JPH10324786A - Polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymer composition capable of providing an aqueous solution of the composition excellent in stability with the passage of time, and further capable of providing a coating film excellent in film properties by formulating a vinyl alcoholic polymer, a starch and saccharides in a specified proportion. SOLUTION: This polymer composition comprises (A) 100 pts.wt. vinyl alcoholic polymer, (B) 0.1-10,000 pts.wt. starch (e.g. oxidized starch) and (C) 0.1-1,000 pts.wt. saccharides, preferably at least one kind selected from monosaccharides, disaccharides and oligosaccharides. For example, the component A is preferably a polyvinyl alcohol modified with a hydrophobic group containing 0.1-20 mol.% α-olefin unit having <=20 carbons (e.g. ethylene), and preferably obtained by saponifying a polymer of a vinyl ester such as vinyl acetate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polymer composition. More specifically, it relates to a polymer composition having very good compatibility.

[0002]

2. Description of the Related Art Compositions of PVA (hereinafter abbreviated as PVA) and starch are used in paper processing agents, warp sizing agents, films and the like. However, the composition of PVA and starch is inferior in compatibility, so that the aqueous solution has poor stability and tends to undergo phase separation. The film obtained from the aqueous solution of the composition has poor transparency and poor film properties. PVA
Starch derivatives such as etherified starch, esterified starch, and cationized starch, and starch decomposed products such as oxidized starch and dextrin have been studied in order to improve the compatibility with PVA, but the compatibility with PVA is sufficient. is not. Carbon number 4-20
A modified PVA copolymerized with a long-chain alkyl group and a raw starch (Japanese Patent Application Laid-Open No. 56-14544), a vinyl alcohol polymer having a long-chain alkyl having 4 to 50 carbon atoms at the end, and a starch. (JP-B 5-75013) is known. However, these compositions have insufficient aqueous solution stability and film properties. The composition of polyvinyl alcohol and starch is used in paper processing agents, warp sizing agents, films, and the like because it is water-soluble and has a film-forming ability. However, polyvinyl alcohol and starch are inferior in compatibility, so that the aqueous solution of the composition has poor stability, and the resulting film has poor transparency and poor film properties. In order to improve the compatibility with polyvinyl alcohol, it has been attempted to use starch derivatives such as etherified starch, esterified starch, and cationized starch and oxidized starch, and starch degradation products such as dextrin. Is not sufficiently compatible.

On the other hand, it is known that the use of a modified polyvinyl alcohol copolymerized with a long-chain alkyl group having 4 to 20 carbon atoms improves the compatibility with raw starch (Japanese Patent Application Laid-Open No. 56-14544). However, although the stability of the mixed aqueous solution is improved as compared with ordinary polyvinyl alcohol, it is still insufficient, and the physical properties of the film produced from the mixed aqueous solution cannot be said to be satisfactory.
The above-mentioned modified starch has no effect. It is known that the use of a vinyl alcohol-based polymer having a long-chain alkyl having 4 to 50 carbon atoms at the terminal improves the compatibility with starch (Japanese Patent Publication No. 5-75013). Is certainly improved as compared with ordinary polyvinyl alcohol, but the physical properties of the film produced from the mixed aqueous solution cannot be said to be sufficiently satisfactory.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer composition having excellent stability over time of an aqueous solution of a composition and excellent physical properties of a film produced from the aqueous solution of the composition.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that 100 parts by weight of a vinyl alcohol-based polymer (A) and 0.1 to 100 parts by weight of a starch (B).
A polymer composition comprising 00 parts by weight and 0.1 to 1000 parts by weight of the saccharide (C) was found, and the present invention was completed.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl alcohol polymer used in the present invention (hereinafter, vinyl alcohol may be abbreviated as PVA) is not particularly limited as long as it is water-soluble or water-dispersible. PVA, anion-modified P
VA and cation-modified PVA can be used.
In particular, when the PVA-based polymer is inferior in the viscosity of the aqueous solution at low to high temperatures, for example, when the non-modified PVA or the hydrophobic group-modified PVA has high crystallinity, the effect of the present invention is remarkably exhibited. As the hydrophobic group-modified PVA, for example, an α-olefin unit having 20 or less carbon atoms is 0.1 to 20.
Mol% of PVA polymer, 0.1 to 20 vinyl ether units having a long-chain alkyl group having 20 or less carbon atoms.
Mol% -containing PVA-based polymer, hydroxy group-containing PVA-based polymer containing 0.1 to 20 mol% of α-olefin units having 20 or less carbon atoms, and having a long-chain alkyl group having 4 to 50 carbon atoms at the terminal But a hydrophobic group-modified PVA containing 0.1 to 20 mol% of α-olefin (preferably ethylene) units having 20 or less carbon atoms is preferable from the viewpoint of productivity. Α having 20 or less carbon atoms
-The content of the olefin unit is suitably from 0.1 to 20 mol%, preferably from 0.2 to 18 mol%,
3-15 mol% is more preferred. When the content of the α-olefin unit is less than 0.1% by mole, the effect of modifying the α-olefin is not exhibited, and when the content of the α-olefin unit is more than 20% by mole, the hydrophobicity is reduced. Is too strong P
The water solubility of the VA polymer itself becomes poor, and the characteristics as PVA are impaired.

