JPH04360632A - Tack-persistent agricultural nonrigid vinyl chloride-based resin film - Google Patents

Abstract

PURPOSE:To obtain the title film not damaging qualities, appearance and transparency even by regeneration and use by providing an anti-fogging agricultural non-rigid vinyl chloride film containing an anti-fogging agent with an adhesion layer of vinyl chloride resin powder having specific average particle diameter. CONSTITUTION:(A) One side or both sides of an anti-fogging agricultural non- rigid vinyl chloride film containing at least one of a defrosting agent and an anti-fogging agent, a fluorine-based surfactant and/or siloxane-based surfactant, are provided with (B) an adhesion layer by applying vinyl chloride-based resin powder having 4-50mum average particle diameter to give the objective film from which the vinyl chloride resin powder on the surface is readily removed by rainwater and water drops, etc., and which can be melted and bonded in a secondary processing using a hot melt bonding machine such as high-frequency sewing machine.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvements in anti-blocking soft vinyl chloride resin films for agricultural use. More specifically, the present invention provides an anti-adhesive agricultural soft vinyl chloride resin film that prevents adhesion while maintaining the smoothness of the film surface, and which does not impair its appearance or transparency even when recycled. It is related to.

0002

[Prior Art] Conventionally, soft vinyl chloride resin films are inexpensive transparent general-purpose resin films.
It is used in large quantities as an agricultural film used to insulate vegetables, flowers, etc.

[0003] This soft vinyl chloride resin film usually contains 40 to 40 parts by weight of a plasticizer per 100 parts by weight of vinyl chloride resin.
It is manufactured continuously by extrusion molding or calendar molding using a resin composition containing approximately 70 parts by weight, and the resulting film is wound into a roll and transported, stored, and used in roll form. has been done. Then, depending on the intended use, the material is cut while being rewound from the roll, and subjected to so-called secondary processing such as welding.

[0004] Such soft vinyl chloride resin films contain a large amount of plasticizer, which bleeds onto the surface over time, increasing surface tackiness and causing problems during secondary processing. In addition to making unwinding and workability difficult, the surfaces of products obtained by secondary processing adhere to each other, causing so-called blocking, which makes handling difficult. In order to solve these problems, for example, a soft vinyl chloride resin film is continuously manufactured using a calendar molding method or an extrusion molding method, and just before it is wound into a roll, talc or starch (unexamined Japanese Patent Application Publication No. (Japanese Unexamined Patent Publication No. 60-8328)
Partially saponified polyvinyl alcohol (JP-A-60-673
Attempts have been made to apply a fine powder for preventing adhesion, such as the method disclosed in Publication No. 4). However, in the case of soft vinyl chloride resin films sprinkled with powders such as talc, starch, tetrasilicon mica, etc., the powder and vinyl chloride resin are not compatible, so if cuttings from processing are recycled and used, fish In addition to unfavorable results such as the formation of eyes and a decrease in transparency, adhesiveness inevitably decreases when melt bonding is performed using a high-frequency sewing machine or the like. Furthermore, even in the case of a film sprinkled with powder of partially saponified polyvinyl alcohol, the quality of the film is impaired when recycled, and the anti-sticking ability is inevitably reduced when the plasticizer bleeds.

By the way, the soft vinyl chloride resin film used for covering agricultural greenhouses needs to transmit as much sunlight as possible into the greenhouse. After the film is used to cover the house, the fine powder is
Within a short period of time, it must be removed from the film surface by rainwater or water droplets generated inside the greenhouse. However, when a film on which the above-mentioned anti-adhesive powder is sprinkled during film production is used to cover an agricultural greenhouse, the fine powder adheres to it due to rainwater or water droplets generated inside the greenhouse. The disadvantage is that it becomes difficult to remove from the surface.

[0006] Therefore, soft vinyl chloride resin films used to cover agricultural greenhouses are usually not coated with anti-adhesive fine powder during film production, but are coated with anti-adhesive powder on the surface of the film during secondary processing such as welding. The method used is to spray a fine powder and deliver it to farmers. However, in this method, a large amount of the fine powder is scattered during the dispersion operation at the secondary processing stage, resulting in a poor working environment.

[0007]

[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of conventional anti-adhesive soft vinyl chloride resin films, has excellent anti-adhesive properties, and prevents the anti-adhesive powder from adhering to the surface. Even if the film is remelted and recycled, its quality, appearance, and transparency will not deteriorate.
In addition to being able to be melted and bonded using a high-frequency sewing machine,
An anti-adhesive agricultural soft vinyl chloride resin whose anti-adhesive fine powder on the surface is easily removed by rainwater or water droplets, and which does not require any anti-adhesive treatment during secondary processing such as welding. It was created for the purpose of providing film.

