JPWO2008142835A1 - Roll of water-soluble polyvinyl alcohol film and storage method thereof - Google Patents

Abstract

Provided is a roll of water-soluble PVA film free from or having tarmi and wrinkles, and a method for producing the same. The roll-like material is formed from a water-soluble polyvinyl alcohol-based film that dissolves by stirring in water at 20 ° C., and the film has a plasticizer content and a water content of 1 to 30 wt. % And 1 to 10% by weight, and the porosity between roll-like films is 4 to 25%. Then, in the winding process, the film is wound around a cylindrical core having a winding tension of 5 to 40 kgf / 1 m to form a roll. In the film unwound from the roll, the total width of the distorted portions of the film existing in the width direction is 10% or less of the total film width.

Description

Related applications

  This application claims the priority of Japanese Patent Application No. 2007-127486 for which it applied on May 14, 2007 in Japan, The whole is referred as forming a part of this application by reference.

  The present invention relates to a roll of water-soluble polyvinyl alcohol film, a method for producing the roll, and a method for storing the roll.

  Water-soluble polyvinyl alcohol film (hereinafter, polyvinyl alcohol film may be abbreviated as PVA film, and polyvinyl alcohol as a raw material may be abbreviated as PVA) is a packaging of agricultural chemicals and detergents (Patent Documents 1 to 3). It is widely used in the application fields such as 3).

  The water-soluble PVA film used for these applications is wound into a roll after production to form a roll, and after being temporarily stored, it is transported to a processing place, and the film is re-rolled from the roll. Unwind and serve for printing machine or automatic bag making machine.

  The film subjected to the printing machine or the bag making machine is processed by passing between nip rolls separated from each other, and the film passes through the air between the nip rolls. In order to prevent the film from wrinkling while passing through the air, an appropriate speed difference is provided between the nip rolls to keep the film stretched. If the film is more slack than the other parts, the stretched film is not maintained, and there is a problem that the film is distorted or distorted in the vertical direction.

  Further, in order to prevent the PVA film from absorbing moisture, the optical PVA film or the like has been devised such as packaging with a highly moisture-proof packaging material (Patent Document 4) or using a dehumidifying agent. For water-soluble PVA films that are even more hygroscopic than PVA films for use, it is still possible to completely prevent moisture absorption by these methods. May occur, causing troubles that reduce the yield in the factory.

Japanese Patent No. 2688557 (claims, paragraph number [0002]) JP-A-6-340899 (claims, paragraph number [0001]) Japanese Patent Laid-Open No. 7-118407 (Claims, paragraph number [0001]) Japanese Patent Laid-Open No. 2001-315885 (Claims)

  Recently, in order to improve the printing accuracy when printing on water-soluble PVA film and to reduce the loss at the time of bag making, water-soluble PVA film has been solved more than ever before. Has come to be required.

Accordingly, an object of the present invention is to provide a roll of water-soluble PVA film that has no or very little distortion and wrinkles during unwinding even after storage for a predetermined period.
Another object of the present invention is to produce a water-soluble PVA film that can reduce the residual stress during storage and prevent the film from being distorted or wrinkled, even if it is a flexible and stretchable water-soluble PVA film. It is to provide a method.
Still another object of the present invention is to provide a storage method capable of storing for a long time even a water-soluble PVA film roll that is easily affected by environmental changes such as humidity and temperature.

  When the present inventors examined the cause of the occurrence of tarmi (or distortion) and wrinkles when a roll of water-soluble PVA film is unwound, such tarmi and wrinkles are stored in a roll. We have found that this is caused by the minute deformation that sometimes occurs.

  For example, the film is wound on a roll-shaped material after film formation, but is wound with a certain tensile force in order to prevent winding deviation. Therefore, a little stress remains in the wound film, and the film shrinks during storage and the whole roll tries to shrink in the winding axis direction. At this time, the thick part of the film rises and is perpendicular to the winding axis (the roll of the roll). It is stretched in the direction of the surface) and rises to a bump shape. In order to prevent this, an effort has been made to make the thickness distribution of the film uniform during film formation. However, since the PVA film is easy to stretch, there is a problem that even if the thickness is made uniform, residual stress is generated due to the tension at the time of winding on the roll.

  On the other hand, if the winding of the film is loosened to prevent the occurrence of residual stress, the gap between the films becomes large, causing a shift called “layer shift”, “bamboo shoot”, “telescope”, etc., or wrinkles. Occurs and the film becomes unusable.

  In addition, as described above, since the water-soluble PVA film reacts extremely sensitively to environmental changes, for example, if the film is affected by changes in temperature or humidity during storage, the film may be deformed by moisture changes or absorb moisture. May cause non-uniform expansion and deformation. As a result, such minute deformation leads to film tarmi (or distortion), and may cause wrinkles during unwinding.

  Therefore, as a result of further intensive studies, the inventors have made a specific plasticizer content and a moisture content even with a PVA film excellent in solubility in low-temperature water, and the winding tension of the film, etc. When a roll-like product is formed by adjusting the porosity between the films within an appropriate range, the film unwound from the roll-like product is found to be extremely free of tarmi and wrinkles. Completed the invention.

That is, the present invention is a roll-shaped product in which a water-soluble polyvinyl alcohol film is wound around a cylindrical core, and the polyvinyl alcohol film has a plasticizer content of 1 to 30% by weight and a moisture content. 1 to 10% by weight and is dissolved by stirring in water at 20 ° C., and the porosity between the films of the roll product defined by the following formula is 4 to 25%,
Porosity (%) = {(π / 4) (H ² −D ² ) / (L × M)} × 100-100
H. Diameter of film roll (mm)
D · · · Core outer diameter (mm)
L. Length of film (m)
M ·· Average thickness of film (μm)
When the polyvinyl alcohol film is unwound from the roll and uniformly applied with a tension of 2 kgf per 1 m width in the film flow direction, the total width of the strained portions of the film existing in the film width direction is 10% of the total film width. % Or less.

  Since the water-soluble polyvinyl alcohol film is highly water-soluble, the polyvinyl alcohol constituting the film may have a saponification degree of about 80 to 99.95 mol%.

  Moreover, in the said roll-shaped material, the said water-soluble polyvinyl alcohol-type film may contain the slip agent in the inside, or may have made the slip agent adhere to the surface, and may contain the boron compound. Good.

  Moreover, this invention includes the method of manufacturing the said roll-shaped thing. That is, a method for producing a roll of a water-soluble polyvinyl alcohol film that is dissolved by stirring in water at 20 ° C., wherein a polyvinyl alcohol film containing polyvinyl alcohol and a plasticizer is dried, and the plasticizer content is A film forming step for forming a polyvinyl alcohol film having a water content of 1 to 10% by weight with 1 to 30% by weight, and a winding for winding the film around a cylindrical core to form a roll A winding step, and in the winding step, the film winding tension is 5 to 40 kgf per 1 m width.

