different caustic concentrations, or slightly higher temperatures will be required to achieve complete desizing. The double wash produced (e.g., corresponding to a longer desizing time) increased desizing.

[0095] In some examples, the glued fabric was heat treated, some with a double water wash. Heat treatment can reduce desizing performance, especially in compositions rich in partially hydrolyzed PVA polymers, especially homopolymers, in some instances.

The desizing time is deliberately short in order to compare the ease of desizing. The desizing amount is indicated as the "apparent" percent size to be removed. This is because during the desizing test a small amount of other material of the fabric, in addition to the size, is removed, so that some values are seen to be slightly greater than 100 percent. The longer the time, the more samples will be completely desizing.

Examples 1, 2, 3, 5, and 10 show the ease of desizing with non-ionomeric PVA polymers with water. Partially hydrolyzed homopolymers remove them most easily, and fully hydrolyzed homopolymers are the most difficult. The other three examples relate to copolymers having two different levels of methyl methacrylate and one relates to copolymers having high levels of methyl acrylate. Examples 6 and 9 show the effect of increasing ionomerization levels of polymer C5M (Example 5 relates to non-ionomerized C5M). Ionomers are easier to desizing, and more highly ionomerized compositions are:
Desized more easily. Example 7 shows that the longer the desizing time (twice desizing), the more desizing occurs, and that complete desizing occurs with a sufficient length of desizing time. . Example 8 shows that the same polymer C
It shows that a higher desizing level of 5M results. This suggests that the ionomerized polymer of size SZ6 is further ionomerized with a base. Examples 11 and 12 relate to ionomerized C9A. Example 12 shows that the desizing amount of the ionomer increases as the desizing temperature increases. Example 15 shows that after heat treatment, the ionomer is not very easily desizing (compared to Example 13), but the higher desizing temperature allows complete desizing again.

In general, ionomers formed from PVA copolymers having high levels of comonomer are more easily desizing, and the greater the ionomerization of the PVA copolymer, the easier it is to desizing. . Non-ionomeric materials that are more easily desizing than some ionomers (e.g., from lower comonomer PVA copolymers and / or using lower levels of base) prepared to have lower ionomer levels On the other hand, ionomers provide an immediate choice for such non-ionomeric PVA polymers or copolymers. The ionomer requires less comonomer in the PVA starting polymer for a given ease of desizing, which is often advantageous in terms of ease of preparation for polymerization, as well as cost. In this sense, significantly less ionomer units are required than non-ionomer comonomer units to allow a given ease of desizing.

The following two tables show mixed size wide range pastes. The first paste is made of another PV
The second paste has the A polymer, and the second paste has the starch.
A similar test of the ease of desizing shows that the ease of desizing is very roughly indicated as being the weight average of the ease of desizing of the components. Of course, when highly ionomerized, highly comonomer copolymer ionomers are used in the mixture, the ease of desizing is very effectively increased. As an example, size S
Z40BS-C and SZ41BS are a mixture of C9A / starch S4. The SZ41BS mixture was subjected to ionomerization conditions, while the control mixture was a non-ionomer mixture, thus ionizing the C9A component. The desizing amount (Examples 51 and 52) increased from 54.8 percent to 94.1 percent. Other embodiments generally follow a similar pattern.

TABLE I: PVA Sample Codes Tested Solutions Viscosity Hydrolysis Molar% Composition Description H88-1 21-26 87-89 Partially hydrolyzed "homopolymer" H88-2 44-50 87-89 Partially hydrolyzed "homopolymer" H99-1 12-15 99-99.8 "Completely" hydrolyzed Homopolymer H99-2 27-33 99-99.8 "Completely" hydrolyzed Homopolymer C3M 24-32 99-99.8 Completely hydrolyzed copolymer 1.9 mol% (about 3 wt%) MMA C5M 12-15 98-99.8 Completely hydrolyzed copolymer 2.8 mol% (about 5 wt%) MMA C9A 15-21 98-99.8 6.0 mol% (about 9 wt%) of completely hydrolyzed copolymer MMA C9AI nm 9 8-99.8 Partially ionomerized C9A (approximately 30% comonomer units) S1-Natural corn starch: CAS 68412-30-6 S2-Chemically modified starch: Ether of hydroxyethyl starch CAS9005-26-0 S3-Chemically modified starch: oxidized carboxymethyl starch ether, CAS9063-38-1 S4--Chemically modified corn starch: Ethioxylated starch ether, CAS 68512-26-5

