JPS5964637A - Production of dust-proof polyvinyl chloride film - Google Patents

Abstract

PURPOSE:To produce a dust-proof PVC film of excellent transparency, by applying an acrylic resin solution to one or both of the surfaces of a PVC base film within a period during which the haze value of the base film is at most a specified times as high as that just after the production. CONSTITUTION:In the production of a dust-proof PVC film comprising application of an acrylic resin, e.g., methyl (meth)acrylate, to one or both the surfaces of the PVC film containing a surfactant; a step of applying an acrylic resin solution (e.g., a solution in an organic solvent such as benzene) is connected directly to a certain step performed within a period during which the haze of the PVC film base is within three times as high as that measured just after its production, preferably to a step of producing the PVC film. It becomes possible to obtain a film completely freed of dewetting and uneven spraying of an acrylic resin solution, and blooming of a paint film after drying, and having improved dust-proof property and light transmission.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for distributing a dust-proof polyvinyl chloride film.

The conventionally used polyvinyl chloride film and sheet (hereinafter referred to as PVC film) are
lwJ, cut, effl agent, Wri++i activator
Although the desired physical properties and functions are transferred to the PVC film by applying volatile additives, the softening agent bleeds out over time and dust adheres to the surface of these PVC films, making it difficult to use them for agricultural purposes. The presence of a single duck will obstruct the transmission of light into the interior of the room, and in other applications will result in a reduction in the penetration of light into the interior and a deterioration of the appearance. Therefore, a dust-proof PVC film coated with an acrylic resin having good dust-proof properties has been proposed and put into practical use.

Conventionally, dust-proof PVC film is produced by applying a dust-proof acrylic resin solution onto the surface of the base material PVC film.1. It is obtained by subsequent drying. If the base material, PVC film, does not contain any surfactant, applying an acrylic resin solution to the surface of the film at any time after the film is made will prevent repellency and uneven coating. However, the phenomenon of whitening of the paint film after drying does not occur, but with the base materials PVC and L7 containing surfactants, an acrylic resin solution is applied several days after manufacture. If this is done, repellency and uneven coating are likely to occur, and problems arise such as whitening after drying. Such problems often occur during the spring and autumn seasons when there is a large temperature difference between day and night, and are relatively rare during the winter and summer seasons when conditions are harsh.

Therefore, in order to solve these problems, the present inventors attempted to improve the acrylic resin, examine the solvent system, and change the film forming aid and surfactant for the acrylic resin solution to be applied. No satisfactory results were obtained. In addition, we tried changing the type and addition k of the surfactant added to the base material, PVC, within a practical range, but
The inventors of the present invention were able to solve the problem in the same way, but under these circumstances, the present inventors further investigated and discovered that although the solvent of the acrylic resin and the composition of the base material PVC film are also important, the base material is even more important. The present invention was finally completed based on the discovery that the properties of the PVC film as a material greatly influence the quality of the coating.

That is, in accordance with the present invention, in the method for producing a dust-proof polyvinyl chloride film by coating an acrylic resin on one side or both sides of a polyvinyl chloride film containing a surfactant, the polyvinyl chloride film as a base material A dust-proof polyvinyl chloride film characterized in that an acrylic resin solution is applied to one side or both sides of the base film within a period of time during which the degree of haze is within 3 times of +1 degree measured immediately after production A manufacturing method is provided.

The polyvinyl chloride used in the present invention is a homopolymer of vinyl chloride, a copolymer of a monomer that can be co-electroconverted or combined with jH-vinyl chloride, and other polymers that are compatible with these polyvinyl chlorides. It also includes compounds blended within the range that does not impair the physical properties of polyvinyl chloride. Monomers copolymerizable with vinyl chloride')t include vinyl esters such as vinyl acetate and vinyl acetate, vinyl ethers such as ethyl vinyl ether and divinyl ether, acrylates such as ethyl acrylate, methyl methacrylate, and glycidyl acrylate, and malein. Examples include diethyl acid, ethylene, propylene, etc., vinylidene chloride, etc., and one or more of these may be polymerized together with vinyl chloride. In addition, examples of polymers that are compatible with polyvinyl chloride include polyvinyl acetate and vinyl acetate.
Examples include ethylene copolymer, polyacrylate, polyvinylidene chloride, polyvinyl needle, and the like.

