JPS5898351A - Polyvinyl chloride film having durable electrostatic adhesion - Google Patents

Abstract

PURPOSE:To provide a PVC film which can retain good electrostatic adhesion over a long period of time and can be repeatedly sticked by electrostatic adsorption without leaving sticked traces behind, by molding a PVC compsn. contg. specified amounts of an organotin stabilizer and other additives blended therewith. CONSTITUTION:Not more than 3pts.wt. (in terms of metallic tin) organotin stabilizer such as an organotin malate ester, a lubicant (in such as amount that film does not exhibit water-resistant whitening phenomenon when immersed in water at 30 deg.C or lower) and other additives are blended with 100pts.wt. PVC to obtain a compsn. which is then molded to obtain the titled film. This film can be sticked on the smooth surfaces of windows, wall surfaces, lockers, etc. by electrostatic adsorption caused by rubbing. Change in places to be sticked and repeated stickihg are possible. USE:Memo paper, seal, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyj-crystalline vinyl film (hereinafter referred to as PVC film) that has excellent electrostatic plate and long-lasting adhesive strength.

General V (It is widely known that plastic materials are insulators and have the property of being easily charged by contact friction, but in the past, they have not been widely used in fields where charging is an obstacle.)
Because of this, problems focused on preventing static electricity. However,
The present invention attempts to actively utilize electrostatic adsorption force.

In order to actively utilize the electrostatic adhesion force, it is necessary that static frost occurs frequently and that the electrostatic adhesion force is strong and lasts for a long time.

On the other hand, as a basic method for determining the lubricating properties of plastics, the surface hardness (+'u'l;
A Pi, IY measurement of frictional charge amount, measurement of charged tube attenuation characteristics E
Other practical methods include the cigarette ash inhalation test and the dirt chamber test.

The measured value of surface resistivity is also used as a measure of anti-static properties, in connection with the fact that the charging phenomenon of plastics is often caused by contact and friction of the surface. When discussing the electrical properties of materials accurately, it is customary to use volume resistivity, and usually ρ = 0 to 10Ω-
A distinction is made between cmi as a conductor and Ω as an insulator.

The larger the volume resistivity value is, the better the insulator is, and generally the amount of frictional electrification of the material itself becomes larger, and the charging tube attenuation characteristics are also poorer due to the poorer conductivity. In the long run, the charging cylinder tends to be difficult to attenuate.

When the L' V C film causes static electricity absorption due to contact friction with objects with smooth surfaces, such as metal plates, glass plates, paper, and wooden boards, there is an electric double layer between the two that are in close contact with each other. This indicates that a potential difference is occurring, and the static electricity trapped in the electric double layer is balanced and stable as a double layer, so it cannot be sensed from the outside that a potential difference is occurring, but it is possible due to the potential difference. The adsorption power of the product is in full effect.

The main purpose is the sustainability of the adsorption force due to this electric double layer, that is, the relationship between the charge decay characteristics of the electric double layer and the volume resistivity of the PvC film, and the size of the volume resistivity. The long duration of the adsorption force does not necessarily mean that there is a proportional relationship V? However, the duration of the adsorption force of the electric double layer is greatly influenced by the Pvc composition.
It has been found that it can be systematized by changing the blending composition, and that it is possible to maintain the adsorption state of the PVC film and other objects for a long period of time.

The present invention was invented based on this knowledge, and its gist is that 3 parts of organotin-based stabilizer is used in place of metal tin for 100 parts of polycyclized vinyl resin. It is characterized in that the ingredients are blended within a range that does not cause water-resistant whitening phenomenon even when immersed in water at temperatures above or below 30°C.

The PVC stabilizers include lead salt-based stabilizers, metal soap-based stabilizers, tin-based stabilizers, and composite stabilizers that are combinations of characteristic compounds.

Now, by changing the type of stabilizer, the volume resistivity (30℃, 70% R, [I) and adsorption force duration (20℃, 55% RII'l[, Table 1 It was on the street.

[Formulation example]

A PVC film with a thickness of 0.1 mm was prepared by blending 100 parts of PVC (degree of polymerization 800) [7 tl, 20 parts of plasticizer (DOP), and 3 parts of stabilizer] and obtained under constant extrusion conditions (100°C, 3 minutes). Table 1 According to the results, the volume resistivity of lead compounds as a stabilizer is clearly higher and the initial adsorption force at saturated charging is also larger, but the adsorption duration is inferior to organotin, and organotin is more effective than lead-based stabilizers. It can be seen that the system stabilizer causes much less charge decay in the electric double layer. Similar experiments have also shown that metal soap stabilizers outside of ship equipment and composite stabilizers other than organotin have inferior adsorption durability compared to organotin.