The names of the polymer codes summarize the properties of the composition; H is a homopolymer, C is 88 mol% of the copolymer 88 hydrolyzed, M is methyl methacrylate comonomer, A is Represents methyl acrylate comonomer.

The solution viscosities were determined by the Hoeppler falling ball method, dry basis,
Measured at 0 ° C., 4 weight percent solution.

All samples have a solution pH between 5 and 7. All samples have a maximum ash level of 0.7 weight percent, calculated on a dry basis as sodium oxide.

The comonomer levels in the copolymer are expressed as weight percent and mole percent, calculated as non-lactonized comonomer units, in the poly (vinyl alcohol) chain.

Codes C3M, C5M, C9A: The numbers refer to the weight percentage of the comonomer.

C9AI = ionomerized C9A comonomer Abbreviation: MMA = methyl methacrylate; MA = methyl acrylate Products Co., Cedar Rapids, Iowa S3 Trade name: Astrogum 3010, Penford Products Co. S4 Trade name: Clinton 712D, ADM Corn Processing Co.

Table IIA Compositions of Sizes Tested Size Composition SZ1-C 8% H88-1 polymer in water> water / 90 ° C./2 hours SZ2-C 8% H99-1 polymer in water> water / 90 ° C./2 hours SZ3-C 8% C3M polymer in water> water / 90 ° C./2 hours SZ4 8% C3M polymer in 0.1% NaOH> solution / 90 ° C./2 hours SZ5-C 8% C5M polymer in water> water / 90 C / 2 min SZ6 8% C5M polymer in 0.1% NaOH> solution / 90 ° C / 2 h SZ7 8% C5M solid NaOH in 0.2% NaOH> RT poly. Slurry + 90 ° C./2 hours SZ8-C 8% C9A polymer in water> water / 90 ° C./2 hours SZ9 8% C9A NaOH solution in 0.045% NaOH> RT poly. Slurry + 90 ° C./2 hours SZ10 8% C9A in 0.1% NaOH polymer> solution / 90 ° C./2 hours SZ11 8% C9AI in water Polymer> water / 90 ° C./2 hours SZ12 0.29% C9A in NaOH Solid NaOH> RT poly. Slurry + 90 ° C / 2 hours SZ13 0.45% C9A polymer in 0.45 NaOH> Solution / 90 ° C / 2 hours SZ14 8% C9A solid in 0.1% KOH KOH> RT poly. Slurry + 90 ° C / 2 hours