The viscosity-average degree of polymerization of a PVA-based polymer (hereinafter referred to as
(Abbreviated as polymerization degree) is preferably 50 to 30,000, and 7
0 to 20,000 is more preferable, and 100 to 15000 is particularly preferable. The degree of polymerization of the PVA polymer is determined according to JIS-K
This is the viscosity average degree of polymerization (P) of the polymer purified after re-saponification according to 6726 and determined by the following equation from the intrinsic viscosity [η] measured at 30 ° C. in water. P = ([η] × 10 ³ /8.29) ^{(1 / 0.62) When the} degree of polymerization is less than 50, the properties of PVA are hardly exhibited in the film properties obtained from the composition. 3000 degree of polymerization
If it is greater than 0, the viscosity of the aqueous dispersion becomes too high and handling becomes difficult. The saponification degree of the PVA-based polymer is not particularly limited as long as the PVA-based polymer is water-soluble or water-dispersible, but is suitably 60 to 99.99 mol%, and preferably 80 to 99.9 mol%. , 90-99.8
Molar% is more preferred. Generally, when the degree of saponification is less than 60 mol%, the water solubility is reduced. Saponification degree 9
When it is more than 9.99 mol%, there is no particular problem in performance, but it is difficult to produce a PVA-based polymer. When water resistance is required for a film produced from the aqueous solution of the composition, the degree of saponification is 8 depending on the presence / absence of modification, modified species and amount of modification.
0 mol% or more is preferable, and 90 mol% or more is more preferable.

The PVA polymer used in the present invention can be obtained by saponifying a vinyl ester polymer. As the vinyl ester, for example,
Vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like;
From the viewpoint of obtaining vinyl acetate, vinyl acetate is preferred. The PVA-based polymer of the present invention may be a copolymer of a copolymerizable ethylenically unsaturated monomer as long as the effects of the present invention are not impaired. Examples of the ethylenically unsaturated monomer unit include ethylene, propylene, 1-butene, 1-hexene,
Α-olefins such as octene, 3-butene-1-
All, 5-hexen-1-ol, 7-octene-1
-Ol, 9-decene-1-ol, 3-methyl-3-
Hydroxyl group-containing olefins such as buten-1-ol, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, and (anhydrous) itaconic acid, or salts or carbon atoms thereof. 1 to
18 mono or dialkyl esters; acrylamide, C 1-18 N-alkylacrylamide,
N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or a salt thereof, acrylamidopropyldimethylamine or a salt thereof or 4
Acrylamides such as quaternary salts; methacrylamide, N-alkylmethacrylamide having 1 to 18 carbon atoms, N, N-
Methacrylamides such as dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or a salt thereof, methacrylamidopropyldimethylamine or an acid salt or a quaternary salt thereof; N-vinylpyrrolidone;
N-vinylamides such as N-vinylformamide and N-vinylacetamide; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxyalkyl vinyl ethers Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and vinyl bromide; vinyl silanes such as trimethoxyvinyl silane; allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3 -Acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid and the like. The content of the monomer having these characteristic groups is usually 20 mol% or less, preferably 18 mol%.
Or less, more preferably 15 mol% or less. Further, the vinyl alcohol polymer of the present invention polymerizes a vinyl ester monomer such as vinyl acetate in the presence of a thiol compound such as thiolacetic acid, mercaptopropionic acid, or an alkyl mercaptan having 50 or less carbon atoms. May be a terminally modified product obtained by saponification of