These polyvinyl chlorides #'', L emulsion polymerization, suspension polymerization,
Any polymer obtained by conventionally known polymerization methods such as solution polymerization and bulk polymerization can be used.

The PVC film that is the base material used in the present invention is
It is manufactured by adding a plasticizer, a surfactant, and other additives such as a stabilizer, a detergent, a coloring agent, etc., as necessary, to tanned vinyl.

There are no particular limitations on the surfactant t added to the PVC film that is the base material in the present invention, and known surfactants can be used as they are.
Depending on the situation, they may be used 111j or a mixture of two or more. Anionic, cationic, nonionic,
Although it does not matter whether they are amphoteric or not, it is preferable to mix and add nonionic materials that have little adverse effect on the heat resistance of polyvinyl chloride. Examples of nonionic surfactants include polyoxyethylene alkyl diacetyl, polyoxyethylene alkyl allyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan ether alkyl esters, glycerin, and pentyl esters. Examples include erythritol, trimethylolpropane, argyl esters of polyhydric alcohols such as sugars, polyoxyethylene derivatives thereof, and polyoxyethylene alkylamides.

The amount of surfactant to be added is not particularly limited and can be changed depending on the purpose, but for dust-proof agricultural PVC films, it is usually 0.5 per 100 kg of polyvinyl chloride.
A weight of ~5.0 liters is appropriate.0 After adding the above various additives to polyvinyl chloride, it is made into a film or sheet. Conventionally known methods such as a calendering method, an inflation silon method, and a T-die method are employed as a method for making a film. The thickness of the film or sort varies depending on the purpose, but for agricultural basic bifilms, it is preferably 0.03 to 0.5 mm.
Of course, it is better to use a glass substitute for I+IF glass which is thicker than this.

The solution of the acrylic resin used in the present invention may be either an aqueous dispersion or a solution of an organic solvent, and more preferably an aqueous dispersion that does not dissolve the plasticizer or polyvinyl chloride.

Acrylic resin made from wood is a polymer mainly composed of acrylates and methacrylates. Examples of monomers include acrylates such as V, methyl acrylate, methyl acrylate, propyl acrylate, n.
- Butyl acrylate, 2-edylhair acrylate, β-hydroxyethyl acrylate, glycidyl acrylate, etc. Methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-bugol methacrylate, β-hydroxyethyl methacrylate, etc. -glycidyl methacrylate, tridecyl methacrylate, etc., and also acrylic acid,
For methacrylic, 1 Itacone M, acrylamide, methacrylamide, N-medylolyl acrylamide, ethylene glycol diacrylate, Fil methacrylate, allyl acrylate, Fil methacrylate, trimegrolpropane triacrylate, Fil methacrylate, vinyl acetate, etc. are mainly used.

The aqueous dispersion of the acrylic resin can be obtained by conventional emulsion polymerization, suspension polymerization, or other common methods for obtaining a dispersion in which the continuous layer is water, such as a colloidal suspension. If the reaction liquid obtained as a result of the polymerization reaction itself is an aqueous dispersion, it is diluted with distilled water if necessary, and additives such as a film-forming agent or a surfactant are added as necessary. ! ! be done. Furthermore, it is of course possible to add ultraviolet absorbers, antioxidants, colorants, and colorants. Construction 11Q 14)
Common agents include megul cellosolve, edyl cellosolve, bugul cellosolve, methyl carpitol, ethyl carpitol, butyl carpitol, hegysilene glycol, and these ``r-sedates''.They are still used as surfactants. Any of the generally used anionic, cationic, nonionic, etc. can be used.

A solution of acrylic resin in an organic solvent can be prepared by ordinary emulsion polymerization,
It is prepared by dissolving a product obtained by suspension polymerization, solution surface polymerization, bulk polymerization, etc. in an organic solvent. Particularly, those obtained by solution polymerization in the solvent used during coating are advantageous because they can be used as they are for coating by preparing the polymer and adding various additives.