Table IIB PVA mixed size composition Size composition SZ15BP-C 8% 1/1 H99-1 / C3M polymer in water> water / 90 ° C./2 hours SZ16BP 0.025% 8% in NaOH 1/1 H99-1 / C3M solution of C3M> RT + H99-1 + 90 ° C./2 hours SZ17BP-C 8% 1/1 H88-1 / C5M polymer> water / 90 ° C./2 hours SZ18BP 0.025% 8% 1/1 H88 in NaOH -1 / C5M Solution of C5M> RT + H88-1 + 90 ° C./2 hours SZ19BP 8% in 0.048% NaOH 1/1 H99-1 / C5M Solid NaOH> RTC5M slurry + H99-1 + 90 ° C./2 hours SZ20BP-C 8 in water % 1/1 C5M / C9A polymer> water / 90 ° C./2 hours SZ21BP 0.02% 8% in C2M / C9A solid NaOH> C 9A slurry + C5M + 90 ° C./2 hours SZ22BP-C 8% 1/1 H99-1 / C9A polymer in water> water / 90 ° C./2 hours SZ23BP 0.058% 8% in NaOH 1/1 H99-1 / C9A C9A> RT + H99-1 + 90 ° C./2 hours SZ24BP-C 8% in water 1/1 H88-1 / C9A Polymer> water / 90 ° C./2 hours SZ25BP 0.058% 8% in NaOH 1/1 H88-1 / C9A C9A > Solution + H88-1 + 90 ° C / 2 hours SZ26BP-C 8% in water 1/1 H99-2 / C9A polymer> water / 90 ° C / 2 hours SZ27BP 8% in water 1/1 H99-2 / C9AI / 90 ° C / 2 hours SZ28BP 8% in 0.45% KOH 1/1 H99-1 / C9AI Solid NaOH> H99-1 / C9A mixed slurry + 90 ° C / 2 hours SZ29BP-C 8% 1/1 H88-2 / C9A polymer in water / 90 ° C./2 hours SZ30BP 0.2% in 8% NaOH 8% 1/1 H88-2 / C9A C9A> solution + H88-2 + 90 ° C./2 hours SZ31BP-C 8% 1/1 in water C3M / C9A polymer> water / 90 C / 2 hours SZ32BP 8% in 0.025% KOH 1/1 C3M / C9A Solid KOH> C9A slurry + C3M + 90 C / 2 hours

Table IIC PVA / starch size composition Size composition SZ33BS-C 8% 1/1 S1 / C3M polymer in water> water / 90 ° C./2 hours SZ34 8% in 0.05% NaOH 1/1 S1 / C3M C3M> solution + S1 + 90 ° C./2 hours SZ35BS-C 8% 1/1 S2 / C5M polymer in water> water / 90 ° C./2 hours SZ36BS 8% 1/1 S2 / C5M C5M in 0.05% NaOH> solution + S2 + 90 ° C./2 hours SZ37BS 8% 1/1 S1 / C5M in 0.1% NaOH Solid NaOH> C5M slurry + S1 + 90 ° C./2 hours SZ38BS-C 8% 1/1 S3 / C9A / 90 ° C./2 hours in water SZ39BS 8% 1/1 S3 / C9A in 0.023% NaOH Solid NaOH> C9A slurry + S3 + 90 ° C. / 2 hours SZ40BS-C 8% 1/1 S4 / C9A polymer in water> water / 90 ° C./2 hours SZ41BS 8% 1/1 S4 / C9A C9A in 0.05% NaOH> solution + S4 + 90 ° C./2 hours SZ42BS- C 8% 1/1 S1 / C9A polymer in water> water / 90 ° C./2 hours SZ43BS 8% 1/1 S1 / C9A C9A in 0.05% NaOH> Solution + S1 + 90 ° C./2 hours SZ44BS-C 8 in water % 1/1 S2 / C9A / 90 ° C / 2 hours SZ45BS 8% 1/1 S2 / C9A C9A in 0.05% NaOH / Solution + S2 + 90 ° C / 2 hours SZ46BS 8% 1/1 S3 / C9AI polymer in water> Water / 90 ° C./2 hours SZ47BS 0.1% NaOH 8% 1/1 S4 / C9A Solid NaOH> C9A slurry + S4 SZ48BS 0.23% NaOH 8% 1/1 S3 / C9A C9A> solution + S3 + 90 ° C / 2 hours SZ49BS 0.05% KOH 8% 1/1 S2 / C9A solid KOH> C9A slurry + S2 + 90 ° C / 2 hours

Description of the method steps: In the rows, the first row in the last column shows the overall composition. The second row shows the process steps and their order.

Example: Solid NaOH> RT Poly. Slurry + 90 ° C./2 hours: Solid sodium hydroxide was added to the polymer slurry at room temperature (>), followed by (+) heating at 90 ° C. for 2 hours.

