JPS6031335B2 - Antistatic method - Google Patents

Description

Detailed Description of the Invention The present invention is durable for various synthetic resin materials such as polyolefins such as polyethylene and polypropylene, vinyl polymers such as styrene resin, vinyl chloride resin, acrylic resin and ABS resin, and polyester resin. The present invention relates to a method for imparting antistatic properties.

In general, these polymeric materials are plastics that are widely used as molding materials for films, molded products, and fibers, but although they have excellent electrical insulation properties, they have the disadvantage of being easily charged with static electricity, and because of this, they have various It is the cause of failure and secondary disasters.

In addition, stains may occur due to electrostatic charge, and it is extremely important in practice to prevent plastic from becoming electrostatically charged.
Conventionally, methods for preventing such electrification have generally included attaching an antistatic agent to the surface or kneading it into a resin.

The method of applying or spraying a solution of an antistatic agent onto the molded resin has the disadvantage that the effect is temporary and the antistatic effect decreases and disappears due to friction, aging, washing, etc. In the kneading method, when melt molding is performed at high temperatures, commonly known antistatic agents not only cause thermal decomposition and color, but also promote yellowing and discoloration of the resin, and are especially difficult to maintain transparency. In the case of resins and the like, there is a tendency for transparency to be impaired. On the other hand, when formed into a film or the like, there are many problems such as deterioration of surface properties such as blocking or slippage, whitening phenomenon on the surface due to constant bleed, and inhibition of film transparency. An object of the present invention is to provide an antistatic processing method that provides durable antistatic properties and does not cause blocking, whitening, or loss of film transparency.

In the antistatic processing method of the present invention, an aliphatic and/or alicyclic epoxy compound containing a compound that releases an active catalyst that initiates polymerization of the epoxy compound upon irradiation is applied to a base resin that has a tendency to become electrically charged. It is characterized by polymerizing the epoxy compound by irradiation.

As the epoxy compound used in the present invention, aliphatic or aliphatic epoxy compounds can be used as appropriate. However, when focusing on the magnitude of the antistatic effect, aliphatic epoxy compounds, especially polyols having about 2 to 8 carbon atoms, may be used. Preference is given to using glycidyl ethers.

Such aliphatic glycidyl ethers include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, butanediol diglycidyl ether, hexanediol diglycidyl ether, propylene glycol diglycidyl ether, neobentyl glycol diglycidyl ether, Examples include trimethylolpropane polyglycidyl ether, glycerol polyglycidyl ether, bentalythritol polyglycidyl ether, diglycerol polyglycidyl ether, and sorbitol polyglycidyl ether.

On the other hand, in the present invention, the epoxy compound is polymerized by irradiation, but there are cases in which high-speed curing (for example, it takes several seconds to become tack-free with an 80W UV lamp), and in this case, It is preferable to use an alicyclic epoxy compound in addition to the above aliphatic epoxy compound.

Preferred examples of such aliphatic epoxy compounds include: ○3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, ○dicyclobentadiene dioxide, ○cyclohexene diepoxide, ○ 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, ○bis(3,
4-Epoxycyclohexylmethyl)adibate,○
Examples include those in which the ratio of ether groups and carbonyl groups to the molecular weight is relatively high, such as bis(3,4-epoxy 6-methylcyclohexylmethyl)adibate, ◯ dibentene dioxide, and the like.

When an aliphatic epoxy compound and an alicyclic epoxy compound are used as a mixture, the appropriate weight ratio is 1:0.1 to 20, preferably 1:1 to 5.

The compound used in the present invention that decomposes under irradiation and releases a catalyst having the effect of causing polymerization or crosslinking of an epoxy compound is not particularly limited, but particularly preferred compounds are those that release a Lewis acid capable of initiating polymerization upon irradiation. It belongs to a group of Enoki salts, which are onium salts that

Such compounds basically have the general formula [R1aR2bR3c
R also Z] Machine [MXn+m]-m [In the formula, the cation is onium, Z is N3N, S, Se, Te, P, ship, Sb
, Bi, 0, halogen (for example, 1, Br, CI), R1, R2, R3, R4 are organic groups that may be the same or different, a, b, c, d are 0 to 3. a+b+c+d is an integer and is equal to the valence of Z. M is a metal or metalloid that is the central atom of the lead halide body (me side 1
oid), B, P, As, Sb, Fe, Sn, B
i, AI, Ga, ln, Ti, Zn, Sc, V, Cr,
Mn, Co, etc. x is a halogen, m is the net charge of the halide chain body ion, and n is the number of halogen atoms in the halide chain body ion. ]. This rule. The body itself is known;
For example, a compound in which Z is N-bow N is disclosed in U.S. Patent No. 3708.
No. 296, No. 3949143, No. 3794576
It is stated in the number etc. Other onium catalyst precursors include Belgian Patent No. 828841, Belgian Patent No. 82866y,
It is described in French Patent No. 227026, etc.
The above diazonium compounds are described in the above-mentioned U.S. Patent No. 3708.
It can be obtained by the method described in No. 296, No. 3949143, etc. Compounds in which Z is S, Se, Te are described in J. J. Knapczyk et al. A. C. S. ,91,
145, (1969), A. L. Maycock et al.
J. ○R bag n with Chemistry, 35, No. 8
, 2532 (1970), G.C.ethals et al., Bul.
．． Soc. chim old elg. , 73,546 (196
4), day. M. J. of Icester et al. A. C. S.
, 513587 (1929), etc. Representative onium salts where Z is P, N, As, Sb, Bj are described by J. G℃erdelier's Method
nderOrganishenChimje, 11/1
2,591-640 (1958), K. It can be produced by the method described in Sasse 12/1, 79-112 (1963). A typical onium salt where Z is halogen is 0. A. Dokl. of Pt ship starvation et al. Adad. Nan
k. , SSSR, 163, 383 (1965), M. D
J. Rexler et al. A. C. S. ,75,2705(
It can be produced by the method described in (1953) et al. Examples of other compounds that can be used to initiate the polymerization of epoxides are iodoform, Q'Q-dibromoparaxylene, bromoform, carbon tetrabromide, hexachloroparaxylene, and other catalysts described in U.S. Pat. No. 3,895,954. ,
Bis(perfluoroalkylsulfonyl)methane salt, and US Pat. No. 3,586,616, German Patent No. 241,927
It is an organic halogen compound such as a diazonium salt of sulfonylmethane as described in No. 4. The base resins that are subject to the present invention and tend to be electrically charged include soft or hard vinyl chloride resins, low-density or high-density polyethylene,
Polyolefins such as polypropylene, vinyl polymers such as polyacrylonitrile, polystyrene, and AS resins,
Examples include various polymeric substances such as copolymers of olefins and vinyl monomers such as Amo resin, and polyester resins.