  The polyvinyl alcohol film may be formed using at least one of a film forming method selected from a casting film forming method, a wet film forming method, a gel film forming method, and a melt extrusion film forming method. Moreover, in the winding process, it is preferable that the tension at the winding end with respect to the winding tension at the beginning of winding is 60 to 90%. Such a roll-shaped product often has a length (L) of the water-soluble polyvinyl alcohol film of about 100 to 3000 m.

  Moreover, in order to reduce distortion and wrinkles at the time of unwinding, the method for producing a roll of water-soluble PVA may further include a step of embossing the dried film. The cylindrical core is preferably, for example, a cylindrical core having an outer diameter of about 10 to 200 mm and a thickness of about 1.5 to 20 mm.

  The present invention includes a roll of a water-soluble polyvinyl alcohol film obtained by the production method described above.

  The water-soluble polyvinyl alcohol film unwound from such a roll can be suitably used as a hydraulic transfer curved surface printing film, an agricultural chemical packaging film, a detergent packaging film, and the like.

The present invention further includes a method for storing a roll-shaped product of a water-soluble polyvinyl alcohol film, wherein the roll-shaped product is a film having a moisture permeability coefficient of 30 g / m ² / day or less. Store in a packaged temperature range. The upper limit of the temperature range during storage is the higher temperature (° C.) of (T-168) ° C. and 18 ° C., and the lower limit is the lower temperature of (T-180) ° C. and 10 ° C. (° C). Here, T is the temperature (° C.) of the main peak obtained by differential thermal analysis of the polyvinyl alcohol film.

  In addition, in this specification, the distortion (or tarmi) of the film means a minute deformed portion which is a portion where reflection is disturbed when light is irradiated on the film surface of the film spread by applying a predetermined tension, More specifically, the judgment is made under the following conditions.

  That is, first, a film is unwound from a roll and is spread between metal rolls arranged at intervals of 40 cm in parallel to the width direction of the film. Next, the film is uniformly fixed in the width direction in one metal roll, and a tension of 2 kgf per 1 m width is uniformly applied in the flow direction of the film at a portion in contact with the other metal roll.

  Then, a fluorescent lamp (36 W, 117 cm, one piece) is placed at a position 1.5 m away upward in the normal direction of the spread film, and light is irradiated, and the reflection of light is disturbed on the film surface of the film. The part is judged as a distorted part in the film. Such disturbance of reflection is caused by the repeated appearance of sagging and tension on the film surface of the film, and can be easily confirmed visually.

  The “full width of the distorted portion” means a width obtained by adding up the widths of the distorted portions that intersect the straight line when a straight line is drawn in the width direction at a position in the arbitrary flow direction of the film.

  Hereinafter, a method for measuring the full width of the distortion portion will be described with reference to the drawings. FIG. 1 is a schematic top view of a film unwound from a roll-like material, in which a part of the film for observing a distortion portion is enlarged. That is, as shown in FIG. 1, the total width of the distorted portion is the strain width (or talmi) that intersects with the straight line at an arbitrary position in the flow direction MD of the spread film when a straight line is drawn parallel to the width direction WD. Width) Indicates the total width of W1, W2 and W3.

In the present invention, when producing a roll of a water-soluble PVA film, a film whose water content is adjusted under specific drying conditions is wound up with a specific tension. However, the residual stress generated in the film at the time of storage can be reduced, and the occurrence of talmi and wrinkles that are problematic when the film is unwound and used can be suppressed.
In addition, since the roll-like material obtained by the above-described production method is not easily deformed during storage, the film is not substantially wrinkled even when unrolled after storage. When the film is unwound from the roll, it is not broken and a homogeneous water-soluble PVA film can be taken out very smoothly.

  The invention will be more clearly understood from the following description of a preferred embodiment with reference to the accompanying drawings. However, the examples and figures are for illustration and description only and should not be used to define the scope of the invention. The scope of the invention is defined by the appended claims.

It is a schematic top view of the film unwound from the roll-shaped thing of this invention.

[Roll of water-soluble PVA film]
The roll-shaped product of the water-soluble PVA film of the present invention can be obtained by winding a water-soluble PVA film having a specific water content and plasticizer content described below under predetermined conditions. In addition, the water-soluble PVA film unwound from the roll-like material has almost no distorted portion, and the total width of the distorted portion of the film existing in the width direction of the film is 10% or less of the entire film width.

(Water-soluble PVA film)
In the present invention, the water-soluble PVA film is dissolved by stirring in water at 20 ° C., and more specifically, the complete dissolution time by stirring in water at 20 ° C. is 500 seconds or shorter, preferably 300 seconds or shorter. Preferably it is 200 seconds or less. Although there is no restriction | limiting in particular about the minimum of complete dissolution time, 1 second or more is suitable, More preferably, it is 2 second or more. The present invention has a particularly remarkable effect when the PVA film having excellent water solubility is made into a roll.

  In the present invention, the complete dissolution time of the water-soluble PVA film is measured as follows. That is, 325 cc of ion-exchanged water is placed in a 500 cc glass beaker and the water temperature is kept at 20 ° C. The water-soluble PVA film used as a sample was conditioned to 65% RH at a temperature of 20 ° C., then cut into a size of 3.5 cm × 4 cm, and the window frame was formed into a slide mount with a size of 2.2 cm × 3.4 cm. In a state where the film is sandwiched, in the center of the glass beaker in the water, using a magnetic stirrer having a rotor having a length of 5 cm, the sample is quickly immersed under stirring at a strength of 280 rpm, and observed. I do. The film soaked in water dissolves on the slide mount over time, or after it breaks, it will come off the slide mount, dissolve gradually while floating in water, and will be invisible to the naked eye, so immediately after soaking the film The time until disappearance with the naked eye is measured, and this is taken as the complete dissolution time.

  The complete dissolution time of the water-soluble PVA film can be adjusted by appropriately selecting the saponification degree, the polymerization degree, the modification degree due to the comonomer, etc. of the PVA used as a raw material.

The polymerization degree (Po) of PVA used as a raw material for the water-soluble PVA film is preferably 500 to 3500, and particularly selected from the range of 500 to 2500. Here, the polymerization degree of PVA is measured according to JIS K 6726. That is, after re-saponifying and purifying PVA, it is obtained by the following formula from intrinsic viscosity [η] (unit: deciliter / g) measured in water at 30 ° C.
P0 = ([[eta]] * 10 < ³ > /8.29) ^{(1 / 0.62)}

  The saponification degree of PVA is preferably 80 to 99.95 mol%, more preferably selected from the range of 83 to 98 mol%, and particularly preferably less than 95 mol. The degree of saponification of PVA indicates the proportion of units that are actually saponified to vinyl alcohol units among the units that can be converted to vinyl alcohol units by saponification. The saponification degree of PVA is measured according to JIS K 6726.