Polymer> solution / 90 ° C./2 hours: The polymer was added to the base solution (>) and subsequently heated (+) at 90 ° C. for 2 hours.

Polymer> Water: The polymer was added to water.

8% 1/1 S1 / C5M in 0.1% NaOH: The composition has a base concentration of 0.1%.
8 of a 1/1 mixture of starch S1 and polymer C5M, prepared using 1% by weight.
% Solution.

Solid NaOH> C5M slurry + S1 + 90 ° C./2 hours: The method step consists in adding solid sodium hydroxide to a slurry of C5M polymer, then adding starch S1 and heating to 90 ° C. for 2 hours. there were.

[0116] Table IIIA desizing Test Example ♯ Size Size% heat desizing desizing Temperature ℃ removed treating medium saw 1 SZ1-C N W 23 65.5 2 SZ2-C N W 22 27.5 3 SZ3 -CNW2229.74SZ4NW2244.4.25SZ5CNW2251.96SZ6NW2275.77SZ6NW / W2288.87SZ6N0.1% NaOH2296 .49 SZ7 NW 22 99.5 10 SZ8-CNW 23 36.6 11 SZ9 NW 23 55.6 12 SZ9 NW 50 93.4 13 SZ10 NW 22 82.2 14 SZ10 NW 50 .5 15 SZ10 YW 22 45 16 SZ10 YW 50 100.4 17 SZ11 NW 22 92.9 18 SZ12 NW 23 87.9 19 SZ12 NW 50 103 20 SZ13 NW 23 105.2 21 SZ14 NW 22 77.2

[0117] Table IIIB desizing tests - Continued Example ♯ size heat desizing desizing Temperature ℃ removed treating medium apparent size% 22 SZ15BP-C N W 22 27.0 23 SZ16BP N W 22 33.4 24 SZ17BP -C NW 22 62.825 SZ18BP NW 22 63.2 26 SZ18BP NW 5096 27 SZ19BP NW 22 51.7 28 SZ20BP-C NW 22 45.8 29 SZ21BP NW 2274 NW 2274 N W / W 22 91.1 31 SZ22BP-C NW 22 43.4 32 SZ23BP NW 22 51.1 33 SZ23BP NW 50 90.7 34 SZ24BP-C NW 22 60.6 35 SZ25BP N W 2281 0.736 SZ25BP N 0.1% NaOH 22 103.1 37 SZ26BP-C NW 22 29.8 38 SZ27BP NW 22 45.6 39 SZ28BP NW 22 56.3 40 SZ29BP-C NW 22 49.3 41 SZ30BP NW 22 77.7 41 SZ31 NW 22 32.2 43 SZ32 NW 22 54.2

[0118] Table IIIC desizing tests - Continued Example ♯ size heat desizing desizing Temperature ℃ size% 44 of the removed treating medium apparent SZ33BS-C N W 22 38.5 45 SZ34BS N W 22 86.8 46 SZ35BS -C NW 22 48.247 SZ36BS NW 22 80.2 48 SZ37BS NW 22 100.2 49 SZ38BS-C NW 22 55.6 50 SZ39BS NW 22 82.8 51 SZ40BS-C NW 2254 .852 SZ41BS NW 22 94.1 53 SZ42BS-C NW 22 35.954 SZ43BS NW 22 96.1 55 SZ44BS-C NW 22 35.8 56 SZ45BS NW 22 82.5 57 SZ46BS 22 84.0 58 SZ47BS NW 22 89.7 59 SZ48BS NW 22 70.0 60 SZ48BS N W 50 101.6 61 SZ48BS Y 0.1% NaOH 22 99.2 62 SZ49BS N W 22 64.9 W = desizing with water W / W = desizing twice