As the starch (B), raw starch, raw starch degradation product, starch derivative and amylose are used. Examples of the raw starch include starch obtained from wheat, corn, rice, potato, sweet potato, tapioca, sago palm, and the like. In general, wheat starch, corn starch, and potato starch are suitable. Examples of raw starch degradation products include oxidized starch and dextrin, and oxidized starch is suitable. Examples of the starch derivative include etherified starch, esterified starch, and cationized starch. The content of (B) in the present invention is:
(A) 0.1 to 10000 parts by weight, preferably 1 to 8000 parts by weight, more preferably 2 to 5000 parts by weight, based on 100 parts by weight. If the content of the starch (B) is less than 0.1 part by weight based on 100 parts by weight of the PVA-based polymer (A), the physical properties of the PVA-based polymer are not changed and the starch is not effective.
If the content of (B) exceeds 10,000 parts by weight, the physical properties of starch do not change and the effect of the PVA-based polymer is not obtained.

Examples of the saccharide (C) include monosaccharides, disaccharides, oligosaccharides and polysaccharides, but monosaccharides, disaccharides and oligosaccharides (preferably those having 10-mers or less) are preferable. Monosaccharides include glucose, fructose,
Examples include isomerized sugar and xylose. Examples of the disaccharide include maltose, lactose, sucrose, trehalose, palatinose, reduced maltose, reduced palatinose, reduced lactose, and the like. Examples of the oligosaccharides include syrup, isomaltigosaccharides, fructooligosaccharides, lactose oligosaccharides, soybean oligosaccharides, xylo-oligosaccharides, coupling sugars, cyclodextrin compounds, and the like, with cyclodextrin compounds being preferred. As polysaccharides,
Pullulan, pectin, agar, konjac mannan, polydextrose, xanthan gum and the like can be mentioned. The content of (C) in the present invention is preferably 0.1 to 1000 parts by weight, preferably 0.2 to 200 parts by weight, more preferably 0.3 to 100 parts by weight, per 100 parts by weight of (A).
Sugar (C) per 100 parts by weight of PVA-based polymer (A)
If the content of is less than 0.1 part by weight, the properties of the mixture of the PVA-based polymer and the starch remain unchanged and the effect of adding the saccharide is not obtained. On the other hand, if the content of (C) exceeds 1000 parts by weight, the effect of the mixture of the PVA-based polymer and the starch will not be attained because the physical properties of the saccharide will be the main component.

The mixing ratio of the PVA polymer (A), the starch (B) and the saccharide (C) is not particularly limited as long as the amount is as described above, but (A) and [(B) + (C) )] And [(B) + (C)] with respect to 100 parts by weight of (A).
Is preferably from 0.1 to 10000 parts by weight, more preferably from 1 to 1000 parts by weight, and the weight mixing ratio of (B) and (C) is such that (C) is 0.1 to 100 parts by weight with respect to (B). 1000
0 parts by weight is suitable, and 1 to 1000 parts by weight is preferable.

The polymer composition of the present invention comprising the composition of the PVA polymer (A), the starch (B) and the saccharide (C) has the following features. The aqueous solution of the composition of the present invention comprises P
Compared with the aqueous solution of the composition of the VA polymer (A) and the starch (B), the aqueous solution has higher transparency, better storage stability, less phase separation, less change in viscosity with time, and easier handling. Easy. This is because the saccharide (C) is a PVA polymer (A)
It is assumed that the starch (B) plays a role as a compatibilizer with the starch (B), and the starch (B) is uniformly dispersed in the aqueous solution without much aggregation. As the polymer composition of the present invention, known PVA-based polymers such as ordinary unmodified PVA, nonionic-modified PVA, anion-modified PVA, and cation-modified PVA can be used. The above effect is particularly remarkable in the case of a hydrophobic group-modified PVA having an anionic group at the same time.

A film formed from an aqueous solution of the composition of the present invention is more uniform and has better transparency than a film formed from an aqueous solution of a mixture of a PVA polymer (A) and a starch (B). The film has high strength, elongation, elastic modulus and toughness, and is excellent in mechanical properties of the film. Further, a film formed from an aqueous solution of the composition of the present invention may have excellent water resistance comparable to that of the used PVA-based polymer alone, and the composition of the present invention has the characteristics of the PVA-based polymer. Do not spoil.