  PVA can be produced by polymerizing a vinyl ester monomer and saponifying the resulting vinyl ester polymer. Examples of vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like. Of these, vinyl acetate is preferred.

  When the vinyl ester monomer is polymerized, other copolymerizable monomers can be copolymerized within a range that does not impair the effects of the invention, if necessary. Examples of the monomer copolymerizable with the vinyl ester monomer include olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene and isobutene; acrylic acid and salts thereof; methyl acrylate and acrylic acid. Acrylics such as ethyl, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc. Acid esters; methacrylic acid and salts thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, methacrylic acid 2-ethylhexyl, dodecyl methacrylate Methacrylic acid esters such as octadecyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidopropyldimethylamine and salts thereof, N-methylolacrylamide and derivatives thereof, etc. Acrylamide derivatives; methacrylamide derivatives such as methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropyldimethylamine and salts thereof, N-methylolmethacrylamide and derivatives thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl Vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl Vinyl ethers such as ether, dodecyl vinyl ether and stearyl vinyl ether; Nitriles such as acrylonitrile and methacrylonitrile; Halogenated vinyls such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; Allyl such as allyl acetate and allyl chloride Compounds; maleic acid and salts thereof or esters thereof; itaconic acid and salts or esters thereof; vinylsilyl compounds such as vinyltrimethoxysilane; isopropenyl acetate and the like.

In addition to the above, suitable copolymerizable monomers include N-vinylformamide, N-vinylacetamide N-vinylamides, and other suitable N-vinylamide monomers include Examples thereof include monomers represented by the following formula (I), N-vinyl-2-pyrrolidones, and N-vinyl-2-caprolactam.
^{_{CH 2 = CH-N (R}} 1) -C (= O) -R 2 (I)
(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms)

In the above formula (I), examples of the alkyl group having 1 to 3 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, and an isopropyl group, and also represented by R ^2. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and an isopentyl group. Examples of the monomer represented by the formula (I) include N-methyl-N-vinylformamide and N-methyl-N-vinylacetamide.

  Examples of N-vinyl-2-pyrrolidones include N-vinyl-2-pyrrolidone, N-vinyl-3-propyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, and N-vinyl. Examples include -3,5-dimethyl-2-pyrrolidone.

  More preferable copolymerizable monomers include sulfonic acid group-containing monomers. Any sulfonic acid group-containing monomer may be used as long as it contains a sulfonic acid group or a salt thereof in the molecule and can be copolymerized with a vinyl ester. Specific examples include 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid and alkali metal salts thereof; ethylenesulfonic acid, allyl Examples thereof include olefin sulfonic acids such as sulfonic acid and methacryl sulfonic acid, and alkali metal salts thereof. Among these, 2-acrylamido-2-methylpropanesulfonic acid and its alkali metal salt are most preferable from the viewpoints of reactivity when copolymerized with a vinyl ester and stability during saponification. Here, examples of the alkali metal include sodium, potassium, and lithium.

  The copolymerization ratio of these copolymerizable monomers is preferably 15 mol% or less, and more preferably 10 mol or less. Further, it is preferably 0.01 mol% or more, and more preferably 0.05 mol% or more.

  In the present invention, it is important that the water-soluble PVA film contains 1 to 30% by weight of a plasticizer, and more preferably 2 to 25% by weight. When the water-soluble PVA film contains the plasticizer in this range, a roll-like product of the PVA film having no or very little tarmi (or distortion) and wrinkles, which is the object of the present invention, can be obtained. Here, the content of the plasticizer is a value calculated by {weight of plasticizer in film / weight of film}} × 100.

  As the plasticizer, polyhydric alcohol is preferably used. Examples of the polyhydric alcohol include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane and the like, and these use one kind or two or more kinds. be able to. Among these, ethylene glycol, glycerin or diglycerin is preferably used. These plasticizers are used by previously blending them with PVA when producing a PVA film.

  In the present invention, it is also important that the water content of the water-soluble PVA film is 1 to 10% by weight, more preferably 1 to 8% by weight, particularly preferably less than 6% by weight, for example, 5%. .5% by weight or less. By adjusting the moisture content within this range, a roll-like product of a PVA film free from or having very little tarmi (or distortion) or wrinkles can be obtained. Here, the moisture content refers to drying for 2 hours at 50 ° C. under a reduced pressure of 1 Pa or less using a vacuum dryer (DP33 manufactured by Yamato Scientific Co., Ltd.) and a vacuum pump (VR16LP manufactured by Hitachi Koki Co., Ltd.). Is calculated from the weight change rate at the time of carrying out the following equation.

Moisture content (%) = (A−B) / A × 100
Here, A represents the weight of the film before drying, and B represents the weight of the film after drying.

  In the present invention, blending a boron compound with PVA is also a preferred embodiment. Examples of the boron compound include boric acid and borates (calcium salt, zinc salt, cobalt salt, ammonium salt, sodium salt, potassium salt, lithium salt, borax, etc.). Of these, boric acid and borax are included. Is preferred. The compounding amount of the boron compound is preferably 0.01 to 3% by weight, more preferably 0.05 to 2% by weight with respect to PVA. By blending the boron compound, the generation of wrinkles and tarmi (or distortion) of the film can be further suppressed.

  A surfactant may be added when the PVA film is produced. Examples of surfactants that can be blended include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Suitable anionic surfactants are, for example, carboxylic acid types such as potassium laurate, sulfate ester types such as octyl sulfate, and sulfonic acid type anionic surfactants such as sodium dodecylbenzenesulfonate and sodium alkylbenzenesulfonate. . Examples of nonionic surfactants include alkyl ether types such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether, alkylphenyl ether types such as polyoxyethylene octylphenyl ether, and alkyl ester types such as polyoxyethylene laurate. , Alkylamine types such as polyoxyethylene lauryl amino ether, alkylamide types such as polyoxyethylene lauric acid amide, polypropylene glycol ether types such as polyoxyethylene polyoxypropylene ether, alkanolamide types such as oleic acid diethanolamide, poly Examples include allyl phenyl ether type such as oxyalkylene allyl phenyl ether. Examples of the cationic surfactant include amines such as laurylamine hydrochloride, quaternary ammonium salts such as lauryltrimethylammonium chloride, and pyridium salts such as laurylbiridinium chloride. Furthermore, examples of the amphoteric surfactant include N-alkyl-N, N-dimethylammonium betaine. Surfactant can be used 1 type or in combination of 2 or more types.

  The blending amount of the surfactant is preferably 0.01 to 7% by weight, more preferably 0.02 to 5% by weight with respect to PVA. By blending these surfactants, the intended roll-like product in the present invention can be obtained more suitably.