In addition, as a method for applying the epoxy compound to the base resin that is effective in the present invention, general methods such as a coating coater, a gravure coater, and a spray coating can be mentioned, and the coating thickness is 0.1 to 30. Approximately 1 to 5 Buddhas, preferably 1 to 5 Buddhas.

Representative examples of the present invention will be explained in more detail below using Examples and Comparative Examples, but prior to that, the measurement method described below will be explained.

All parts in the examples are parts by weight. (Attachment test) After rubbing a 15 cm x 15 cm test piece with gauze 20 times, the height (unit: side) at which tobacco ash is adsorbed was measured.

After the test sample was left for a long time under constant temperature and humidity of 40% RH and 2500, it was measured under the same conditions.

(Surface specific resistance value) After the test sample was left in an atmosphere of 60% RH and 230° for 24 hours or more, it was measured using a transcendent green meter.

Example 1 100 parts of bis(3,4-epoxycyclohexylmethyl)azibate (epoxy equivalent weight 190-205) and p-
Mix 1 part of chlorobenzesodiazonium hexafluorophosphate, apply it to each coated plastic film so that it has a film thickness of 5 layers, and apply a high-pressure mercury lamp (IKW, 380 side length) from a distance of 15 cm to 2 parts of the plastic film.・Irradiate for a while,
The surface resistivity of the plastic surface after curing was measured and an ash test was conducted using ash adhesion.

The results are shown in Table 1. Examples 2-3 Same as Example 1, except that 1,4-
Butanediol diglycidyl ether (epoxy equivalent 1
36) Alternatively, tests were conducted using 1,6-hexanediol diglycidyl ether (epoxy equivalent weight 150-160).

The results are shown in Table 1. Comparative Examples 1 and 2 The same procedure as in Example 1 was carried out using diglycidyl ether of bisphenol A or polyglycidyl ether of phenol formaldehyde novolak as the epoxy compound, and the surface was as shown in Table 1. No decrease in specific resistance was observed, and no antistatic effect was shown in the ash test.

As is clear from Table 1, the surface resistivity of Examples 1 to 3 is significantly lower than that of Comparative Examples 1 and 2, and they also show antistatic effects in the ash test.

Furthermore, no changes over time were observed 30 days after sample preparation. Example 4 Bis(3,4-epoxycyclohexylmethyl)azibate (epoxy equivalent weight 190-205) 5 Ikarikou and 1,4
- A resin composition obtained by mixing a mixture of 5 parts of butanediol diglycidyl ether (epoxy equivalent: 136) and 1 part of p-chlorobenzenediazonium hexafluorophosphate was applied to a plastic sheet or film so that the film had a thickness of 5 mounds. It was placed 10 cm away from the same IKW high-pressure mercury lamp as in Example 1, and the resin composition-coated surface was irradiated with a 1-hour spacing.

The same tests as in Example 1 were conducted on the cured plastic, and the results are shown in Table 1. Example 5 In the same manner as in Example 4, bis(3,4-epoxycyclohexylmethyl)azibate (epoxy equivalent: 1) was used as the epoxy resin.
The test was conducted using a mixed resin of 50 parts of 1,6-hexasodiol diglycidyl ether (epoxy equivalent: 150 to 160) and 5 fat B.

The results are shown in Table 1. Comparative Example 3 Unique #122 (manufactured by Arakawa Paint Co., Ltd.), a conventional solvent-based PVC varnish, was applied to hard and soft polyvinyl chloride sheets and Tetron film so that the cured film thickness was 5:1, and after drying. , surface resistivity measurements and ash tests were conducted.

As is clear from the results in Table 1, no antistatic performance was exhibited. Comparative Example 4 Table 1 shows the surface resistivity values and ash test results of uncoated polyvinyl chloride (soft and hard) sheets and Tetron films.

Table 1

Claims (1)

[Claims] 1 An aliphatic and/or alicyclic epoxy compound containing a compound that releases an active catalyst that initiates polymerization of the epoxy compound upon irradiation is applied to a base resin that tends to be electrically charged, and then irradiated to polymerize the epoxy compound. A method for preventing static electricity on resin that tends to become static.