The solvent used during coating is preferably one that dissolves the acrylate resin well and has low solubility for the plasticizer and polyvinyl chloride. Examples of preferred solvents include methanol, ethanol, propanol, isopropanol,
(lower alcohols such as n-butanol, aromatic hydrocarbons such as benzene, toluene, and ghylene), ketones such as a7tone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, methyl propionate, and ethyl glopionate. Examples include esters of lower fatty acids such as methyl cellosolve, ethyl cellosolve, nithione oxide derivatives such as methyl cellosolve, ethyl cellosolve, ethyl carpitol, ethyl carpitol, butyl carpitol, and the same acetate. It is used as a mixture of two or more types.

Other diluents include ethers such as diethyl ether, dioxane, and tetrahydrofuran, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene, ortho-dichlorobenzene, and hydrocarbons such as hexane, octane, and petroleum ether. You may also use

A solution of acrylic 4t'J resin in an organic solvent may contain a film additive, a surfactant, an ultraviolet absorber, an RFF, if necessary.
Antioxidants, colorants, stabilizers, etc. are added and applied.

Since the acrylic resin solution applied as described above is applied to the surface of the base material PVC film, the τT%
It is required that the acrylic resin solution be applied while the properties of the PVC film change within a certain range during storage.

Changes in properties of PVC film, JIS-6714
If the PVC film is treated with an acrylic resin solution within a period when the seismic intensity of the PVC film is within 3 times the manufacturing time, preferably within 2 times the manufacturing time, the coating solution Good results are obtained in that no bullets or uneven coating occur at all, and the whitening phenomenon of the coating 14 after drying is strong.

According to the present invention, the haze level H of the PVC film immediately after production is usually 0.
．． Since it falls within the range of 3 to 3.0%, 91 degrees of PVC film, which is used as a tea scoop when applying acrylic resin solution, is 0.
．． The coating is performed while rc is in the range of 3 to 9.0%, preferably 0.3 to 6.0 inches above t.

The step of applying an acrylic resin solution to the surface of a PVC film does not require any special equipment, and a conventionally known coater can be used as is.

(7) As the head, any of a key coater, knife coater, rod coater, spray coater, gravure coater, kiss coater, etc. can be used. There are various types of drying equipment such as air flow drying method, heat transfer drying method, and infrared heating method, but the one that is suitable for the solvent used in the acrylic resin solution is selected. In addition,
When using a coating liquid using an organic solvent, it is necessary to take various measures against the organic solvent. Also from this point of view, it is preferable that the coating liquid be an aqueous dispersion of an acrylic resin.

The drying temperature will vary depending on issues such as acrylic type (grease resistance, solvent used, thickness of the coating film, etc.), but if an aqueous dispersion is used, it should be at least the temperature at which a coating film is formed, preferably L < e, j, i
o o: greater than or equal to c.

The I9 of the acrylic resin coating is o, 1 to 20 after drying.
It is desirable to use O cloth so that the thickness of 1 μm is 10.3 to 10 pm, and the weather resistance, dust resistance, etc.
) Anxious i4 hills are determined.

According to the present invention, the haze of the PVC film that is the base material is close to the value immediately after production, and the most desirable form is the manufacturing process of the base material, Hanawa Bifilno. The process of applying the acrylic resin solution to the surface of the film is done in two continuous steps. In such a continuous process, the repelling of the coating solution will not cause any uneven coating, and the whitening of the cold water will not be a problem at all. Even more conveniently, in the production of tB bifilm, t
Conventionally, it is necessary to take the time and effort of winding it up onto a roll, transporting it to the coating process, and then rewinding it for the unfinished process, but this time and effort can be omitted, and the manufacturing cost can be significantly reduced.

The method for producing a dust-proof PVC film of the present invention solves the problems of uneven coating and repellency of acrylic resin solutions, which have been problems in the past.
Whitening of the coated IM after drying is no longer a problem, and it is dust-proof and transparent compared to conventional 1171-proof PVC film.
Sexuality has also improved. Furthermore, by applying the vinyl chloride film and acrylic resin in a continuous manner at L14, wasteful transportation and unwinding of the roll can be omitted, which is very preferable.