  As a method for producing a PVA film, for example, using a PVA solution in which PVA is dissolved in a solvent, a casting film forming method, a wet film forming method (discharging into a poor solvent), a gel film forming method (PVA aqueous solution) Once the gel is cooled and gelled, the solvent is extracted and removed to obtain a PVA film), and a combination of these methods and a PVA containing a plasticizer (which may contain water, organic solvents, etc.) are melted. And melt extrusion film forming method. Among these, the casting film forming method and the melt extrusion film forming method are preferable because the intended roll-like product can be obtained more suitably in the present invention.

  As a PVA solvent used for producing the PVA film, water is typical, but organic solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone can also be used. When using these organic solvents, it is preferable to use together with water.

In the present invention, in addition to the above-described complete dissolution time of the PVA film in water, the plasticizer content, and the moisture content, when the polyvinyl alcohol film is unwound from the roll, the width direction of the film It is important that the total width of the distorted portions of the film present in is 10% or less of the total width of the film.
When the distorted portion of the film unwound from the roll is within a predetermined range, it is possible to effectively suppress the formation of wrinkles on the unwound film and reduce the product loss.

  Further, in order to obtain a roll-like material having such properties, it is necessary that the porosity between the films at the time of winding is 4 to 25%, preferably 5 to 20%. The reason why the porosity between the films at the time of winding satisfies such a condition is not clear, but as will be apparent from the examples described later, there is no film sagging or wrinkles. Or an extremely small number of rolls can be obtained. In the present invention, by setting the porosity between the films in the above range, it is highly industrially significant that a roll-like product that can exhibit such excellent effects can be obtained.

Here, the porosity between the films of the roll-like product is a value defined by the following formula.
Porosity (%) = {π (H / 2) ² −π (D / 2) ² } / (L × M) × 100-100
That is,
Porosity (%) = {(π / 4) (H ² −D ² ) / (L × M)} × 100-100
H. Diameter of roll of film (mm)
D. ・ Outer diameter of cylindrical core (mm)
L. Length of film (m)
M ·· Average thickness of film (μm)

  H, D, L, and M are preferably selected from the ranges shown below, depending on the application of the roll.

H ··· 10 to 500 mm, preferably 50 to 300 mm
D ... 10-200mm, preferably 20-150mm
L · · 200-3000m, preferably 300-2000m
M ··· 10 to 150 μm, preferably 15 to 100 μm
Here, the diameter (H) of the film roll and the outer diameter (D) of the cylindrical core are average values of two lengths orthogonal to each other in an arbitrary cross section.

  The diameter (H) of the film roll is preferably 10 to 500 mm. When the diameter of the film roll is smaller than this, the unevenness of the film core and the effect of moisture absorption from the core are increased, and there is a possibility that tarmi and wrinkles are likely to occur over the entire length of the film. Furthermore, the film itself is easily affected by the winding stress, and there is a possibility that tarmi and wrinkles are likely to occur. On the other hand, if it is larger than this, the winding stress is excessively applied to the portion close to the core of the film, so that tarmi and wrinkles are likely to occur.

  The outer diameter (D) of the core is preferably 10 to 200 mm. When the outer diameter of the core is smaller than this, since the curvature of the portion of the wound film close to the core is large, there is a possibility that it is easily deformed, and that tarmi and wrinkles are likely to occur. On the other hand, if it is larger than this, it is likely that tarmi is likely to occur after storage, probably because the balance of the residual stress after winding of the portion close to the core and the portion far from the core is poor. By adjusting the surface roughness and storage conditions of the film, tarmi is less likely to occur, but the adjustment range may be narrowed.

  The length (L) of the film is preferably 200 to 3000 m. This range is similar to the idea of the preferred range of roll diameters (H). When the film is thin, the diameter of the roll may be in the above range even if the length exceeds 3000 m. However, since the number of windings increases and deformation tends to occur, there is a risk that tarmi and wrinkles are likely to occur. There is. On the other hand, when the film is thick, the diameter of the roll may fall within the above range even if the length is less than 200 m. However, at this time, since the number of windings is too small, it is difficult to equalize minute winding fluctuations. There is a risk that tarmi and wrinkles are likely to occur during winding.

  The thickness (M) of the film is preferably 10 to 150 μm. When the film is thinner than this, the film is easily deformed due to the influence of the tension during winding, the influence of the residual stress during storage of the roll, and the influence of the environment during storage, and as a result, there is a possibility of causing tarmi and wrinkles. On the other hand, if it is thicker than this, it is necessary to increase the tension at the time of winding to pull the film in order to keep it within the above-mentioned porosity, and the force of the residual stress received at that time remains strong in the roll and easily deforms. May be likely to occur.

Since the average thickness (M) of the film is uneven, the value measured by the following method is the average thickness. That is, a film 1 m ² was cut out from a roll-like material, and the weight was measured within 1 minute without adjusting the humidity {film weight (g / m ² )}. On the other hand, the dry density of the film was determined by Micrometrics Multivolume manufactured by Shimadzu Corporation. Measured using Pycnometer 1305 {dry density (g / cm ³ )} and calculated by the following formula.
Average film thickness (μm) = film weight (g / m ² ) / dry density (g / cm ³ )

  In the present invention, the width (W) of the water-soluble PVA film is preferably 100 to 2000 mm, and more preferably 200 to 1600 mm.

  In the present invention, a roll-like material having such a porosity is obtained by adjusting the film surface roughness, the presence or absence of slip agent adhesion, the amount of slip agent adhesion, the winding condition, etc. in a well-balanced manner. Can do.

The roughness of the film surface can be appropriately adjusted by embossing at least one surface of the film, that is, one or both surfaces, but it is preferable to emboss one surface. By embossing, for example, it is preferable to give a satin pattern with small unevenness to the surface of the film, or give a kinematic pattern with clear unevenness. For example, when embossing is performed, the roughness of the film surface may be about 0.05 to 0.5 μm, preferably about 0.1 to 0.4 μm.
As another method of adjusting the roughness of the film surface, there is also a method of previously containing a slip agent to be described later in the film, which can omit the embossing process, reduce defects and loss due to the embossing process. Is often economical. In this case, the addition amount of the slip agent is 0.1 to 5% by weight, preferably 0.5 to 4% by weight, based on PVA. In order to adjust the roughness of the film surface, one of an embossing method and a slip agent adding method may be employed, or both methods may be used in combination.