In addition, even with the same organotin stabilizer, there are differences in the persistence of layer formation depending on the compound, and those with good compatibility with the PvC resin tended to have good persistence in culm adsorption.

Furthermore, when the blending ratio of the stabilizer to the PVC resin is increased or decreased, even if it exceeds 10 parts, the volume resistivity does not decrease, but the sustained performance of electrostatic adsorption decreases to 5@-.

In the case of organotin-based stabilizers, up to 3 parts in terms of metallic tin gave the best adsorption durability, and at more than 3 parts, the electrostatic adsorption durability decreased. The reason for using 3 parts F in terms of metal tin stabilizer is as follows.

In addition, there are two types of lubricants: internal lubricants and external lubricants. Internal lubricants have good compatibility with PVC, and external lubricants have high compatibility with PVC.
It is said that it has the effect of reducing the friction during melting of the material wall in contact with VC, but it is necessary to maintain a good balance between both functions when molding PVC.

Regarding the sustainability of electrostatic adsorption, internal lubricants with good compatibility tended to be better than external lubricants, but with both γL, the adsorption sustainability decreased with increasing blending amount.

If the amount of plasticizer added is up to 5 parts, no significant change in adsorption sustainability was observed, but it clearly decreased from 10 parts to tsubo.

Furthermore, the adsorption sustainability of vinyl acetate and its copolymers decreases as the amount added increases, and a similar trend was observed for polymer blends such as ethylene derivatives and acrylic rubber. .

As described above, the relationship between the sustaining properties of electrostatic adsorption force and the blending amounts of lubricants, plasticizers, and other polymers is as follows.
Since the relationship between the water-resistance whitening phenomenon and the formulation of lubricants, plasticizers, and other polymers is well-matched, in the formulation display, 3 parts of organotin-based stabilizer should be listed below P. 30
It was found that blending the lubricant and other additives within a range that does not cause water-resistant whitening even when immersed in water at ℃υ is the preferred range for achieving good electrostatic adsorption force sustainability. Therefore,
It is preferable to use a material that does not exhibit water-resistance to whitening unless exposed to hot water at a higher temperature than 30 DEG C., or does not exhibit water-resistance to whitening even in hot water at a temperature up to the melting point.

Next, a PC film with a thickness of 50μ according to the formulation shown in each example was formed and cut into a size of 10cm both lengthwise and widthwise,
As shown in Fig. 1, the film piece 1 is pressed against the glass plate 2 at a constant pressure V (more than the saturation voltage) (continuing contact friction until the film piece 1 is in a state of static electricity adsorption, vertically moving the glass plate). The duration of electrostatic adsorption when maintained at 20° C. and released under 65% Al1 conditions is shown for each implementation system.

[Example-1] PVC (P2F30 (1) 1 (10 parts epoxy plasticizer 5) Organotin malate ester 2 //Organic tin laurate tono2domium stearate 03) Transparent lubricant
0.2/' (Adsorption duration: 32 days n11) [Example-2] PVC (Pm2O3) 100 parts Organotin malate ester 15 Organotin laurate
0.51/Epoxy soybean oil 2〃 Transparent lubricant 1〃 (Adsorption duration near 5 days) [Example-3] PVC (p=+05o'+ 1oO part organotin malate ester 2) Organotin mercaptide
Q, 5 u organotin laurate
1//Epoxy fat bean oil 3〃Tinuvin p O,01//(Adsorption duration near 0 days) [Example-4] PVC (P=soo) Loo part organotin malate ester 25/l organotin laurate
0.5/' stearic acid
Q, 5//butyl stearate 1.
0 Tinuvin p O, Q l t
t (adsorption duration 2180 days or more) [Example-5] I) VC (Pm8O0) 100 parts Organotin mercaptide 2.51/organotin malate ester 1.57/butyl stearate
07 parts stearic acid 0.3
M B S 5 u (adsorption duration: 180 days or more) [Example-6] I) VC (Pm7O0) loo moiety organotin malate ester 3. organotin mercaptide
11 Nobutyl sterile rate Q,
7 tt higher fatty acids 0. ,(,
.