[0008]

[Means for Solving the Problems] As a result of extensive research into preventing the stickiness of vinyl chloride resin films, the present inventors found that conventionally, vinyl chloride resin powder was used as a soft vinyl chloride resin for preventing stickiness. When used in films, it was thought that the anti-adhesive performance would not be fully demonstrated due to the transfer of plasticizer from the film, but it has been found that anti-stick properties cannot be fully demonstrated due to the transfer of plasticizer from the film. When vinyl chloride resin powder is attached, it is possible to exhibit unexpectedly excellent anti-adhesive properties and long-lasting anti-adhesive properties, and a soft vinyl chloride resin film that has anti-fog and anti-fog properties has even better effects. They discovered that the film coated with this vinyl chloride resin powder can be melted and bonded using a high-frequency sewing machine, and is extremely advantageous for recycling. Based on this, the present invention was completed.

That is, the present invention provides an adhesive layer of vinyl chloride resin powder having an average particle size of 4 to 50 μm on at least one side of an antifogging agricultural soft vinyl chloride resin film containing an antifogging agent. The present invention provides an anti-stick agricultural soft vinyl chloride resin film characterized by the following characteristics.

In the method of the present invention, it is necessary to use a soft vinyl chloride resin film that has antifogging properties or antifogging properties. There are no particular restrictions on the vinyl chloride resin that serves as the base material for the film, and conventionally known resins such as vinyl chloride homopolymers, highly chlorinated vinyl chloride polymers, partially crosslinked vinyl chloride polymers,
Alternatively, any copolymer of vinyl chloride and a copolymerizable monomer can be selected and used.

Examples of copolymerizable monomers in the copolymer include fatty acid vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate; acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, and butyl acrylate; Methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate, vinyl cyanides such as acrylonitrile and methacrylonitrile, alkyl vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, α-olefins such as ethylene, propylene and styrene, and acrylics. acids, unsaturated carboxylic acids such as methacrylic acid, maleic anhydride or their acid anhydrides, vinylidene chloride, vinyl bromide, etc.
A species may be used, or two or more species may be used in combination.

[0012] There are no particular restrictions on the plasticizer to be added to the vinyl chloride resin, and any plasticizer can be selected from those conventionally used in vinyl chloride resins. Examples of such plasticizers include alkyl esters of aromatic polybasic acids such as butyl phthalate, dioctyl phthalate, diisodecyl phthalate, diisononyl phthalate, diundecyl phthalate, trioctyl trimellitate, triisooctyl trimellitate, and pyromet; Alkyl esters of aliphatic polybasic acids such as dibutyl adipate, dioctyl adipate, diisononyl adipate, dibutyl azelate, dioctyl azelate, diisononyl azelate, phosphate esters such as tricresyl phosphate, tricylenyl phosphate, adipic acid, azelain acids, polycarboxylic acids such as sebacic acid and phthalic acid, and polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, and 1,4-butylene glycol. molecular weight of 600
- Polyester plasticizers such as polycondensates of about 8000 whose terminals are blocked with monohydric alcohol or monohydric carboxylic acid, epoxidized soybean oil, epoxidized linseed oil, epoxidized tall oil fatty acid-2-ethylhexyl, etc. Examples include epoxy plasticizers and chlorinated paraffins.

[0013] These plasticizers may be used alone or in combination of two or more, and the amount thereof is usually 40 to 70 parts by weight per 100 parts by weight of the vinyl chloride resin. Selected within the department. This amount is 40
If it is less than 7 parts by weight, the plasticizing effect will not be sufficiently exhibited.
If it exceeds 0 parts by weight, the mechanical properties of the film tend to deteriorate and it becomes difficult to mold.

A nonionic surfactant is preferably used as the antifogging agent for imparting antifogging properties to the soft vinyl chloride resin film. Examples of the nonionic surfactant-based antifogging agent include polyhydric alcohols such as sorbitan, polyethylene glycol, glycerin, pentaerythritol, and trimethylolpropane, and esters of condensates of these and fatty acids. Furthermore, ester ethers obtained by further adding alkylene oxide to these esters can also be used.

[0015] Examples of the raw fatty acids used in the ester type antifogging agent include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, etc., and the number of moles of alkylene oxide added in the ether type antifogging agent. is usually selected within the range of 2 to 10 moles.