The present invention will be explained below with reference to Examples.

In this implementation film, PVC film was heated at 35℃/12hr.
Heat treatments were performed alternately to promote changes in the physical properties (changes in seismic intensity) of the PVC film.

Reference example 1゜ [i+ of aqueous dispersion of acrylic resin, ice making water 2 manufactured by '4
0.5 parts by weight of potassium persulfate and 1.0 parts by weight of a polyoxyethylene alkyl phenyl ether derivative were charged into a reaction vessel, and the temperature was raised to 170°C under a nitrogen stream. In this, 59 parts by weight of methyl methacrylate, 33 parts by weight of n-butyl methacrylate, 6 parts by weight of hydroxyethyl methacrylate, and methacrylic j1.2
22 weight of the mixture was added dropwise with stirring over a period of 3 hours, and after the completion of the addition, the reaction was continued for an additional 3 hours. t) An emulsion containing about 45 weight 1% of the acrylic resin was obtained. P this with ammonia water
After neutralization to H7.0, 5 parts by weight of methyl carbitol and 3 r% of polyoxyethylene alkyl phenyl ether conductor per 100 parts by weight of the neutralized solution, ', Ii
Add 1 part of acrylic resin and dilute with water to bring the concentration of acrylic resin to 2 parts.
It was adjusted to 0% by weight.

Reference Example 2 - 125 parts by weight of methyl niger ketone (acrylic resin organic solvent solution manufactured by HPJ) was placed in a reaction vessel and refluxed under a nitrogen stream. Methyl methacrylate 5 in it
9 parts by weight, 33 parts by weight of n-butyl methacrylate, 6 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of methacrylic acid.
A mixture of parts by weight and 0.3 parts by weight of azobisisobutyronitrile was added dropwise over 3 hours, and after the dropwise addition was completed, the reaction was continued under reflux for another 3 hours to form a solution of acrylic iso (approximately 45M in fat solubility) Isopropyl alcohol was added to this solution to adjust the degree of embedding of the acrylic resin to 20% by weight.

Example 1 Polyvinyl chloride (9=xzoo) loo parts by weight Dioctyl phthalate 45 I tricresyl phosphate 5 #Epoxidized soybean oil 21 Zinc stearate
0.51 stearin rffi2 barium
0.51 Ultraviolet absorber 0.1
1 Sorbitan monostearate 2.5
l (Surfactant) The above mixture was heated to a thickness of 0.1 mm using an inverted calender. Lo
w film 1. I gave it an A. 35 to this film IA
C/12 hr and 5 C/12 hr cold cycles (hereinafter simply referred to as cold cycles) were applied 5 times and 9 times to obtain films IB and IC, respectively. The aqueous dispersion of acrylic <11 fat prepared in Reference Example 1 was applied to one side of these films 1A to IC, and the thickness of the coating after drying was 2. O
It was coated by a rod coater method so that the coating amount was pm.

The coated films were dried by passing them through a 20 m long oven heated to 140 °C using a dry air jet nozzle method at a line speed of 40 m/min. Haze ratio to IA, acrylic 4. ) (Repellency of the coating liquid when an aqueous dispersion of fat is applied (hereinafter simply referred to as coating liquid repellency) and whitening of the coating film of the film obtained by drying the coated film (hereinafter simply referred to as coating film) (expressed as whitening) are shown in Table 1.

In addition, the degree of haze is shown in JIS-6714, and Toyo f#
It was measured using a direct reading type haze meter made by Ki Seisakusho ((1). Also, the repellency of the coating liquid and the whitening of the coating film were visually observed as 11.

Comparative Example 1゜The film prepared in Example 1 was subjected to 18 cold cycles for one person.
The test was carried out twice and 37 times to obtain film ID and IE, respectively. Thereafter, a film coated with an acrylic resin was obtained in the same manner as in Example 1. Film ID, IE film IA
Table 1 also shows the ratio of W to JPY, the repellency of the coating solution, and the whitening of the coating film after drying.

Table 1 As shown in Table 1, if the haze ratio exceeds 3, the coating solution will be repelled and the coating will become white, making it unusable, whereas if it is less than 3, no problems will occur. I understand that.