[0119]Table IV Properties of PVA polymer under ionomerization conditions NaOHPolymer slurry 35 ° C Dissolution time IR (cm-1) IR (cm-1) GOr % Soluble / ＠ ° C 1725-50 1550-75 solution  0 C3M slurry 6.7 25.3 / 18.7 ° ++++ + 0.84 C3M "34.4 8.5 / 18.7 +++ +++ 0.63 C3M" 19.9 nm nm nm 0.42 C3M "7.2 nm nm nm 0 C5M" 6.2 3.8 / 22.8 +++ + + 1.21 C5M "84.0 5.1 / 21 +++ +++ 0.91 C5M" 54.5 nm nm nm 0.61 C5M "23.9 2.5 / 21 +++++ 0.30 C5M" 11.8 nm nm nm0 C9A "8.15 2.8 / 22.3 ++ ++ + 2.56 C9A "60.34 0.8 / 18.1 ++ +++ 1.28 C9A" 88.2 nm nm nm 0.64 C9A "62.0 nm nm nm 0.16 C9A" 24.6 2.0 / 19.8 ++++++ 0 C3M solution nm 60 / 21.7 nm nm 0.08 C3M "nm 7.9 / 21/7 +++++ 0 C9A" nm 1.8 / 20.9 +++++ + 0.13 C9A "nm 0.9 / 20.5 0 +++++  nm-not measured ++++++ maximum peak, ++++ very large peak, ++ large peak, ++ medium peak, + small peak

Claims (20)