Whether or not to attach the slip agent to the film surface depends on the application of the roll-like material, and when the roll-like material is used for the hydraulic transfer film, the slip agent is often not adhered, and the packaging film for agricultural chemicals, When used for packaging films for detergents, slip agents are often attached. Therefore, the presence or absence of adhesion of the slip agent to the film surface and the amount of adhesion when the slip agent is adhered to the film surface are appropriately selected depending on the application of the roll-like material. When the amount of slip agent attached increases, the porosity increases, and when the amount of slip agent decreases decreases the porosity decreases. Here, the slip agent is attached to the surface of the PVA film for the purpose of improving the slip property between the rolled PVA films. For example, various starch-based organic powders, calcium carbonate, calcium sulfate, carbonate Examples thereof include inorganic powders such as magnesium, magnesium sulfate, silicic acid, talc, and clay. The average particle size of the slip agent is preferably 1 to 100 μm, more preferably 4 to 20 μm. The adhesion amount of the slip agent on the surface of the PVA film is preferably 0.1 g / m ² or less, and more preferably 0.08 g / m ² or less. The adhesion amount of the slip agent is preferably 0.001 g / m ² or more.

[Method for producing roll of water-soluble PVA film]
The roll-form thing of the water-soluble PVA-type film mentioned above can be manufactured with the following method.
First, a polyvinyl alcohol film containing polyvinyl alcohol and a plasticizer is dried (hereinafter, this process is referred to as a film drying process). The plasticizer content is 1 to 30% by weight and the moisture content is 1 to 10%. A PVA-based film having a weight percentage is formed. As described above, the PVA film may be a casting film forming method, a wet film forming method, a gel film forming method, and a combination thereof, or a PVA containing a plasticizer (including water, an organic solvent, etc.). The film can be formed by suitably utilizing a melt extrusion film forming method or the like carried out by melting (good).

The water content of the PVA film can be determined by appropriately adjusting the amount of water used as a PVA solvent when the PVA film is produced, and further the drying conditions of the PVA film after film formation. The drying temperature in the film drying step may be, for example, about 90 to 140 ° C, preferably about 95 to 135 ° C, and the drying time is about 2 to 10 minutes, preferably about 3 to 8 minutes. Also good.
After film formation, the PVA film formed through the film drying process forms a roll-like product through a winding process in which the film is wound around the cylindrical core with a predetermined winding tension.

  In the winding process, in a part of the process, the film winding tension needs to be 5 to 40 kgf / 1 m width, and preferably 10 to 35 kgf / 1 m width. The winding tension is appropriately adjusted in proportion to the width of the film. The winding tension may be the same from the start to the end of winding of the water-soluble PVA film, but it is preferable to gradually decrease the tension from the start of winding because the internal stress and the porosity can be made uniform. When the tension is gradually lowered from the winding start, the tension ratio (taper) at the winding end with respect to the winding start tension is preferably in the range of 60 to 90%, preferably 65 to 80%. When it deviates from this, the porosity in the vicinity of the core and the porosity in the vicinity of the unwinding tend to be nonuniform. Although it can be adjusted to some extent by the touch roll and speed described later, there are cases where the adjustment is limited.

In the winding process, in addition to adjusting the winding tension, the winding speed and the touch pressure of the touch roll may be adjusted. For example, the winding speed is preferably adjusted to 5 to 100 m / min, more preferably 10 to 80 m / min. If the winding speed is slower than this range, there is a risk of non-uniform rotation such as a gearing of the winding device, and if it is faster than this range, the film may flutter or cause uneven tension. In addition, the touch pressure of the touch roll is preferably 1 to 5 kgf / cm ^{2 and} more preferably 1.5 to 4 kgf / cm ² from the viewpoint of eliminating air entrained in the roll. If the touch pressure is lower than this range, it may be difficult to eliminate the entrapped air. Conversely, if the touch pressure is high, the film is pressed against the roll with excessive force, so that wrinkles are likely to occur during winding. .

  Examples of the material of the cylindrical core used for winding the water-soluble PVA film include paper, plastic, and metal. Among these, the core made of paper is particularly suitable. The surface of the paper core may be moisture-proofed with polyethylene or the like.

  Examples of metals used for the core material include iron and iron alloys such as carbon steel, high-tensile steel, and stainless steel, aluminum and aluminum alloys such as aluminum and duralumin, copper and copper alloys such as copper, brass, and bronze. It is done. The metal core may be laminated with soft polyvinyl chloride, low density polyethylene or the like, or may be plated with nickel, chromium, zinc, tin or the like.

  Examples of the plastic used for the core material include hard polyvinyl chloride, polypropylene, high density polyethylene, ultrahigh molecular weight polyethylene, polycarbonate, polyester, and polysulfone. Plastic core is a film whose outer surface is coated with hard polyvinyl chloride, soft polyvinyl chloride, polypropylene, low density polyethylene, high density polyethylene, ultra high molecular weight polyethylene, polycarbonate, polyester, polysulfone, polyvinylidene chloride, etc. Further, a film such as an aluminum vapor deposition film, an alumina vapor deposition film, or a glass vapor deposition film may be laminated (the coated surface or the vapor deposition surface may face either the core side or the anti-core side). The core structure is typically a tube.

  The thickness of the core varies depending on the material, but is preferably 1.5 to 20 mm, more preferably 2 to 15 mm, and most preferably 3 to 10 mm. When the thickness of the core satisfies this range, it is easy to suppress the occurrence of tarmi and wrinkles on the PVA film.

  The method for producing a roll of water-soluble PVA film may include at least the above-described film drying step and winding step in order to reduce the strained portion seen in the film unwound from the roll. It does not deny any process other than these processes.

  Further, in the winding process, it is possible to make a roll-shaped product by slitting to a predetermined width and winding it around a cylindrical core continuously with the film-forming drying process, or once, a long and wide master roll It is good also as a roll-shaped thing by slitting to a predetermined width off-line within several days, and winding around a cylindrical core. In addition, also when winding around a master roll, it is preferable to wind up by the above-mentioned winding conditions (for example, winding tension, winding speed, or touch roll touch pressure).

  Furthermore, it is preferable to include an embossing process for embossing the film in addition to the above-described film drying process. In the embossing process, the dry film is passed over an embossing roll (for example, a roll with a satin pattern or a silk pattern) that has been subjected to a predetermined process, thereby providing a predetermined surface roughness to the dry film. Give. Thereafter, the surface-roughened film may be cut as necessary and subjected to a winding process.

Moreover, when storing the said roll-shaped object, the water-soluble PVA which unwound from the roll-shaped object by storing in a fixed temperature range in the state packaged with the film whose moisture permeability coefficient is 30 g / m < ² > / day or less. It is possible to suppress the occurrence of tarmi (or distortion) and wrinkles on the film.

  The upper temperature range is the higher of (T-168) ° C and 18 ° C (° C) when the temperature of the main peak obtained by differential thermal analysis of the polyvinyl alcohol film is T (° C). The lower limit is (T-180) ° C. and 10 ° C., which is the lower temperature (° C.).