The composition of the present invention is preferably used mainly in the form of an aqueous solution.
0% by weight is preferred. 1.5% by weight as the lower limit of concentration
, Preferably 2% by weight, more preferably 3% by weight. The upper limit of the concentration is preferably 45% by weight,
It is more preferably 40% by weight, particularly preferably 30% by weight. The PVA-based polymer (A), the starch (B) and the saccharide (C) are mixed with a powder by mixing the three components, and then adding water or putting into water to form an aqueous solution, component (A) And adding component (B) as a powder and adding water or putting into water to form an aqueous solution, then dissolving component (C) in the aqueous solution after adding the component (C) to the powder, After mixing and adding water or throwing into water to form an aqueous solution, an arbitrary method such as mixing the remaining one component aqueous solution, separately forming the three components into aqueous solutions, and then mixing is adopted. The compositions of the present invention may include plasticizers, colorants, fillers, salts, boric acid or borax, other water-soluble polymers, surfactants, defoamers and other additives.

The composition of the present invention can be used as a paper processing agent, a film forming agent, a fiber sizing agent, particularly a warp sizing agent, an adhesive or a molded product.

[0016]

EXAMPLES The present invention will be described in more detail with reference to Examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified. In the following, the viscosity is a value measured using a B-type viscometer manufactured by Tokyo Keiki at 30 ° C. and a rotor rotation speed of 12 rpm. Table 1 shows details of the PVA-based polymer used.

[0017]

[Table 1]

Example 1 PVA having a degree of polymerization of 1750 and a degree of saponification of 98.4 mol% (P
-1), oxidized starch (manufactured by Nippon Shokuhin Kako Co., Ltd., trade name: MS)
-3800) and trehalose (trade name: trehalose, manufactured by Hayashibara Co., Ltd.) were heated and dissolved in hot water at 95 ° C. for 2 hours to prepare an aqueous solution having a solid content of 5%. The transmittance of this aqueous solution at 20 ° C. was measured. Table 2 shows the results.
Shown in (Method of measuring transmittance of aqueous solution) Using Hitachi spectrophotometer (manufactured by Hitachi, Ltd.) Wavelength: 650 nm Cell width: 10 mm

Examples 2-3 and Comparative Examples 1-3 Modified PVA (P-2) containing 5 mol% of ethylene, oxidized starch (trade name: MS-3800, manufactured by Nippon Shokuhin Kako Co., Ltd.)
And β-cyclodextrin (Nippon Shokuhin Kako Co., Ltd.,
With respect to the mixture (product name: Celdex B-100) (Example 2), the transmittance of the aqueous solution was measured in the same manner as in Example 1. 16 mol% ethylene and 3 maleic anhydride
A mixture of modified PVA (P-3), oxidized starch (manufactured by Nippon Shokuhin Kako Co., Ltd., trade name: MS-3800) copolymerized with mol% and glucose (Example 3) was produced in the same manner as in Example 1. The transmittance of the aqueous solution was measured. About the mixture (Comparative Examples 1-3) from which the saccharide was removed from the mixed compositions of Examples 1 to 3, the transmittance of the aqueous solution was measured in the same manner as in Example 1. Table 2 shows the results.

It can be seen that the solution prepared from the mixture comprising the PVA-based polymer, starch and saccharide has a higher aqueous solution transmittance than the solution prepared from the mixture of the PVA-based polymer and starch. From this, it is presumed that the saccharide has a specific interaction with the PVA-based polymer and the starch and has improved compatibility.

[0021]

[Table 2]

Example 4 Modified PVA (P-4) containing 10 mol% of ethylene, oxidized starch (manufactured by Nippon Shokuhin Kako Co., Ltd., trade name: MS-380)
A mixture of 0) and β-cyclodextrin at a ratio of 50:50:10 (weight basis) was heated and dissolved in hot water at 95 ° C. for 3 hours to prepare an aqueous solution having a solid content of 7%. The viscosity of this aqueous solution at 20 ° C. was measured immediately after the preparation of the aqueous solution and one week later. The state of the aqueous solution one week later was also observed.
Table 3 shows the results.

Examples 5 to 6 and Comparative Examples 4 to 6 A mixture in which the modified PVA and the saccharide in Example 4 were changed to the modified PVA (P-5 to P-6) and the saccharide shown in Table 1 (Examples 5 to 6) 6) Investigation was conducted in the same manner as in Example 4. For the mixtures (Comparative Examples 4 to 6) obtained by removing the saccharides from the mixed compositions of Examples 4 to 6, the viscosity change of the aqueous solution was measured in the same manner as in Example 4. Table 3 shows the results.

An aqueous solution prepared from a mixture of a PVA-based polymer and starch has a large change with time in viscosity, is easily separated, and has a problem in handling. On the other hand, it can be seen that the aqueous solution prepared from the mixture comprising the PVA-based polymer, starch and saccharide has a small change in viscosity over time and good storage stability.