[Claims] 1. A sizing composition comprising 1 to 20 weight percent of an aqueous polymer solution comprising water and a first polymer, wherein the first polymer is a precursor vinyl acetate. A poly (vinyl alcohol) copolymer ionomer that is hydrolyzed by 90 to 100 percent based on the vinyl acetate units remaining from the copolymer, wherein the copolymer ionomer comprises 0.1 to 10 mole percent anion. A sizing composition comprising a functional carboxylic acid metal salt unit. 2. The sizing composition according to claim 1, wherein the poly (vinyl alcohol) copolymer ionomer has from 2 to 10 mole percent of anionic metal carboxylate units. 3. The polymer solution further comprising a second polymer in an amount of 10 to 90% by weight based on the total weight of the second polymer and the first polymer. The union is C1-C8 alkyl (meth) acrylate, or C1-C3
10 units derived from dialkyl fumarate or dialkyl maleate
A non-ionomeric poly (vinyl alcohol) polymer which is a poly (vinyl alcohol) homopolymer or a poly (vinyl alcohol) copolymer containing up to mole percent, or a mixture of these polymers. Item 6. A gluing composition according to Item 1. 4. The method according to claim 1, wherein the second polymer is not contained in the polymer solution.
In addition to the third polymer, the third polymer further comprises 10 to 90 weight percent based on the total weight of the third polymer and the first polymer, and the third polymer is: A sizing composition according to claim 1, characterized in that it is a starch which is a natural starch, a synthetic starch, a physically modified starch, or a chemically modified starch, or a mixture of such starches. 5. The method according to claim 1, wherein the second polymer and the third polymer are further included in a total amount of 10 to 90% by weight based on the total weight of the first, second, and third polymers. The sizing composition according to claim 1, characterized in that: 6. A process for preparing a poly (vinyl alcohol) copolymer ionomer containing 0.1 to 10 mole percent anionic metal carboxylate units and isolated in the form of fine particles, comprising: a. C.) mixing 1 to 90 percent of solids, liquid reaction medium, and solid particulate starting poly (vinyl alcohol) copolymer to form a slurry containing the copolymer; Wherein said liquid reaction medium comprises: (i) an alcohol) copolymer and a poly (vinyl alcohol) copolymer ionomer formed in the future, provided that both are soluble in the reaction medium at 30 ° C. at less than 5 weight percent. C1-C3 alkanols, (ii) a mixture of C1-C3 alkanols, (iii) C1-C3 aliphatic ketones, (iv) C1-C3 aliphatic ketones (Vi) a mixture of one or more C1-C3 alkanols and water, (vi) one or more C1-C3
The solid fine particles selected from the group consisting of a mixture of three aliphatic ketones and water, and (vii) a mixture of one or more C1 to C3 alkanols and one or more C1 to C3 aliphatic ketones and water. Is a poly (vinyl alcohol) starting copolymer represented by (i) C1-C
(Ii) C1-C8 alkyl methacrylate, (ii)
i) a precursor poly (vinyl acetate) copolymer containing 0.1 to 10 mole percent of a comonomer selected from the group consisting of C1 to C3 dialkyl fumarate, and (iv) a C1 to C3 dialkyl maleate. Is a product that is 90 to 100 percent hydrolyzed with respect to vinyl acetate units, and b) reducing the base material from 0.1 to 20 per 100 moles of units derived from monomers in the starting PVA polymer. Adding in molar amounts, but no more than twice the number of moles of units derived from comonomer or lactone units derived therefrom in the starting PVA copolymer, wherein the base material is (I)
A step selected from the group consisting of an alkali hydroxide, (ii) a hydroxide of an alkaline earth metal, and (iii) a hydroxide of a quaternary ammonium, c) at least 10 minutes at 15 to 30 ° C. A method of preparing a poly (vinyl alcohol) copolymer ionomer, comprising: agitating; and d) filtering and drying the formed particulate poly (vinyl alcohol) copolymer ionomer. 7. The comonomer in the precursor copolymer is methyl acrylate or methyl methacrylate at a level of 2 to 20 mole percent, the reaction medium is aqueous methanol, and the slurry is Percent, wherein the base is sodium hydroxide or potassium hydroxide in an amount of 0.5 to 2 moles per mole of copolymer or derived lactone in the starting copolymer and stirring is from 30 minutes to 3 hours. The method of claim 6, wherein the method is performed. 8. A process for preparing a solution of a poly (vinyl acetate) copolymer ionomer containing 0.1 to 10 mole percent anionic metal carboxylate units, comprising: a) solid particulate starting poly. Forming an aqueous mixture containing from 1 to 90 weight percent of the (vinyl alcohol) copolymer, wherein the solid particulate poly (vinyl alcohol) copolymer comprises: i) a C1-C8 alkyl acrylate; (Ii) C1-C8 alkyl methacrylate, (iii) C
A precursor poly (vinyl acetate) copolymer containing 0.1 to 10 mole percent of a comonomer selected from the group consisting of 1 to C3 dialkyl fumarate, and (iv) a C1 to C3 dialkyl maleate; 9 per vinyl acetate unit