  By satisfying such humidity conditions and temperature conditions, the quality of the roll-like product is stably maintained. As a result, even a water-soluble PVA film that requires delicate handling is wound from the roll-like product. It is possible to more reliably suppress the occurrence of tarmi (or distortion) and wrinkles on the film when it is taken out.

It is important that the film used for packaging the roll-shaped material has a moisture permeability coefficient of 30 g / m ² / day or less, preferably 20 g / m ² / day or less, more preferably 15 g / m. ² / day or less. When the moisture permeability of the film exceeds 30 g / m ² / day, the moisture and plasticizer in the PVA film are volatilized during storage of the roll-like material, or the PVA film absorbs moisture from the outside air, and the roll-like product The composition of the PVA film changes between the surface portion and the core portion. Here, the moisture permeability coefficient is measured according to JIS Z 0208, and represents the difference between the moisture permeability in a 90% RH atmosphere and the moisture permeability in a 0% RH atmosphere at a temperature of 40 ° C.

  In addition, DSC Q1000 manufactured by TA Instruments was used for differential thermal analysis, and 6-8 mg of a sample PVA film was placed in an aluminum container and held at -30 ° C, and then from -30 ° C to 260 ° C at 10 ° C. The maximum endothermic peak measured at that time is taken as the main peak temperature (° C.).

  Films used in the packaging described above include laminated films of polyester, aluminum foil and polyethylene, laminated films of aluminum-deposited polyester and polyethylene, laminated films of alumina-deposited polyester and polyethylene, laminated films of glass-deposited polyester and polyethylene, and polyvinylidene chloride. Examples thereof include a laminated film of a coated polypropylene and polyethylene, a polypropylene film, a high density polyethylene film, and a low density polyethylene film. Moreover, the laminated product of these films, a burif, paper, a nonwoven fabric, etc. can also be illustrated. Furthermore, these films and laminates may be packaged on the outside with paper or may be housed in a carton box, a wooden box, a metal case, a frame, or the like.

  As a result of maintaining the quality of the roll-like product stably by storing the roll-like product packaged using the above-described film having excellent moisture-proof property in the above-mentioned specific temperature range, tarmi (or distortion) The object of the present invention to provide a roll of water-soluble PVA film free from or very little wrinkles is more reliably achieved.

  When transporting a roll-shaped product packaged using the above-described film having excellent moisture resistance, it is preferable to maintain the environmental temperature within the specific temperature range described above. As for the environmental humidity, it is preferable to avoid high humidity and low humidity. Specifically, it is preferably 30 to 90% RH, and more preferably 40 to 75% RH.

  Wrinkles of rolls of water-soluble PVA film are caused by uneven thickness in the width direction and length direction, the film is very hard or soft on the contrary, or the film has a large thickness and creases are generated during the process. Occurs. In order to eliminate this, it is possible to improve the uniformity of the thickness, bring the film hardness to an appropriate range, and reduce the tarmi as in the present invention. The wrinkles of the roll-shaped material are confirmed by visual observation while unwinding the film with respect to the roll-shaped material after storage, thereby confirming the presence or absence of wrinkles. In the initial stage of winding a water-soluble PVA film on a cylindrical core or master roll, the film may be slightly wrinkled due to fluctuations in the winding speed and winding tension. Wrinkles are eliminated when the film is wound up to a length of 100 m, so that when wrinkles are not recognized when the film is unwound from a roll of the film except for about 100 m on the winding core side, it is determined that there are no wrinkles. .

  A roll of water-soluble PVA film may absorb a small amount of moisture during storage, but a film unrolled 100 m or more from the roll is hardly affected by moisture absorption. (Or tarmi) is determined for a film unrolled 100 m. That is, a film unrolled 100 m from a roll-like material is spread between metal rolls arranged in parallel at an interval of 40 cm in the unwinding direction of the film, and after fixing one side uniformly, 2 kgf per 1 m width on one side Under the irradiation of a fluorescent lamp (36 W, 117 cm, 1 piece) placed at a position 1.5 m away from this, the reflection state of the film is visually observed, and sagging and tension are alternately applied to the film surface of the film. A portion where reflection is repeatedly disturbed is regarded as distortion (or talmi), the length in the width direction (film width direction) is measured, and the state of distortion (or talmi) is determined by the magnitude of the value. In addition, distortion (or tarmi) may occur independently in a plurality of vertically long shapes in the direction in which the film is unwound. In that case, the widths of all the distortions (or tarmi) are summed up. When the film is long, it is unwound every 200 m and averaged. A case where the total width of distortion (or tarmi) is 10% or less of the total width of the film is regarded as acceptable.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
Example 1
An aqueous solution having a PVA concentration of 15% by weight containing 15 parts by weight of PVA having a saponification degree of 88 mol% and a polymerization degree of 1700 and 0.65 parts by weight of glycerin is cast on a conveyor belt, and hot air at 120 ° C. is applied on the belt. The film was then dried for 5 minutes, then passed through a satin-finished (150 mesh sandblasted) metal roll, embossed on one side, and then cut at both ends with a leather blade. The film width (W) is 500 mm, the film thickness (M) is 30 μm, the roughness is an embossed surface of 0.3 μm, and the non-embossed surface is 0.15 μm (SE1700 manufactured by Kosaka Laboratories, with a stylus radius of 2 μm, a measurement speed of 0 PVA film {length (L) 1000 m (no excess)} of .5 m / second, measured with a cutoff value λc = 0.8), This is a cylindrical paper tube whose outer surface is processed with polyethylene {paper tube outer diameter (D) 88.2 mm, wall thickness 6 mm}, initial winding tension 15 kgf, winding speed 40 m / min, touch pressure 3 kgf / m. ² By rolling under the condition of a taper of 75%, a roll of water-soluble PVA film {diameter (H) 221 mm of cross section of roll) was obtained. When the winding tension is converted into a winding tension per 1 m of film width, the value is 30 kgf / 1 m width.

  The composition of the water-soluble PVA film was PVA / glycerin / water content = 93/4/3 (% by weight). Using a DSC Q1000 manufactured by TA Instruments, 7 mg of a film piece cut from a roll was put in an aluminum pan and held at -30 ° C for 1 minute, and then heated to 260 ° C at a heating rate of 10 ° C / min. As a result of differential thermal analysis, the temperature of the main peak was 186 ° C.

The roll-like material obtained above is doubled using a low-density polyethylene film (TUX # 40 manufactured by Tosero Co., Ltd., moisture permeability coefficient 10 g / m ² / day) having a width of 1400 mm and a thickness of 40 μm. The package was wound and the remaining part in the width direction was pushed into the core.

  This package was stored in a warehouse for six months in an atmosphere having a temperature of 17 ° C. and a humidity of 50% RH. After storage, the roll was taken out of the package and used as a hydraulic transfer film (curved surface printing film). Table 1 shows the state of wrinkles of the water-soluble PVA film unwound 100 m from the roll (1000 m long) and the state of distortion of the film unwound every 100 m to 200 m. While unwinding the water-soluble PVA film from the roll, 5 color gravure printing was performed, followed by water pressure transfer. There were no problems such as poor printing or poor transfer. .