[0025]

[Table 3]

Example 7 PVA having a polymerization degree of 1750 and a saponification degree of 98.4 mol% (P
-1), oxidized starch (manufactured by Nippon Shokuhin Kako Co., Ltd., trade name: MS)
-3800) and β-cyclodextrin at various ratios were heated and dissolved in hot water at 95 ° C. for 3 hours to prepare an aqueous solution having a solid content of 5%. This aqueous solution was poured onto a glass plate on which polyethylene terephthalate was adhered, and water was evaporated at 20 ° C. to form a film.
The film was conditioned at 20 ° C. and 84% RH for one week, and the elongation of the film was measured. Table 4 shows the results. (Measurement method of physical properties of film) Shimadzu Autograph DSC-100 (manufactured by Shimadzu Corporation) used Sample: width 10 mm, thickness 45 ± 5 μm, measurement length 50 mm Peeling speed: 500 mm / min

Example 8 and Comparative Examples 7 to 8 In the same manner as in Example 7, ethylene-modified PVA (P-2)
A mixed composition of oxidized starch MS-3800 and trehalose (Example 8) was examined. About the film | membrane produced from the composition (Comparative Examples 8-9) which removed the saccharide | sugar from the mixed composition of Examples 8-9, it is 20 degreeC like Example 8, 8 degreeC.
The strong elongation of the film conditioned at 4% RH for one week was measured. Table 4 shows the results.

Compared with a film prepared from a composition comprising a PVA polymer and a starch, a film prepared from a composition comprising a PVA polymer, starch and a saccharide is excellent in uniformity and transparency,
It can be seen that strength, elongation, elastic modulus, and toughness are large and have excellent film properties. Further, it can be seen that the change with time of the viscosity is small and the storage stability is also good.

[0029]

[Table 4]

1) Judgment of the transparency of the film: Judgment by visual observation in 5 steps 5: Transparent 4: Almost transparent 3: Translucent 2: Ground glass 1: No transparency

Example 9 Modified PVA (P-2) having 5 mol% of ethylene, oxidized starch (trade name: MS-3800, manufactured by Nippon Shokuhin Kako Co., Ltd.)
An aqueous solution was prepared from the mixture of lactose and lactose at various ratios in the same manner as in Example 7 to form a film. The film was taken out after being immersed in water at 20 ° C. for 24 hours,
The degree of swelling and the dissolution rate of the film were measured. Table 5 shows the results. (Measurement method of swelling degree and dissolution rate of film) Sample: 50 mm × 30 mm, thickness of 45 ± 5 μm Water: 100 ml, 20 ° C., 24 hours Swelling degree (fold) = (weight of film after water immersion) ÷ (water immersion) Later, 10
Elution rate (%) = {(pure weight of coating before immersion in water) − (weight of coating after immersion in water at 105 ° C. for 5 hours)} × 100} ( Pure weight of film before water immersion)

Example 10 and Comparative Examples 1 to 3 Ethylene-modified PV having different amounts of ethylene modification and different degrees of polymerization
A (P-7) was examined in the same manner as in Example 7 (Example 10). A single film of the same ethylene-modified PVA as in Examples 9 and 10 was produced, and the swelling degree and the dissolution rate of the film were examined (Comparative Examples 1 and 2). Degree of polymerization 175
0, a single film of PVA (P-1) having a saponification degree of 98.4 mol% was prepared, and the swelling degree and the dissolution rate of the film were examined (Control Example 3). Table 5 shows the results.

Since the coating of the present invention composed of the PVA polymer, starch and saccharide has almost the same degree of swelling as the coating of the PVA polymer alone, the PVA-based polymer composition of the present invention is a PVA-based polymer. It can be seen that the original characteristics of the polymer are retained. Further, it can be seen that the coating of the present invention has excellent water resistance as compared with a single coating of fully saponified PVA (P-1) which is usually used as a water-resistant PVA.

[0034]

[Table 5]

[0035]

The polymer composition of the present invention has good compatibility of each component, no phase separation of the aqueous solution of the composition, no increase in viscosity over time, and excellent workability. Further, the film obtained by forming an aqueous solution of the composition is excellent in transparency, film properties, and water resistance, and is therefore a paper processing agent, a film forming agent, a fiber sizing agent (particularly, a warp sizing agent). , Adhesives and molded articles.