From 0 to 100 percent hydrolyzed product; b) adding the base material in an amount of from 0.1 to 20 moles per 100 moles of units derived from monomers in the starting PVA polymer, with the proviso that A step of adding the moles of the unit derived from the comonomer or the lactone unit derived from the comonomer in the PVA copolymer to twice or less the number of moles, wherein the basic material is (i) an alkali hydroxide; (Ii) a step selected from the group consisting of hydroxides of alkaline earth metals, and (iii) hydroxides of quaternary ammoniums. C) heating the mixture at a temperature between 15 ° C and 45 ° C. D) optionally heating the aqueous mixture with stirring until the insoluble solids remaining in the aqueous mixture are dissolved; A step of causing a solution,
A method for preparing a poly (vinyl acetate) copolymer ionomer solution, comprising: 9. The method of claim 8, wherein the formation of the aqueous solution of step d) is achieved by heating to 85-95 ° C. and maintaining that temperature for at least one hour. 10. The aqueous mixture contains from 5 to 25 percent of the starting copolymer and the comonomer in the precursor copolymer is a level of 2 to 10 mole percent of methyl acrylate or methyl methacrylate. The base is present in the starting copolymer in an amount of from 0.5 to 2 per mole of copolymer or derived lactone.
A molar amount of sodium hydroxide or potassium hydroxide, characterized in that the complete aqueous solution of step d) is achieved by heating to 85-95 ° C. and maintaining that temperature for at least 1 hour. The method according to claim 9. 11. The method of claim 1, wherein the aqueous polymer solution is sized with a sizing solution comprising 1 to 20 weight percent aqueous polymer solution, wherein the aqueous polymer solution comprises water and a first polymer. The polymer is a poly (vinyl alcohol) copolymer, wherein the copolymer is 90 to 100 percent hydrolyzed with respect to any remaining vinyl acetate units from the precursor vinyl acetate copolymer. Has from 0.1 to 10 mole percent of anionic carboxylic acid metal salt units, optionally with a second polymer or a third polymer;
Or a size containing both the second polymer and the third polymer. 12. The size of claim 11, wherein the sizing solution comprises a poly (vinyl alcohol) copolymer ionomer containing 2 to 10 mole percent anionic metal carboxylate units. . 13. The method according to claim 12, wherein the second polymer in the polymer solution is the first and second polymers.
The second polymer is a non-ionomeric poly (vinyl alcohol) polymer, wherein the second polymer is a C1-C8 (meth) ) Poly (vinyl alcohol) homopolymers or poly (vinyl alcohol) containing up to 10 mole percent of units derived from alkyl acrylates, C1 to C3 dialkyl fumarate or dialkyl maleate, or mixtures of such polymers The size according to claim 11, which is a copolymer. 14. The sizing solution does not include a second polymer in the polymer solution, and further comprises a third polymer in addition to the first polymer, Present in an amount of 10 to 90 weight percent based on the total weight of said first polymer;
The starch of claim 3, wherein the third polymer is a natural starch, a synthetic starch, a physically modified starch, or a chemically modified starch, or a starch that is a mixture of such starches. The size described in 11. 15. The method according to claim 11, wherein the sizing solution for treating the size contains both the second polymer and the third polymer in addition to the first polymer. The stated size. 16. A method of treating a fabric with a sizing solution, wherein the sizing solution comprises 1 to 20 weight percent of an aqueous polymer solution, wherein the aqueous polymer solution comprises:
Water and a first polymer, wherein the first polymer is a poly (vinyl alcohol) copolymer ionomer, wherein the ionomer is based on residual vinyl acetate units from the precursor vinyl acetate copolymer. From 90 to 100 percent hydrolyzed, wherein the copolymer ionomer comprises from 0.1 to 10 mole percent anionic metal carboxylate units and optionally a second or third polymer. Alternatively, a method of treating a fabric with a sizing solution, comprising both the second polymer and the third polymer. 17. The method of claim 16, wherein the sizing solution comprises a poly (vinyl alcohol) copolymer ionomer containing 2 to 10 mole percent anionic metal carboxylate units. . 18. The method of claim 18, wherein the second polymer in the polymer solution is a non-ionomeric poly (vinyl alcohol) polymer, wherein the polymer is 10% based on the total weight of the first and second polymers. From 90 to 90 weight percent, wherein the second polymer is a C1-C8 alkyl (meth) acrylate, a C1-C3 dialkyl fumarate or a dialkyl maleate, or a mixture of such polymers. 17. The method of claim 16, wherein the method is a poly (vinyl alcohol) homopolymer or poly (vinyl alcohol) copolymer containing up to 10 mole percent of the derived units. 19. The sizing solution does not include a second polymer in the polymer solution, and further includes a third polymer in addition to the first polymer, Present in an amount of 10 to 90 weight percent based on the total weight of said first polymer;
The starch of claim 3, wherein the third polymer is a natural starch, a synthetic starch, a physically modified starch, or a chemically modified starch, or a starch that is a mixture of such starches. 17. The method according to item 16. 20. The method according to claim 19, wherein the sizing solution includes the second polymer in addition to the first polymer.
17. The method of claim 16, further comprising a third polymer and a third polymer.