(Example 2)
In the same manner as in Example 1 except that the winding tension when winding the PVA film around the paper tube in Example 1 was set to 10 kgf, the roll-like product of the water-soluble PVA film {the cross-sectional diameter (H) of the roll-like product] 228 mm} was obtained. The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1. When the winding tension is converted into a winding tension per 1 m of film width, the value is 20 kgf / 1 m width.

(Example 3)
A roll of water-soluble PVA film {diameter of the cross-section of the roll ( H) 219 mm}. The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

Example 4
In Example 1, after embossing one surface of the film, the surface of Nikka's starch powder was applied to 0.05 g / m ² using Nikka's electrospray K-III. A roll-like water-soluble PVA film {diameter of cross section of roll (H) 230 mm} was obtained in the same manner as in Example 1 except that the coating was applied. The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Example 5)
In Example 1, instead of an aqueous solution having a saponification degree of 88 mol%, a polymerization degree of 1700 PVA of 15 parts by weight, and a PVA concentration containing glycerin of 0.65 parts by weight of 15% by weight, a saponification degree of 88 mol% and a polymerization degree of 1700 Water-soluble in the same manner as in Example 1 except that an aqueous solution containing 15 parts by weight of PVA, 0.7 parts by weight of glycerin and 0.5 parts by weight of corn starch (average particle size of about 15 μm) and having a PVA concentration of 15% by weight was used. A roll of PVA film {diameter (H) 231 mm of the cross section of the roll] was obtained. The composition of the water-soluble PVA film was PVA / glycerin / water / starch = 90/4/3/3 (% by weight).

  The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Example 6)
In Example 1, instead of an aqueous solution having a saponification degree of 88 mol%, a polymerization degree of 1700 PVA of 15 parts by weight, and a PVA concentration containing glycerin of 0.65 parts by weight of 15% by weight, a saponification degree of 88 mol% and a polymerization degree of 1700 A roll of water-soluble PVA film in the same manner as in Example 1 except that an aqueous solution containing 15 parts by weight of PVA, 0.7 parts by weight of glycerin and 0.05 parts by weight of boric acid and having a PVA concentration of 15% by weight was used. {The diameter (H) 228 mm of the cross section of the roll-like material] was obtained. The composition of the water-soluble PVA film was PVA / glycerin / water / boric acid = 90/4/3 / 0.3 (% by weight).

  The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Example 7)
In Example 1, a roll of a water-soluble PVA film was prepared in the same manner as in Example 1 except that PVA having a saponification degree of 88 mol% and a polymerization degree of 2000 was used instead of PVA having a saponification degree of 88 mol% and a polymerization degree of 1700. A shaped product {diameter (H) of cross section of roll-like product 225 mm} was obtained. The composition of the water-soluble PVA film was PVA / glycerin / water content = 93/4/3 (% by weight).
The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Example 8)
In Example 1, the amount of PVA used was changed from 15 parts by weight to 13 parts by weight, and the amount of glycerin was changed from 0.65 parts by weight to 2.4 parts by weight. To 116 ° C., and after embossing one side of the film in the same manner as in Example 4, Nikka's electrospray K-III was used, and Nikka's starch powder was added at 0.05 g / m. A roll-like product of a water-soluble PVA film {diameter (H) 229 mm in cross section of the roll-like product) of a water-soluble PVA film was obtained in the same manner as in Example 1 except that it was applied to the surface so as to have an adhesion amount of ² . The composition of the water-soluble PVA film was PVA / glycerin / water content = 80/15/5 (% by weight).

  The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1. When agricultural chemicals were packaged using a water-soluble PVA film unwound from a roll, no problems were found in bag-making properties, solubility, and the like.

Example 9
In Example 8, instead of PVA having a saponification degree of 88 mol% and a polymerization degree of 1700, modified PVA having a saponification degree of 88 mol% and a polymerization degree of 1700 modified with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) ( Degree of modification: In addition to using 2: 100 (= 2 mol%) as the ratio of the number of monomer groups / the number of units of the whole modified PVA, the temperature of the hot air was changed from 116 ° C. to 140 ° C., and the drying time Was extended from 5 minutes to 10 minutes in the same manner as in Example 8 to obtain a roll of water-soluble PVA film {diameter (H) of cross section of roll-like material (336 mm)}. PVA / glycerin / moisture = 80/15/5 (% by weight) The film thickness (M) of the water-soluble PVA film was 80 μm.

  The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1. When 100 g of liquid detergent was packaged using a water-soluble PVA film unwound from a roll, no particular problem was found in bag-making property, solubility and the like.

(Example 10)
In Example 1, it was stored in the warehouse for six months in the same manner as in Example 1 except that the temperature when storing the package was 40 ° C. and the humidity was 55% RH. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1. The water-soluble film after storage was confirmed to have some wrinkles, but the wrinkles disappeared easily due to the tension during printing, and the wrinkles were such that there was no problem in processing the film.

(Example 11)
In Example 1, a roll was obtained in the same manner as in Example 1 except that the winding tension was 7 kgf. Table 1 shows the results of determining the state of the water-soluble PVA film at that time in the same manner as in Example 1.

(Example 12)
In Example 1, a roll was obtained in the same manner as Example 1 except that the taper was 85%. Table 1 shows the results of determining the state of the water-soluble PVA film at that time in the same manner as in Example 1.

(Example 13)
A roll-like product was obtained in the same manner as in Example 1 except that 0.49 parts by weight of the starch powder used in Example 4 was further added to the aqueous solution used in Example 1. Table 1 shows the results of determining the state of the water-soluble PVA film at that time in the same manner as in Example 1.

(Comparative Example 1)
In the same manner as in Example 1 except that the winding tension when winding the PVA film around the paper tube in Example 1 was set to 30 kgf, the roll-like product of the water-soluble PVA film {the cross-sectional diameter (H) of the roll-like product] 217 mm} was obtained. The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1. When the winding tension is converted into a winding tension per 1 m of film width, the value is 60 kgf / 1 m width.

(Comparative Example 2)
In the same manner as in Example 1 except that the initial winding tension when winding the PVA film around the paper tube in Example 1 was 2 kgf and the taper was 85%, a roll-like product of the water-soluble PVA film {roll-like product A cross-sectional diameter (H) of 240 mm} was obtained. The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1. When the winding tension is converted into the winding tension per 1 m of film width, the value is 4 kgf / 1 m width.