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[Procedure amendment]

[Submission date] June 3, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0002

[Correction method] Change

[Correction contents]

[0002]

2. Description of the Related Art Compositions of PVA (hereinafter abbreviated as PVA) and starch are used in paper processing agents, warp sizing agents, films and the like. However, the composition of PVA and starch is inferior in compatibility, so that the aqueous solution has poor stability and tends to undergo layer separation. The film obtained from the aqueous solution of the composition has poor transparency and poor film properties. PVA
Starch derivatives such as etherified starch, esterified starch, and cationized starch, and starch decomposed products such as oxidized starch and dextrin have been studied in order to improve the compatibility with PVA, but the compatibility with PVA is sufficient. is not. Carbon number 4-20
A modified PVA copolymerized with a long-chain alkyl group and a raw starch (Japanese Patent Application Laid-Open No. 56-14544), a vinyl alcohol polymer having a long-chain alkyl having 4 to 50 carbon atoms at the end, and a starch. (JP-B 5-75013) is known. However, these compositions have insufficient aqueous solution stability and film properties. The composition of polyvinyl alcohol and starch is used in paper processing agents, warp sizing agents, films, and the like because it is water-soluble and has a film-forming ability. However, polyvinyl alcohol and starch are inferior in compatibility, so that the aqueous solution of the composition has poor stability, and the resulting film has poor transparency and poor film properties. In order to improve the compatibility with polyvinyl alcohol, it has been attempted to use starch derivatives such as etherified starch, esterified starch, and cationized starch and oxidized starch, and starch degradation products such as dextrin. Is not sufficiently compatible.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0003

[Correction method] Change

[Correction contents]

On the other hand, it is known that the use of a modified polyvinyl alcohol copolymerized with a long-chain alkyl group having 4 to 20 carbon atoms improves the compatibility with raw starch (Japanese Patent Application Laid-Open No. 56-14544). However, although the stability of the mixed aqueous solution is improved as compared with ordinary polyvinyl alcohol, it is still insufficient, and the physical properties of the film produced from the mixed aqueous solution cannot be said to be satisfactory.
The above-mentioned modified starch has no effect. End it is known that the number of carbon atoms is increased compatibility with starch With the vinyl alcohol polymer having a long chain alkyl 4-50 in (Kokoku 5-75013), the stability of the mixed aqueous solution Although it certainly improves as compared with ordinary polyvinyl alcohol, the physical properties of the film produced from the mixed aqueous solution cannot be said to be sufficiently satisfactory.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

The polymer composition of the present invention comprising the composition of the PVA polymer (A), the starch (B) and the saccharide (C) has the following features. The aqueous solution of the composition of the present invention comprises P
Compared with the aqueous solution of the composition of the VA polymer (A) and the starch (B), the aqueous solution has higher transparency and better storage stability.
It is difficult to separate layers , the change in viscosity with time is small, and handling is easy. This is because the saccharide (C) is a PVA polymer (A)
It is assumed that the starch (B) plays a role as a compatibilizer with the starch (B), and the starch (B) is uniformly dispersed in the aqueous solution without much aggregation. As the polymer composition of the present invention, known PVA-based polymers such as ordinary unmodified PVA, nonionic-modified PVA, anion-modified PVA, and cation-modified PVA can be used. The above effect is particularly remarkable in the case of a hydrophobic group-modified PVA having an anionic group at the same time.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0027

[Correction method] Change

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Example 8 and Comparative Examples 7 to 8 In the same manner as in Example 7, ethylene-modified PVA (P-2)
A mixed composition of oxidized starch MS-3800 and trehalose (Example 8) was examined. The film made from the composition, excluding sugar from mixed composition of Example 7-8 (Comparative Example 7-8), 20 ° C. in the same manner as in Example 7, 84
The strong elongation of the film conditioned at% RH for one week was measured. Table 4 shows the results.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction contents]

[0035]

The polymer composition of the present invention has good compatibility of each component, no layer separation of the aqueous solution of the composition, no increase in viscosity over time, and excellent workability. Further, the film obtained by forming an aqueous solution of the composition is excellent in transparency, film properties, and water resistance, and is therefore a paper processing agent, a film forming agent, a fiber sizing agent (particularly, a warp sizing agent). , Adhesives and molded articles.

Claims (2)

[Claims] 1. A vinyl alcohol polymer (A) 100
A polymer composition comprising, by weight, 0.1 to 10000 parts by weight of starch (B) and 0.1 to 1000 parts by weight of saccharide (C). 2. The polymer composition according to claim 1, wherein the saccharide (B) is at least one selected from monosaccharides, disaccharides and oligosaccharides.