[0016] Examples of antifogging agents include, for example, fluorosurfactants containing a fluoroalkyl group or a fluoroalkenyl group. In addition, low molecules having at least three or more siloxane bonding units in the molecule,
Polymeric siloxane surfactants can also be used.

[0017] The above-mentioned antifogging agent and antifogging agent may be used alone or in combination of two or more. The content of antifogging agent is 1 per 100 parts by weight of vinyl chloride resin.
The content of the antifogging agent is in the range of ~4 parts by weight, preferably 1.5 to 3 parts by weight, per 100 parts by weight of vinyl chloride resin.
．． Each is selected in an amount of 5 parts by weight or less, preferably in the range of 0.03 to 0.4 parts by weight. When the content of the antifogging agent and antifog agent is within the above range, the vinyl chloride resin powder used as the antiblocking agent has good antiblocking properties and washout properties.

The soft vinyl chloride resin film having anti-fog or anti-fog and anti-fog properties used in the method of the present invention is
A resin composition is prepared by blending a plasticizer, an antifogging agent, an antifogging agent, and various additive components used as desired, such as a stabilizer, a filler, a lubricant, a coloring agent, etc. with the above-mentioned vinyl chloride resin. Thereafter, it can be manufactured by forming a film by a method conventionally used in the production of vinyl chloride resin films, such as extrusion molding methods such as T-die method and inflation method, calender method, casting method, etc. .

[0019] Examples of the stabilizer include metal soaps,
Ba-Zn system, Ca-Zn system, Ca-Zn-Ba system, B
Examples of fillers include a-Mg-Al type fillers, and examples of fillers include heavy calcium carbonate, clay, silica, and carbon black. Furthermore, examples of the lubricant include fatty acid amides such as stearic acid amide, palmitic acid amide, oleic acid amide, and ethylene bistearamide, as well as solid higher alcohols.

In the method of the present invention, an anti-blocking agent having an average particle diameter of 4 to 50 μm is added to at least one side of the thus obtained soft vinyl chloride resin film having anti-fog or anti-fog properties. Preferably, vinyl chloride resin powder having a particle size in the range of 5 to 30 μm is sprinkled to form an adhesion layer.

[0021] Such vinyl chloride resin powder, together with the anti-fog or anti-fog and anti-fog properties of the film, has the effect of preventing the film surfaces from adhering to each other, and also makes it possible to use the film in agriculture. When used as a coating material for greenhouses, it has the property of being easily removed from the film surface by rainwater or water droplets. Further, since the resin of this powder and the base resin of the film are of the same type, when the film coated with the resin powder is recycled and used, the transparency and appearance of the film will not be impaired. Further, the film to which the vinyl chloride resin powder is attached can be melt-bonded during secondary processing using a melt-bonding machine such as a high-frequency sewing machine.

If the average particle diameter of the vinyl chloride resin powder is less than 4 μm, the anti-adhesion effect will be poor;
If the particle exceeds the particle size, even if the particles adhere uniformly to the film surface, the particles will dig into the film surface while the film is rolled, stored, and transported, and the film surface will become indented.
Smoothness may be lost and the commercial value of the film may be reduced, and the durability of the anti-adhesive properties may also be reduced. In addition, products containing emulsifiers produced by emulsion polymerization tend to aggregate,
It is preferable to remove the emulsifier since it tends to reduce uniform dispersion.

[0023] As a method for producing such vinyl chloride resin powder, emulsion polymerization, suspension polymerization, bulk polymerization, etc. are generally used. In addition, the vinyl chloride resin powder may be a vinyl chloride homopolymer, a highly chlorinated vinyl chloride polymer, a partially crosslinked vinyl chloride polymer, or a copolymer of a monomer copolymerizable with vinyl chloride. It may be of. Examples of monomers copolymerizable with vinyl chloride include those exemplified in the explanation of the vinyl chloride resin used as the base material of the film.

Regarding the method of dispersing the vinyl chloride resin powder, for example, the soft vinyl chloride resin film having antifogging properties is coated with an extrusion molding method such as a T-die method or an inflation method, a calender method, a casting method, or the like. After forming a film and cooling it, the vinyl chloride resin powder is sprinkled on at least one side of the film to form an adhesion layer thereof,
Next, by winding this up into a roll, a desired anti-blocking soft vinyl chloride resin film can be obtained. The film is preferably wide and long, and its thickness is usually selected within the range of 0.05 to 0.2 mm.