(Comparative Example 3)
In Example 1, except that the amount of glycerin used was changed from 0.65 parts by weight to 0.08 parts by weight, in the same manner as in Example 1, a roll of water-soluble PVA film {diameter of the cross section of the roll (H) 223 mm} was obtained. The composition of the water-soluble PVA film was PVA / glycerin / water content = 96.5 / 0.5 / 3 (% by weight).
The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Comparative Example 4)
In Example 1, except that the amount of glycerin used was changed from 0.65 parts by weight to 7.4 parts by weight, in the same manner as in Example 1, a roll of water-soluble PVA film {diameter of the cross section of the roll (H) 220 mm} was obtained. The composition of the water-soluble PVA film was PVA / glycerin / water content = 65/32/3 (% by weight).
The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Comparative Example 5)
In Example 1, except that the temperature of the hot air was changed from 120 ° C. to 170 ° C., a water-soluble PVA film roll-like product {diameter (H) 231 mm of the cross-section of the roll-like product) of the water-soluble PVA film was obtained. It was. The composition of the water-soluble PVA film was PVA / glycerin / water content = 95.3 / 4.1 / 0.6 (% by weight).
The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Comparative Example 6)
In Example 1, except that the temperature of the hot air was changed from 120 ° C. to 70 ° C., in the same manner as in Example 1, a roll of water-soluble PVA film {diameter of cross section of roll (H) 224 mm} was obtained. It was. The composition of the water-soluble PVA film was PVA / glycerin / water content = 84.4 / 3.6 / 12 (% by weight).
The obtained roll was packaged in a double roll using a low density polyethylene film in the same manner as in Example 1, and further stored in a warehouse for six months in the same manner as in Example 1. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Comparative Example 7)
In Comparative Example 2, the package was stored in a warehouse for six months in the same manner as in Example 1 except that the temperature when storing the package was 40 ° C. and the humidity was 55% RH. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Comparative Example 8)
In Comparative Example 2, it was stored in a warehouse for six months in the same manner as in Example 1 except that the temperature when storing the package was 5 ° C. and the humidity was 55% RH. A water-soluble PVA film was unwound from a roll-like material taken out from the package after storage. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Comparative Example 9)
In Example 1, it was stored in the same manner as in Example 1 except that the roll was packaged with biaxially stretched nylon (30 μm, moisture permeability 134 g / m ² / day). Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

(Comparative Example 10)
In Example 1, the taper was set to 50%, and thereafter a roll was obtained in the same manner. Table 1 shows the results of determining the distortion and wrinkle of the water-soluble PVA film at that time in the same manner as in Example 1.

  Table 2 shows the contents of the water-soluble PVA films obtained in the above examples and comparative examples.

The roll of the water-soluble PVA of the present invention has no or very little tarmi (or distortion) and wrinkles, and is used for various applications such as hydraulic transfer films, agricultural chemical packaging films, detergent packaging films, In particular, it is extremely useful as a hydraulic transfer curved surface printing film.

Claims (15)

A water-soluble polyvinyl alcohol film is a roll-like material wound around a cylindrical core,
The polyvinyl alcohol film has a plasticizer content of 1 to 30% by weight and a water content of 1 to 10% by weight, and dissolves by stirring in water at 20 ° C.
A roll-like product having a porosity of 4-25% between films of the roll-like product defined by the following formula,
Porosity (%) = {(π / 4) (H ² −D ² ) / (L × M)} × 100-100
H. Diameter of film roll (mm)
D. ・ Outer diameter of cylindrical core (mm)
L. Length of film (m)
M ·· Average thickness of film (μm)
When the polyvinyl alcohol film is unwound from the roll and uniformly applied with a tension of 2 kgf per 1 m width in the film flow direction, the total width of the strained portions of the film existing in the film width direction is 10% of the total film width. % Roll or less.
Here, the distorted portion refers to a film film when a fluorescent lamp (36 W, 117 cm, one piece) is placed at a position 1.5 m away upward in the normal direction of the spread film and irradiated with light. This refers to the part of the surface where light is irregularly reflected.   The roll-shaped product according to claim 1, wherein the polyvinyl alcohol constituting the water-soluble polyvinyl alcohol film has a saponification degree of 80 to 99.95 mol%.   The roll-shaped product according to claim 1 or 2, wherein at least one surface of the water-soluble polyvinyl alcohol film is embossed.   The roll-shaped product according to any one of claims 1 to 3, wherein the length (L) of the water-soluble polyvinyl alcohol film is 100 to 3000 m.   The roll-shaped product according to any one of claims 1 to 4, wherein the water-soluble polyvinyl alcohol film contains a slip agent therein or has a slip agent attached to the surface thereof.   The roll-shaped product according to any one of claims 1 to 5, wherein the water-soluble polyvinyl alcohol film contains 0.01 to 3% by weight of a boron compound.   The roll-shaped product according to any one of claims 1 to 6, wherein the water-soluble polyvinyl alcohol film is any one of a hydraulic transfer curved surface printing film, an agricultural chemical packaging film, and a detergent packaging film. A method for producing a roll of a water-soluble polyvinyl alcohol film that dissolves in water at 20 ° C. by stirring,
A film drying step of drying a polyvinyl alcohol film containing polyvinyl alcohol and a plasticizer to form a polyvinyl alcohol film having a plasticizer content of 1 to 30% by weight and a water content of 1 to 10% by weight;
The film is wound around a cylindrical core, and a winding process for forming a roll is provided.
In the winding process, the film winding tension is 5 to 40 kgf per 1 m width.   9. The polyvinyl alcohol film according to claim 8, wherein the polyvinyl alcohol film is formed using at least one of a film forming method selected from a casting film forming method, a wet film forming method, a gel film forming method, and a melt extrusion film forming method. Production method.   The manufacturing method according to claim 8 or 9, wherein a winding end tension with respect to a winding start winding tension is 60 to 90%.   The method according to any one of claims 8 to 10, wherein the length (L) of the water-soluble polyvinyl alcohol film is 100 to 3000 m.   The manufacturing method according to any one of claims 8 to 11, further comprising a step of embossing the dried film.   The manufacturing method according to any one of claims 8 to 12, wherein the core has an outer diameter of 10 to 200 mm and a wall thickness of 1.5 to 20 mm.   The roll-form thing of the water-soluble polyvinyl alcohol-type film obtained by the manufacturing method as described in any one of Claims 8-13. A method for storing a roll of the water-soluble polyvinyl alcohol film according to any one of claims 1 to 8,
The roll-like material is stored in a certain temperature range in a state where it is wrapped with a film having a moisture permeability coefficient of 30 g / m ² / day or less,
The upper limit of the temperature range during storage is the higher one of (T-168) ° C and 18 ° C (° C), and the lower limit is the lower one of (T-180) ° C and 10 ° C ( ° C)
A storage method in which T is a temperature (° C.) of a main peak obtained by differential thermal analysis of a polyvinyl alcohol film.

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