Stialyl alcohol 0.3n Hoechstwax 01llhi B S
51/(Adsorption duration 2180 days or more) [Example-7] pvc (P=soo) 100 parts organotin mercaptide 3'l organotin malate ester 2 organotin laurate
l〃Butyl stearate 0.5
tt stearic acid 05 parts liquid paraffin 0.1" (adsorption duration: 18
0 days above) As mentioned above, when you rub a PvC film, peel it off from the friction object, and measure the amount of charge, a considerable potential difference is measured. When the film is tightly packed against a metal plate, the film causes strong electrostatic adhesion to the metal surface, and the amount of charge that can be received from the outside becomes almost unmeasurable. This is thought to be due to the fact that the static electricity on the film caused by friction becomes stable as a charge on the electric double layer due to its close contact with the metal plate, and the static electricity loses its influence on areas other than the double layer. Also, P
If a coating film of a surfactant is uniformly formed on one side of a VC film to prevent charging, even if the opposite non-coated surface is rubbed and the film is separated from the abrasive object, it will not be able to prevent charging due to the influence of 11. Although static electricity cannot be measured, it has been found through actual soap testing that when the rubbed uncoated surface is brought into close contact with a metal plate or the like again, the static electricity adsorption force is lost.

This is a charged μno! Even if the electrostatic force in the direction perpendicular to the film surface is erased by the anti-scratching coating, the amount of charge on the electric double layer remains, and it is considered that it exhibits adsorption force.

Therefore, it is difficult to directly determine d(1) of the static electricity trapped in the electric double layer, so the suction force can be measured indirectly by measuring the peel strength or sliding friction force of the film. However, since the peel strength and sliding friction force also give a new contact charge to the film, the decay of the static electricity in the electric double layer must be continuously measured. 77 (is an inappropriate method.

When the surface of a PvC film and another object that is electrostatically attracted is placed parallel to gravity, the adsorption force of the electric double layer is stronger than the PVC film's own weight.lj'l Id sThe adsorption state continues, but due to discharge The electrostatic adhesion force attenuates with time, and finally, when the adhesion force exceeds the film's own weight by T1, the PvC film peels off and falls.

Therefore, in the present invention, constant friction is continuously applied l)
By applying V C to the film, the frictional charge between the surface of another object and the surface of another object is brought to a saturation state, and after stopping the friction starting from the electrostatic adsorption at that time, the electrostatic adhesion force of the electric double layer is attenuated and the film peels off and falls. The time required for
and n were used as the criteria for determining the quality of the I) VC film according to the present invention.

The PVC film according to the above-mentioned invention has a strong electrostatic adsorption force that lasts for a long time, so it can be attached to any suitable flat surface such as a window surface, wall surface, locker, furniture, desk, bookshelf, etc. by applying frictional electrostatic adsorption. It is also possible to change the location, repeat the application, or use a single application. Furthermore, there is no trace of adhesion after peeling off.

Therefore, the present invention is applicable to items that are pasted, and items that are used after being pasted or peeled off, such as paper for advertisements and guidance, paper to replace blackboards and message boards, memo paper, and thin stickers for various types of openings. is optimal.

At this time, it goes without saying that the spoon must be processed according to the type of item to be used.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram of an effect test of the present invention. 1... PVC film piece according to the present invention 2... Glass plate patent applicant Norio Mera Patent applicant Ma Itagaki Agent Patent attorney Sadanobu Shimizu 5,”;゛・(・ %, 1↓ Figure 1 Procedural Amendment Document February 10, 1980 Commissioner of the Japan Patent Office, Shima 1) Zonjuden 1 Display of case 1988 % Relationship with case No. 197394
Patent applicant name: Yoshiyuki Yoshio and 1 other person4, agent5, date of amendment order Voluntary8, content of amendment - 7 copies attached; the scope of the patent claims is amended as follows: . Add up to 3 parts of organotin stabilizer to 10 parts of polyvinyl chloride resin (1) and 3 parts or less of other compounding agents using a metal tin exchanger.
A long-lasting, water-resistant film with a water resistance of f=6', which is formulated in a range that does not cause water-resistance whitening even when immersed in water at 0°C for 10 minutes at 1+J. m; Details 1 Condolence 4 White line 2 ``...Water below 30℃ V
Next to "C", add -1 within 10 minutes.
Add "within 10 minutes" to the arrow of "τ". (ii) Page 7 of the specification, line 13, "...therefore," followed by 13
0℃ν] force that does not show water-resistant whitening phenomenon even if immersed in water for 10 minutes on a wharf) is added. (S) Page 7 of the detailed total, line 15, “or” after “does not indicate?”
join. (12) "One or more of lines 11 and 4 of the specification" shall be deleted in their entirety.

Claims (1)

[Claims] Bo'Jt = 3 parts or less of organotin stabilizer (calculated as metal tin) and 3 parts of lubricant and other compounding agents per 100 parts of chloride resin.
A polyvinyl chloride film with durable electrostatic adhesion that is formulated in a range that does not cause water-resistant whitening even when immersed in water at temperatures below 0°C.