[0025] The vinyl chloride resin powder may be used alone or in combination of two or more types, and other types may be used as desired within the scope of not detracting from the object of the present invention. Known anti-blocking agents such as starch, talc, tetrasilicon mica, partially saponified polyvinyl alcohol powder, acrylate resin powder, etc. can also be used in combination.

The amount of the vinyl chloride resin powder deposited is usually selected within the range of 0.02 to 1 g per 1 m 2 of the film. If the amount is less than 0.02 g, the anti-adhesive effect will not be sufficiently exhibited, and if it exceeds 1 g, no improvement in the effect will be recognized for the amount; rather, the powder will partially accumulate on the film, In addition to damaging the transparency of the film, it is also economically disadvantageous. A particularly preferred range is 0.05 to 0.5 g.

The vinyl chloride resin powder can be attached to the film surface by, for example, directly scattering the powder onto the film surface, or by placing the vinyl chloride resin powder in a vinyl chloride resin-insoluble solvent such as an aqueous medium. After a dispersion in which powder is homogeneously dispersed is attached to the film surface by a spraying method or coating method, the solvent may be dried and removed, or a method in which the powder is attached by charging the film can be used. can.

The film having the vinyl chloride resin powder as an anti-tack agent adhered to its surface in this way is wound up by a conventional film winding method such as a center winder or a surface winder.

[0029]

According to the present invention, a soft vinyl chloride resin film having anti-fog or anti-fog and anti-fog properties is used, and vinyl chloride having a specific particle size is applied as an anti-blocking agent to the surface of the film. By spraying PVC-based resin powder, it has excellent anti-adhesive properties, and the quality, appearance, and transparency will not be affected even when recycled, and the vinyl chloride-based resin powder on the surface can be easily removed by rainwater or water droplets. It also has excellent properties, such as being able to be melt-bonded during secondary processing using a melt-bonding machine such as a high-frequency sewing machine, and the anti-stick properties of the film are unlikely to deteriorate due to oozing of the plasticizer in the film during storage. An anti-blocking soft vinyl chloride resin film having these characteristics can be easily obtained.

[0030] Furthermore, the present invention eliminates the need to spray anti-adhesive fine powder during secondary processing such as welding, so that it is possible to eliminate adhesion during the distribution stage, which was conventionally used in agricultural vinyl chloride resin films. The effort of dispersing the preventive fine powder is saved, and the fine powder scattering into the air does not have any adverse effects on the human body.

The anti-adhesive soft vinyl chloride resin film of the present invention is suitable as an agricultural film for use as a heat-insulating coating for rice, vegetables, flowers, etc., for example.

[0032]

EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way. The physical properties of the film were determined as follows.

(1) Anti-adhesive property Evaluation was made according to the following criteria. ○: Almost no stickiness △: Slightly sticky ×: Significant stickiness

(2) Surface smoothness The surface of the film was visually observed and evaluated according to the following criteria. ○: The surface is extremely smooth. △: Some unevenness is observed on the surface due to powder penetration. ×: Considerable unevenness is observed on the surface due to powder penetration and adhesion.

(3) Recycled The film with the anti-blocking agent powder still attached to the surface was melted again to form a film, and its transparency was evaluated according to the following criteria. ○: Good transparency △: Slightly poor transparency ×: Poor transparency

(4) Run-off A water tank kept at a water temperature of 40°C is covered with a film inclined at 30 degrees so that the side to which the anti-adhesive agent is attached is on the inside (aquarium side), and the film is kept at a temperature of 23°C. The film was placed for 5 hours in a room maintained at a temperature of 100°C, and the degree of loss of the anti-tack agent was evaluated based on water droplets that condensed and flowed down inside the film, according to the criteria shown below. ○: No residual anti-adhesive agent is observed △: Some residual anti-adhesive agent is observed ×: Significant residual anti-adhesive agent

(5) High-frequency adhesion Using a high-frequency sewing machine (manufactured by Nippon Koshuha Co., Ltd., model RHM-500), the adhesion status of the film (two layers) was measured under the conditions of a voltage of 80 V and a film feed speed of 13 m/min. I performed an adhesion test by adjusting the tuning knob to get the best results. Two films were stacked so that the anti-adhesion agent surfaces faced each other, and after being adhesively processed over a length of 30 cm, the adhesive portion was strongly peeled off from side to side, and evaluated according to the following criteria. ○: No peeling occurs △: Slight peeling occurs locally ×: Easy peeling