Example 2 Real h'Jr f! 1 except that 2.0 parts by weight of sorbitan monopalmitate was used as a surfactant.
(f) Two films with a thickness of 0.075111 m were obtained in the same manner as in Example 1. These two films were subjected to a heating and cooling cycle for 6
The process was repeated twice and 11 times to obtain film 2812C, respectively. An aqueous dispersion of acrylic resin was applied to these films 2A to 2C in the same manner as in Example 1. Table 2 shows the haze ratio, coating liquid repellency, and whitening of coating Br4 for these films 2A to 2C for two people.

Comparative Example 2 The film of Example 2 was subjected to cold and hot cycles 19 times and 42 times.
This was repeated to obtain 2p and 2g of films, respectively.

An aqueous dispersion of acrylic (bt) fat was applied to these films 2D and 2E in the same manner as in Example 1. Table 2 shows the whitening of N.

Table 2 Example 1 In Example 1, 0.6 parts by weight of polyethylene glycol monostearate, 1.2 parts by weight of sorbitan monostearate, and 0.6 parts by weight of polyoxyethylene adduct of sorbitan monostearate were used as surfactants. A film 3 having a thickness of 0.1511F was prepared in the same manner as in Example 1 except that the groove was used.
I got an A. This film was subjected to 6 and 13 cold cycles.
Film 3B each.

3C was obtained 1. An aqueous dispersion of acrylic resin was applied to these films 38 to 3C in the same manner as in Example 1.

Table 3 shows the haze ratio, coating liquid repellency, and coating whitening of these films 3A to 3C with respect to film 3A.

Comparative Example 3 Film 3A of Example 3 was subjected to cold and hot cycles for 21 times and 4 times.
It was applied five times to obtain films 3p and 3E, respectively. These films 3D13] were treated with acrylic yarn 4. in the same manner as in Example 1. An aqueous dispersion of &f fat was applied.

These film 3D, haze ratio of 3g to film 3A, coating liquid 911 and coating IK! The whitening is shown in Table 3.

Table 3: 1.0 parts by weight of sorbitan monostearate and 1 part by weight of sorbitan monostearate as surfactants in Example 1
．． The thickness was 0.5 parts by weight in the same manner as in Example 1 except that 5 parts by weight was used.
A film 4A of 131+m was obtained. This film 4AK
The film 4 was subjected to 3 and 8 cycles of cooling and heating, respectively.
B and 4C were obtained. An aqueous dispersion of acrylic 4-leaf fat was applied to the films 4A to 4C in the same manner as in Example 1.

Table 4 shows the haze ratio, coating liquid repellency, and coating whitening of these films 4A to 4C with respect to film 4A.

Comparative Example 4゜The film of Example 4 was subjected to cold and hot cycles for 18 and 2
I ran it 9 times and got films 4D and 4E respectively. An aqueous dispersion of acrylic resin was applied to these films 4D14E in the same manner as in Example 1.

Table 4 shows the seismic intensity ratio of these films 4D and 4E with respect to film 4A, the thickness of the coating solution, and the whitening of 1 μm of coating.

Table 4 Example 5゜Real IJ1 The same procedure as in Example 1 was carried out except that 0.4 parts by weight of pentaerythritol monooleate and 1-27Rt m of sorbitan monostearate were used as surfactants in Example 1. A Row film 5A was obtained. This film was subjected to cooling and heating cycles by 5 people 8 times, 17 times, and 28 times to obtain films 5B, 5C, and 5D, respectively.

An aqueous dispersion of acrylic resin was applied to these films 58 to 5D in the same manner as in Example 1.

r of these films 58 to 5D relative to film 5A
Table 5 shows the repellency ratio, the repellency of the coating solution, and the whitening of the coating film.

+1:1 dazzle part 1 momme Film 5A of Example 5 was subjected to 45 cycles of cooling and heating to obtain film 5E. An aqueous dispersion of acrylic resin was applied to this film 5E in the same manner as in Example 1.

h' degree ratio of this film 5E to film 5A,
Table 5 shows the repellency of the coating solution and the whitening of the coating film.

Table 5 Example G.

The film obtained in Example 1 was coated with an aqueous dispersion of acrylic resin in two consecutive roll coaters without being wound up with a roll, and the thickness of the coating film after drying was 2.0 μm.
It was applied so that The coated film was dried using a dry air jet nozzle method during and after the opening of a length of 107 m heated to 140°C using infrared paper of 1 to 5 m in length. Continuous dryer twin speed 40 m /
This was done by passing it through at min.

G;7 There was no repellency of the fabric liquid at all, and the coated film obtained was of good quality with excellent brightness, and no change was observed even after two years of use outdoors. Ta.

Fruit 1ii 1 many! ]7° Film 3A obtained in Example 3 was coated with an aqueous dispersion of acrylic resin continuously using a roll coater without winding up the film 3A with a roll. Drying was carried out in the same manner as in Example 6. No repellency of coating ability was observed at all, and the coated film obtained was also of good quality with excellent transparency.

Example 8. and Comparative Example 6゜Using the films IA to IE obtained in Example 1 and Comparative Example 1, the solution of the acrylic resin in the organic solvent prepared in Reference Example 2 was dried, and the thickness of the coating film was 2. It was applied so that the thickness was 0 μm.

Drying after application is done using a dry air jet nozzle method.
The test was carried out by passing the coated film through a 20 m long open chamber heated to 40° C. at a line speed of 40 m/min.

Table 6 shows the uneven coating of the coating liquid and the whitening of the coating.

Table 6 Example 9 and Comparative Example 7 Using the films 3A to 3E obtained in Example 3 and Comparative Example 3, a solution of an acrylic resin in an organic solvent was applied in the same manner as in Example 8.

The uneven coating of the coating solution and the whitening of the coating film are shown in Table h) 7.

7th) Tomi Example 10゜The film IA obtained in Example 1 was coated with an acrylic film (,・I
After drying, apply a solution of an organic solvent to the fat 1iI/! The thickness of
．． It was applied so that it became Op m. The coating film is dried using a dry air jet nozzle method in a 20 m long open chamber heated to 140°C at a line speed of 40 m.
I decided to run it at /min.

No uneven coating of the coating solution was observed at all, and the coated film obtained was also of good quality with excellent transparency.

41 Applicant Mitsui Toatsu Chemical Co., Ltd. - Company procedures? li official document (method) February 28, 1980 Mr. Kazuo Wakasugi, Commissioner of the Patent Office ■, Indication of the case Patent Application No. 173.928 of 1982 2, Name of the invention Method for producing dust-proof polyhinyl chloride film 3, ? Relationship with the case of a person who makes illegal corrections Patent applicant address: 3-2-5 Kasumigaseki, Chiyoda-ku, Tokyo, February 220, 1982 (shipped) 5. Specification subject to amendment 1-1 331-

Claims (1)

[Scope of Claims] 1. A method for producing a dust-proof polyvinyl chloride film comprising surfactant-containing polyvinyl chloride film coated with an acrylic resin on one side or both sides, comprising: a base material; If the hardness of a certain polyvinyl vinyl film is within 3 times the temperature measured immediately after production, an acrylic (6) solution is applied to one or both sides of the film. A method for producing a dust-proof polyvinyl chloride film, characterized in that: 2. The step of applying an acrylic resin solution to one or both sides of the base polyvinyl chloride film is directly connected to the JPL production process of the base film. The manufacturing method according to claim 1 nL, characterized in that the manufacturing method is carried out continuously. Claim 1 or 2, wherein the solution of λ acrylic (<iJ fat) is an aqueous dispersion. B (manufacturing method described in this article) 4' Acrylic (0)
2. The method of seasoning according to claim 1 or 2, which is a solution containing '41 Mobile solvents 75 (benzene, toluene, xylene, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methanol, ethanol, gropanol, 'isopropanol, n-butanol, methyl cellosolve, ethyl cellosolve, butyl cellonorb, methyl The claim is one or a mixture of two or more members from the group consisting of calpitol, methyl calpitol, butyl calpitol, methyl cellosolve acetate, ethyl cellonorbu acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cycloheyazanone. How to manufacture the fourth spear.