(6) Sustainability of anti-sticking After the roll-shaped product was left in a constant temperature room at 40° C. for 3 months, it was evaluated according to the following criteria. ◎: No tackiness ○: Almost no tackiness △: Slight tackiness ×: Significant tackiness

Example 1 100 parts by weight of vinyl chloride resin (p=1300), 45 parts by weight of dioctyl phthalate, 5 parts by weight of tricresyl phosphate, 2 parts by weight of epoxy resin, 4 parts by weight of calcium-zinc stabilizer, anti-fog After mixing 2 parts by weight of sorbitan monostearate as an agent and 0.1 part by weight of an ultraviolet absorber in a super mixer for 10 minutes, the mixture was kneaded on a roll heated to 165°C, and by an L-type calender,
A transparent soft polyvinyl chloride film with a thickness of 0.075 mm was formed.

[0040] Next, the film pulled out from the calender roll is placed on a cooling roll to cool the film temperature to 50°C or less, and then one side of the film is coated with
Vinyl chloride resin powder (manufactured by Nippon Zeon Co., Ltd., Plastisol Blend Resin No. 52) having an average particle diameter of 20 μm was applied to the film at an amount of 0.1 g per 1 m 2 of the film, and then wound into a roll using a winder. Table 1 shows the results of evaluating the physical properties of this film.

Example 2 The same procedure as in Example 1 was carried out except that in Example 1, a vinyl chloride resin powder having an average particle diameter of 40 μm (manufactured by Nippon Zeon Co., Ltd., Plastisol Blend Resin No. 51) was used. carried out. The results are shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated, except that a vinyl chloride resin powder with an average particle diameter of 1 μm (manufactured by Mitsubishi Kasei Vinyl Co., Ltd., emulsion polymerization resin No. P-450) was used. It was carried out in the same manner. The results are shown in Table 1.

Comparative Example 2 In Example 1, except that a vinyl chloride resin powder with an average particle size of 70 μm (Nippon Zeon Co., Ltd., plastisol blend resin No. 103EPF) was used.
It was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 3 A test was carried out in the same manner as in Example 1, except that talc having an average particle diameter of 20 μm was used instead of the vinyl chloride resin powder. The results are shown in Table 1.

Comparative Example 4 A test was carried out in the same manner as in Example 1, except that starch powder having an average particle size of 20 μm was used instead of the vinyl chloride resin powder. The results are shown in Table 1.

Comparative Example 5 A test was conducted in the same manner as in Example 2, except that the soft vinyl chloride film resin film did not contain the antifogging agent sorbitan monostearate. The results are shown in Table 1.

Example 3 In Example 1, except that the vinyl chloride resin powder containing no emulsifier and having an average particle diameter of 10 μm (manufactured by Sumitomo Chemical Co., Ltd., Emulsion Polymerization Resin Millet EX-M) was used. , carried out in the same manner as in Example 1. Table 1 shows the results.
Shown below.

[Table 1]

Examples 4 to 6 Fluorine surfactant A (manufactured by Daikin Corporation, DS-403) and fluorine surfactant B (manufactured by Daikin Corporation, DS451) were added to the film composition of Example 1 as antifogging agents. Or siloxane surfactant (manufactured by Toshiba Silicone Co., Ltd., YF-391
Add 0.1 part by weight of 3) and process in the same way to a thickness of 0.07
A 5 mm flexible polyvinyl chloride film was produced. The physical properties of this product are shown in Table 2.

[Table 2]

Claims (3)

[Claims] Claim 1: At least one side of an antifogging agricultural soft vinyl chloride film containing an antifogging agent has an average particle size of 4 to 4.
An anti-stick agricultural soft vinyl chloride resin film characterized by having an adhesive layer of 50 μm vinyl chloride resin powder. 2. An anti-fog and anti-fog agricultural soft vinyl chloride film containing at least one type of anti-fogging agent selected from fluorine-based surfactants and siloxane-based surfactants and an anti-fogging agent. Average particle size 4-50μm on one side
A soft vinyl chloride resin film for agricultural use with anti-adhesive properties, characterized in that it has an adhesive layer of vinyl chloride resin powder. 3. The soft vinyl chloride film contains 100 parts by weight of a vinyl chloride resin, 40 to 70 parts by weight of a plasticizer, 1 to 4 parts by weight of an antifog agent, and 0 to 0.5 parts by weight of an antifog agent. The anti-stick agricultural soft vinyl chloride resin film according to claim 1 or claim 2, which is formed by: