JP2002012686A - Resin sheet or film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a styrene-based resin-containing resin sheet/film suppressed in stickiness/blocking while maintaining its transparency/color tone, improved in antistaticity, especially frictional antistatic performance, under low humidities, with charge voltage half-life and frictional charge voltage proofness effect balanced therebetween. SOLUTION: This resin sheet/film is such as to be coated with a mixed coating composition comprising an antistatic composition comprising (A) a fatty acid amide and (B) a polyoxyethylene-polyoxypropylene block copolymer, (C) a silicone oil and (D) a blue colorant so as to satisfy the following requirements (1) to (4) : (1) the weight ratio for the components A and B: 0.90>=A/(A+B)>=0.40, (2) the coating level of the antistatic composition is 2-30 mg/m2, (3) the coating level of the silicone oil C is 1-25 mg/m2, and (4) the coating level of the water-soluble blue colorant D is 0.05-5 μg/m2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a biaxially oriented film having excellent antistatic properties, which is mainly used for various packaging containers (obtained by secondary molding of sheets), packaging films, envelope window covering films and the like. The present invention relates to transparent resin sheets and films such as styrene resin sheets and films.

[0002]

2. Description of the Related Art It is generally known that a surfactant is kneaded or applied to prevent static electricity, that is, antistatic of plastics. For example, "Supplementary Guide to Electrostatic Safety Guide" (written by the Industrial Safety Research Institute, Ministry of Labor) states that N, N-bis (2-hydroxyethyl) alkylamine and polyoxyethylene alkyl are the main surfactants for antistatic agents. Amine, fatty acid ester of polyoxyethylene alkylamine, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, etc., anionic, cationic, amphoteric surfactant Agents and the like are described.

Various studies have been made on the kneading or coating of a surfactant to prevent the charge of a resin used in a sheet or film, for example, a styrene resin. Japanese Patent Application Laid-Open No. 9-1655 discloses an example in which an antistatic agent is kneaded into a styrene resin.
No. 70 describes an antistatic composition comprising fatty acid diethanolamide, a random copolymer of ethylene oxide and propylene oxide, a styrene resin, and a metal oxide. When such a composition is kneaded into a transparent styrene resin sheet / film,
It tends to deteriorate the transparency of the film. For this reason,
When importance is placed on transparency, it is necessary to reduce the amount of the antistatic agent added, and as a result, it is difficult to obtain a sufficient antistatic effect. Also, when a known surfactant described in the above-mentioned “Electrostatic Safety Guidelines, Supplement to the Application” is kneaded, the transparency of the sheet / film must be sacrificed in order to obtain a sufficient antistatic effect. In most cases you have to.

[0004] For this reason, for transparent sheets and films,
In particular, in the case of styrene-based resin sheets and films, it is common to apply a surfactant to impart an antistatic agent. As a technique of applying a surfactant to a transparent styrene-based resin sheet / film to impart antistatic properties, for example, a sucrose fatty acid ester and a coconut oil fatty acid diethanolamide are applied as surfactants (Japanese Patent Publication No. 61-1986). 36864
), Sucrose fatty acid ester, hydroxyethyl cellulose and sorbitol are applied (JP-A-8-1).
No. 57639) has been proposed.

[0005]

SUMMARY OF THE INVENTION The above mentioned Japanese Patent Publication No. Sho 61-3
No. 6,864, or a sheet / film coated with a surfactant described in JP-A-8-157039,
When the relative humidity is about 50% or more at 20 ° C., effects such as a decrease in the surface resistivity and a decrease in the half-life of the charged voltage begin to appear. However, when the relative humidity is about 30% or less, the antistatic property measured by the surface resistivity, the half-life of the charged voltage, and the like tends to be significantly reduced. If the coating amount is increased to compensate for this, stickiness, deterioration of the transparency of the sheet / film and the like occur, and the practicality of the sheet / film is reduced.
Furthermore, under low humidity, in addition to the decrease in the antistatic performance measured by the surface resistivity and the half-life, the amount of triboelectric charge increases, so that when a styrene-based resin sheet or film is used (for example, secondary molding of the sheet) In some cases, high-voltage static electricity tends to be generated (indicating a high charged voltage) when the film is used in an envelope window machine.

[0006] This tendency is not limited to styrene resin sheets and films, but also applies to general resin sheets and films. For this reason, at present, various troubles due to the generation of static electricity have not been completely solved when using sheets and films. This tendency is the same when the above-mentioned generally known surfactant is used, and further, depending on the type of the surfactant used, the stickiness of the sheet / film,
In some cases, blocking on a roll around which the sheet / film is wound, whitening (deterioration of the transparency of the sheet / film) due to a coating agent, and the like may occur. As described above, when a known surfactant is applied to a transparent sheet or film represented by a styrene-based resin sheet or film, the charged voltage is reduced by half under low humidity (20 ° C., relative humidity of about 30% or less). At present, it is difficult to obtain a satisfactory antistatic property in which the antistatic property and the antistatic property are balanced.

Further, among known surfactants, those containing nitrogen in the molecule, such as amine surfactants, and surfactants having a yellowish brown or brownish color such as sorbitan fatty acid esters, are added to sheets and films. When coated, the color tone of the end face when the sheet / film is wound on a roll or the end face when stacking the molded product obtained by secondary forming the sheet takes on a yellowish brown or brownish color. There is also a disadvantage. For this reason, the coating amount of the antistatic agent may be significantly limited. The present invention maintains the transparency of resin sheets and films including styrene-based resin sheets and films, suppresses stickiness and suppresses blocking of sheets and films, and under low humidity (20 ° C., relative humidity of about 30% or less). Resin sheet with improved antistatic properties, especially frictional antistatic performance, balanced half-life of charged voltage and antistatic effect of frictional electrostatic voltage, and suppressed deterioration of color tone of sheet and film by coating with antistatic agent. It is intended to provide a film.

[0008]

Means for Solving the Problems The present inventors have solved the above problems.
As a result of various studies, the surface of the resin sheet or film
Low humidity by coating with specific composite antistatic agent
The anti-friction property under
It can be seen that the balance between
As a result, the present invention has been completed. That is, in the present invention
Adopted the following: Fatty acid amide (A), polyoxyethylene and poly
From block copolymer (B) made of oxypropylene
Antistatic composition, silicone oil (C), water
Mixed coating composition comprising a soluble blue colorant (D)
Is on at least one surface of the resin sheet or film,
Coated to satisfy the following (1), (2), (3) and (4)
Providing a resin sheet or film characterized by that
You. (1): In the antistatic composition comprising (A) and (B),
The weight mixing ratio of (A) is 0.90 ≧ (A) / ｛(A) +
(B) The relationship of｝ ≧ 0.40 is satisfied. (2): coating of an antistatic composition comprising (A) and (B)
The amount is 2 to 30 mg / m ^Two. (3): The coating amount of the silicone oil (C) is 1 to 25 m
g / m^Two. (4): The coating amount of the water-soluble blue colorant (D) is 0.05 to
5 μg / m^Two. The aliphatic amide (A) is a C8-C18 fatty acid
Also characterized by the fact that it is a condensation product of
Having. Further, the water-soluble blue colorant (D) is a brilliant blue
-FCF (edible blue No. 1), indigo carmine (edible blue)
Color No. 2), a small amount selected from sodium copper chlorofin
It is also unique in that it is at least one kind. Further, the resin sheet or film is biaxially stretched styrene.
Another characteristic is that it is a resin sheet or film
You.

Hereinafter, the resin sheet or film of the present invention will be described in detail. The present invention relates to an antistatic composition obtained by mixing a specific amount of an aliphatic amide (A) and a block copolymer (B) composed of polyoxyethylene and polyoxypropylene coated on a sheet and a film in a specific amount. By the action, there is no side effect such as deterioration of the transparency of the sheet or film, stickiness, slipperiness and the like, and further, the color tone of the sheet / film deteriorates (yellow) by coating the component (A) which generally has a brownish color. ) By adding the component (D) to provide antistatic properties (half-life of charged voltage and low frictional charged voltage) under low humidity (20 ° C. and relative humidity of 30% or less) which cannot be obtained by the conventional technology. It is intended to provide a sheet and a film which have been prepared.

First, the components (A) to (D) will be described. The fatty acid amide (A) used in the present invention is C8
Fatty acid alkanolamides, which are condensation products of C22 to C22 fatty acids with alkyl alcoholamines such as diethanolamine, monoethanolamine and isopropanolamine, or ethylene oxide addition reaction of C8 to C22 fatty acid amides, or C8 to C22 fatty acid amides It is a polyoxyethylene fatty acid amide obtained by a dehydration reaction with polyoxyethylene and a mixture containing these as main components (50% by weight or more). Of these, seats
From the viewpoint of the transparency and the slipperiness of the film, preferably C8
To C18 fatty acid alone or as the main component (50
Wt% or more) and a condensation product (fatty acid diethanolamide) of diethanolamine, more preferably capric acid, lauric acid, or myristic acid alone or a mixture containing these as main components (50 wt% or more). For example, the condensation product of 1 mole of a fatty acid of coconut oil fatty acid) with 2 moles of diethanolamine, or a similar fatty acid 1
It is a condensation product of mol and 1 mol of diethanolamine.

These fatty acid amides (A) are converted to (B)
It is possible to impart to the sheet / film the antistatic property represented by the half-life of the charged voltage and the specific resistance of the surface and the property of being less likely to be triboelectrically charged even under low humidity. The block copolymer (B) composed of polyoxyethylene and polyoxypropylene used in the present invention refers to a polyoxyethylene chain having 10 to 90% by weight, preferably 40 to 85% by weight. Is 90
A block copolymer having a weight average molecular weight of 1,000 to 20,000, preferably 2,000 to 16,000, comprising from 10 to 10% by weight, preferably from 60 to 15% by weight,
Preferably, the polyoxyethylene block-polyoxypropylene block-polyoxyethylene block 3
It is a block copolymer composed of blocks. The mixing ratio and the weight average molecular weight of the polyoxyethylene chain and the polypropylene oxide chain are in the range necessary for obtaining the intended antistatic property, particularly the effect of lowering the frictional voltage, in the sheet of the present invention. By using such a block copolymer (B) in a mixture with the above-mentioned fatty acid amide (A), the frictional voltage can be reduced even under low humidity without deterioration in transparency, slipperiness or stickiness. In addition, antistatic properties can be provided.

In the sheet / film of the present invention, the weight mixing ratio of (A) in the antistatic composition comprising the fatty acid amide (A) component and the block copolymer (B) component is as follows:
It is preferable that the relationship 0.90 ≧ (A) / {(A) + (B)} ≧ 0.40 is satisfied. By setting the above-mentioned weight mixing ratio of the fatty acid amide (A) component to 0.90 or less, especially under low humidity conditions (20 ° C., relative humidity of about 30%), the effect of preventing a frictional band voltage (the amount of static electricity generated by friction is reduced). Holding effect) can be obtained. Further, the weight mixing ratio of the component (A) is set to 0.1.
By setting it to 40 or more, it becomes possible to impart antistatic performance measured by the half-life of the charged voltage. Therefore,
If the mixing ratio of the fatty acid amide (A) component and the block copolymer (B) component is out of the above range, the frictional antistatic effect and the antistatic performance measured by the half-life of the charged voltage are balanced. In some cases, it is difficult to perform the cleaning, and the transparency and the slipperiness may be reduced. Furthermore, in order to balance the effect of lowering the frictional charged voltage and the antistatic performance measured by the half-life of the charged voltage at lower humidity (about 20 ° C. and relative humidity of about 20%), the fatty acid amide (A) and the block The weight mixing ratio of the component (A) in the antistatic composition composed of the copolymer (B) is 0.80 ≧ (A) / {(A) + (B)} ≧ 0.
More preferably, it is set to 45.

The silicone oil (C) used in the present invention is preferably dimethylpolysiloxane, diphenylpolysiloxane, phenylmethylpolysiloxane, polyether-modified silicone oil or the like. From the viewpoints of safety and economy, dimethylpolysiloxane is more preferable. The polyether-modified silicone oil is a silicone oil (dimethylpolysiloxane) in which some of the methyl groups have been modified with polyoxyethylene and / or polyoxypropylene. From the viewpoint of application, a water-soluble one is preferred. When a water-soluble polyether-modified silicone oil is added to the antistatic agent composed of the above (A) and (B), the antistatic effect is further improved and may be more preferable. Further, when the sheet / film of the present invention is used for window covering an envelope, a polyether-modified silicone oil is particularly preferred as the silicone oil from the viewpoint of maintaining the adhesiveness between the film and the envelope.

The viscosity of the silicone oil (C) at 25 ° C. is preferably from 100 to 100,000 cp, more preferably from 300 to 20,000 c, from the viewpoints of imparting releasability to sheets and films and preventing stickiness.
p. When the viscosity of the silicone oil is less than 100 cp, it is a region where the effect of imparting releasability is small, and also a region where safety cannot be guaranteed when the sheet / film is used for food packaging. When the viscosity of the silicone oil exceeds 100,000, stickiness tends to occur on the sheet / film, and especially when the sheet is formed in a secondary form, the silicone oil is transferred to a molding machine, which causes a molded article to be formed. Is a region that may reduce the appearance of the image. Among these silicone oils (C), those which are insoluble in water are prepared by using a silicone emulsion emulsified by a known method, using a fatty acid amide (A) and a block copolymer (B).
It is preferable to mix with the antistatic coating composition of the present invention and coat the sheet as an aqueous solution. Further, the water-soluble silicone oil (C) can be directly mixed with an antistatic coating composition comprising a fatty acid amide (A) and a block copolymer (B), and coated on a sheet as an aqueous solution.

The water-soluble blue colorant (D) used in the present invention is preferably a blue synthetic colorant, a natural colorant, a dye, or the like, which is soluble in water at 20 ° C. in 0.1% or more. The blue color of the water-soluble blue colorant (D) used in the present invention means that the color of the aqueous solution having at least one concentration selected from 0.1 to 100 ppm aqueous solution of the colorant (D) is JIS-Z81.
Basic color names "blue" and "blue-green", "blue-violet" shown in 02
Say any of the following: Among these blue colorants (D), the sheet or film of the present invention is more preferably brilliant blue FCF (edible blue No. 1) or indigo carmine (edible blue No. 2) from the viewpoint of being frequently used in the food packaging field. And a coloring agent recognized as at least one food additive selected from sodium copper chlorofin, and more preferably brilliant blue FCF (edible blue No. 1) from the viewpoint of heat resistance.

The resin sheet or film of the present invention is a mixed coating comprising an antistatic composition comprising the fatty acid amide (A) and the block copolymer (B) and a silicone oil (C) and a water-soluble colorant (D). The composition is coated on at least one surface. The coating amount of each component is
Determined from the viewpoints of antistatic properties, slip properties, color tone of sheets and films, stickiness, transparency, etc., at least one surface has a fatty acid amide (A) and a block copolymer (B).
Antistatic coating composition comprising 2 to 30 mg /
It is preferable that m ² , the silicone oil (C) is 1-25 mg / m ² , and the water-soluble colorant (D) is 0.05-5 μg / m ² . The coating amount of the antistatic composition comprising (A) and (B) is poor in antistatic performance and transparency,
Determined from sheet and film properties such as stickiness,
(A) + (B) The coating amount of the antistatic composition is 30 mg / m
If it exceeds ² , it is an area where problems such as deterioration of transparency of the sheet / film, stickiness, blocking and the like occur.
On the other hand, if it is less than 2 mg / m ^2, it is difficult to obtain the desired antistatic performance. Furthermore, the friction band voltage lowering effect,
From the viewpoint of balancing the antistatic performance measured by the half-life of the charged voltage at a lower humidity (about 20 ° C. and a relative humidity of about 20%), the coating amount is more preferably 3 to 30 mg / m ² , and furthermore, When the sheet / film of the present invention is subjected to secondary molding and used for containers, etc., it is necessary to prevent the generation of static electricity due to friction between the molding machine and the sheet / film during molding, and to prevent contamination of the mold, hot plate, etc. of the secondary molding machine. From the viewpoint of prevention (generated by transfer of a coating material coated on a sheet or film to a hot plate or a mold), the coating amount is more preferably 3 to 20 mg / m ² .

The coating amount of the silicone oil (C) is determined in consideration of imparting the sheet with slipperiness, stickiness of the sheet, whitening of the sheet, and the like.
less than mg / m ^2, an area can not be obtained sliding property improving effect by silicone oil, if it exceeds 25 mg / m ^2, stickiness and the sheet or film with a silicone oil, due to the influence of the emulsifier in the silicone emulsion This is an area where whitening starts to occur. Further, when a mixture of the antistatic coating composition and the silicone oil is coated on a biaxially stretched styrene resin sheet which is secondarily formed by a hot plate pressure forming method, a releasing effect from the molding machine and a peeling of the molded product are required. It is more preferable to adjust the silicone oil coating amount to 4 to 18 mg / m ² from the viewpoint of the effect and prevention of contamination of the hot plate and the mold of the molding machine.

The amount of the water-soluble blue colorant (D) is determined by the change in the color tone of the sheet or film due to the coating of the fatty acid amide (A). Of the water-soluble blue colorant is less than 0.05 μg / m 2, the above-mentioned change in color tone is insufficient. If the concentration exceeds 5 μg / m2, the color of the colorant is too strong, and the commercial value of the sheet, film, or molded product from the sheet is adversely affected by the color of the colorant. This is an area that may be reduced. From the viewpoint of highly reducing the change in color tone of the sheet due to the coating of the antistatic composition, the coating amount of the coloring agent (D) is more preferably 0.1 to 3 μg / m 2, and still more preferably 0.2 to 2 μg / m 2. is there.

The sheet of the present invention coated with an antistatic composition of a fatty acid amide (A) and a block copolymer (B)
The film is characterized in that side effects such as deterioration of transparency and stickiness are suppressed, and the effect of lowering a frictional charged voltage is large. For this reason, it is possible to reduce the amount of static electricity generated during the use of sheets and films under low humidity conditions, for example, in a secondary molding machine, a packaging machine, an envelope window machine, etc., and to reduce the charged voltage. Even if the half-life is somewhat longer (about 120 to 300 seconds), the absolute level of generation of static electricity (charged voltage) is low, and there is little practical problem. On the other hand, when (A) and (B) used in the present invention are used alone (see Comparative Examples 9, 10, and 11) at a level at which stickiness and transparency do not deteriorate in sheets and films, When a surfactant is used (see Comparative Examples 12 and 13), the triboelectric voltage tends to increase. For this reason, sheets and films coated with a surfactant other than those used in the present invention, even if the half-life of the charged voltage is at a level close to the sheets and films of the present invention, a secondary molding machine, a packaging machine, At the time of practical use in an envelope window wrapping machine or the like, the amount of static electricity generated and accumulated due to friction between various machines and sheets / films often makes a large difference. The great effect of the resin sheet or film of the present invention is exhibited by suppressing the triboelectric charging to a low level.

The coating of the component (D), which alleviates the deterioration of the color tone of the sheet due to the coating of the component (A), involves mixing pigments and dyes into the resin, which is conventionally used for correcting the color tone of the resin. Compared with the above, there is a feature that a color tone improving effect can be obtained with a small amount. For example, as in Comparative Example 2 described below, an anthraquinone-based blue dye (C.I.
B. 97) is mixed with 25 ppb of polystyrene biaxially stretched sheet (0.21 mm thick), (A) + (B) 6 mg / m ^{2 of} antistatic composition and silicone oil (C)
When the molded articles obtained from the sheets coated with 12 mg / m ² are stacked, the end face turns brown and the effect of the anthraquinone dye cannot be obtained. On the other hand, the same amount of (A), (B), (C) and brilliant blue FCF as the blue colorant (D) were added to the above biaxially stretched polystyrene sheet containing no dye at 0.6 μg / when stacking the resulting molded article from the m ² coated sheet, the end face becomes pale milky, (a) the effect of discoloration due to component coating is relaxed is obtained (example 1). What should be noted here is
0.6 μg of coloring agent per m ² (about 220 g) of a sheet having a thickness of 0.21 mm, that is, about 2.7 parts by weight of resin.
The point is that the color tone improving effect is obtained with a very small amount of ppb.

The composition comprising the antistatic coating composition, silicone oil (C) and colorant (D) is as follows:
Other coating agents, for example, antifoggants (sucrose fatty acid esters, polyglycerin fatty acid esters, mixtures thereof, etc.), lubricants, viscosity modifiers (methyl cellulose,
Carbomethoxycellulose, casein, alginate,
Polyacrylates, etc.) and other surfactants can be mixed and coated on sheets and films.
The sheet / film of the present invention is a sheet / film coated on both sides or one surface with a mixed composition comprising (A) + (B) an antistatic agent composition, silicone oil (C) and coloring agent (D). is there.

In the case of a sheet / film having one surface coated with a mixed composition comprising the (A) + (B) antistatic agent composition, silicone oil (C) and colorant (D), the opposite surface is (1): Silicone oil (silicone emulsion) is coated. (2): An antifogging agent (sucrose fatty acid ester, polyglycerin fatty acid ester, a mixture thereof, etc.) is coated. (3): A mixture of a silicone oil (silicone emulsion) and an antifogging agent is coated. (4): Coating with (A) + (B) antistatic compositions having different compositions. (5): Other known surfactants, coating agents and the like are coated. (6): Perform corona treatment (the coating agent may or may not be coated). (7): There is no particular limitation, such as no processing.

When the sheet / film of the present invention is secondarily formed into a container and used, the above-mentioned forms (2) and (3) are preferable. In the case of the form (2), it is preferable to coat the antifogging agent with 4 to 40 mg / m ² , and in the case of the form (3), the coating amount of the silicone oil is 1 to 25 mg / m ² , It is preferable to adjust the coating amount so as to be ⁴ to 40 mg / m ² before coating.

The method for producing the resin sheet / film of the present invention is not particularly limited. For example, the (A) + (B) antistatic composition adjusted to an appropriate concentration and a silicone oil (preferably a silicone emulsion or aqueous solution) Rolls, air knife coaters, knife coaters, spray coaters, gravure roll coaters, hand coaters, and the like. It can be performed by a method of drying after coating on at least one surface. The drying is not particularly limited, but a hot air drier is generally used. In particular, from the viewpoint of improving the uniformity of the coating film, it is preferable to apply an antistatic composition or the like by the above method after corona treatment of the sheet / film. For example, when applied to a styrene-based resin sheet / film, the surface of the sheet / film is subjected to a corona treatment so that the contact angle with water is 75 to 40 °, and then the antistatic composition is prepared by the above method or the like. Is preferred because the coating film becomes uniform when applied. The upper limit of the contact angle with water is a value for improving the uniformity of the coating film, and the lower limit of the contact angle is a value for preventing blocking when the sheet is wound in a roll.

For the quantitative analysis of the antistatic agent composition and the silicone oil coated on the sheet / film manufactured as described above, a calibration curve is prepared from the sheet / film of which the coating amount is known, and IR analysis (ATR method) is performed. The method can be carried out by a method or a method in which the coating is washed and recovered from the sheet or film with an appropriate solvent, and then separated and analyzed by cam chromatography, GPC or the like. In the case of a styrene-based resin sheet / film, the silicone oil is analyzed by IR analysis (ATR method) from the characteristic absorption (1263 cm ^-1 ) of the silicone oil, and the antistatic agent composition is obtained by washing the sheet / film with methanol or ethanol. After collecting the washing solution, it is preferable to separate and analyze the solution by column chromatography. In addition, when the mixing ratio of each component in the coating is known, it is also possible to perform quantitative analysis of any one of the components and obtain the value by calculation.

The resin constituting the base sheet / film of the resin sheet / film coated with the antistatic agent composition of the present invention includes polystyrene resin, polyester resin, polyvinyl chloride resin, polypropylene resin and the like.
In general, various packaging containers obtained by secondary forming the sheet,
There is no particular limitation on the range of the transparent material used for the packaging film, the envelope window covering film and the like, but a styrene resin sheet / film is preferable from the viewpoint of transparency and rigidity.
Even if the styrene resin sheet / film is not stretched,
It may be uniaxially or biaxially stretched, or may be a multi-layer sheet made of a known styrene-based resin, and may be appropriately selected depending on the desired physical properties. Preferably, it is a biaxially stretched styrene resin sheet / film. The stretching may be performed by a known tenter method, bubble method, or the like, and is not particularly limited.
The styrene resin used in the styrene resin sheet / film includes general-purpose polystyrene (GPPS),
Resins containing 50% by weight or more of styrene, such as high-impact polystyrene (HIPS), styrene-conjugated diene (butadiene, isoprene, etc.) copolymer, styrene- (meth) acrylic acid (ester) copolymer, and mixtures thereof. is there.

[0027]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of examples. Here, the effect of the sheet / film of the present invention will be described for an example of a biaxially stretched polystyrene sheet which is one of the embodiments, but the present invention is not limited to this use. Confirmation of coating amount in Examples,
And the evaluation method is as follows. (1) Confirmation of coating amount Using FTIR, the infrared absorption spectrum of the sheet treated surface was measured by the ATR method (ATR crystal ZnSe, 16 times of integration), and a silicone oil of styrene (dimethylpolysiloxane) near 1263 cm ^-1 was measured. Absorption and 13
The silicone oil coverage was determined from the ratio of the absorbance of styrene to the absorbance of styrene near 72 cm ^-1 . Further, the coating amount of the antistatic composition is shown in Tables 1 and 2 based on the amount of silicone oil.
It was calculated from the addition ratio of the mixed composition described.

(2) Evaluation method (a) Triboelectricity In conformity with JIS L1094, a friction material having a thickness of 0.0
Using a 2 mm stainless steel tape (manufactured by Irie Trading Corporation), the friction band voltage of the sheet-treated surface was measured under the environmental conditions of a temperature of 20 ° C. and a humidity of 20% RH. ：: less than 200 V ：: less than 400 V △: less than 600 V ×: 600 V or more (b) Half life According to JIS L1094, temperature 20 ° C., humidity 20%
The half-life of the charged voltage on the sheet processing surface was measured under the RH environmental conditions, and the results were shown in the following four stages. ◎: less than 120 seconds ○: less than 300 seconds △: less than 600 seconds ×: more than 600 seconds (c) Slipperity Contact area 64 mm × 1 according to JIS K-7125
A stainless steel slide with a mirror surface of 00 mm (600 mm
g), the dynamic friction coefficient of the sheet-treated surface was measured under environmental conditions of a temperature of 23 ° C. and a humidity of 50% RH, and the results were shown in the following four stages. ◎: less than 0.15 ：: less than 0.20 △: less than 0.25 ×: 0.25 or more,

(D) Transparency The haze was measured in accordance with ASTM-D1003, and the results were shown in the following four stages. ◎: less than 1.5% ○: less than 2.0% △: less than 2.5% ×: 2.5 or more, (e) Stickiness ・ The stickiness when the sheet processing surface is pressed with a finger and separated is the following. In four stages. ◎: no stickiness ○: moist △:
X: Slightly sticky x: Sticky (f) Sheet color standard color sample of acceptable level for the color of the end face of the sheet roll manufactured in Production Example 3 below and the end face of a molded product (stacked 100 food packs) from the sheet The test sheets were visually compared under the same conditions, and those having the same color tone were regarded as acceptable (◎), and those having a distinctly brownish, yellow, yellow-brown, or blue color were rejected (×). did.

The used antistatic agent, silicone oil and coloring agent are as follows. Fatty acid amide (A-1): condensation product of coconut oil fatty acid (1 mol) and diethanolamide (2 mol) Fatty acid amide (A-2): coconut oil fatty acid (1 mol) and diethanolamide (1 mol) POE.POP block polymer (B-1): polyoxyethylene polyoxypropylene block copolymer, average molecular weight about 15,000, EO hydrophilic group ratio 80 wt%, POE.POP block polymer (B- 2): Polyoxyethylene polyoxypropylene block copolymer, average molecular weight of about 1300, EO hydrophilic group ratio of 50 wt%, POE / POP block polymer (B-3): polyoxyethylene polyoxypropylene block copolymer, average molecular weight About 8000, EO hydrophilic group ratio 85 wt%,

POE fatty acid ester (X-1): polyoxyethylene (40 mol) laurate, POE sorbitan laurate (X-2): polyoxyethylene (20 mol) sorbitan laurate, silicone oil (C- 1): Silicone emulsion containing 30% by weight of dimethylpolysiloxane component, viscosity 50
00 cs, silicone oil (C-2): water-soluble polyether-modified silicone having a viscosity of 400 cs modified with polyoxyethylene, coloring agent (D): brilliant blue FCF (food blue 1)
issue),

[0032]

[Stretched sheet production example 1] Polystyrene (GPPS) is supplied to an extruder, extruded from a T-die, stretched 2.8 times vertically by a speed ratio between rolls, and then stretched 3.0 times horizontally with a tenter. A 0.21 mm biaxially oriented polystyrene sheet was obtained.

[Stretched sheet production example 2] 25p of anthraquinone blue dye (CI Solvent B.97) was added during polymerization.
A biaxially stretched sheet was obtained in the same manner as in Stretched Sheet Production Example 1 except that pb-added polystyrene (GPPS) was used.

[Stretched Sheet Production Example 3] The sheet produced in Stretched Sheet Production Example 1 was subjected to corona treatment so that the contact angle with pure water was 45 to 50 °, and then 0.6% by weight of silicone oil (a). Spray coat the aqueous solution (wet coverage 2g / m
² ) and a drying treatment was performed to obtain a sheet (rolled roll) for comparing the color tone of the sheet and the molded product.

[0033]

Example 1 The sheet prepared in Production Example 1 of stretched sheet was subjected to corona treatment so that the contact angle with pure water was 45 to 50 °, and then 0.1% of fatty acid alkanolamide (A-1) was obtained.
2% by weight of the polyoxyethylene / polyoxypropylene (POE / POP) block polymer (B-1).
1% by weight, 0.6% by weight of silicone oil (C-1)
And an aqueous solution composition containing 0.3 ppm of the colorant (D) is coated with a spray coater (coating amount at wet time: 2 g / m ² ), dried, and coated with an antistatic coating composition-coated sheet (roll on a roll) I got The obtained sheet is coated with 12 mg / m ^{2 of} silicone oil (antistatic composition: 6 mg / m ² , colorant: 0.6 μg)
/ M ² ). The frictional voltage, half-life, slipperiness, transparency, and stickiness of the obtained sheet were all at the level of “」 ”. Further, the end surface of the obtained sheet was pale milky white, and had a color tone almost equal to that of the sheet of Stretched Sheet Production Example 3. Further, the sheet of the stretched sheet production example 3 and the sheet of the example 1 were each formed into a food pack by a hot plate press forming machine. The end faces when 100 molded food packs were punched and stacked were pale milky white with no difference between the sheet of Example 1 and the sheet of Production Example 3 of stretched sheet. In addition, the contact angle of the sheet used the solid surface energy analyzer CA-XE manufactured by Kyowa Interface Science Co., Ltd.

[0034]

Comparative Example 1 An aqueous solution composition supplied to a spray coater was prepared by adding 0.2% by weight of fatty acid alkanolamide (A-1) to polyoxyethylene / polyoxypropylene (PO).
(E.POP) The procedure was the same as in Example 1, except that the block polymer (B-1) was replaced by 0.1% by weight and the silicone oil (C-1) was replaced by 0.6% by weight.

Comparative Example 2 The same operation as in Comparative Example 1 was carried out except that the sheet to be used was changed to the sheet of the stretched sheet production example 2.

Comparative Example 3 0.2% by weight of fatty acid alkanolamide (A-1) was added to an aqueous solution composition supplied to a spray coater, and polyoxyethylene / polyoxypropylene (PO) was used.
Example 1 except that 0.1% by weight of (E.POP) block polymer (B-1), 0.6% by weight of silicone oil (C-1) and 10 ppm of colorant (D) were used. Performed similarly.

Comparative Examples 1 and 2 (both coloring agents: 0)
(μg / m ² coating), the triboelectric voltage, half-life, slipperiness, transparency and stickiness were all at the level of “◎”. However, in both sheets, the end face of the sheet roll had a brownish tint and was clearly inferior in commercial value to the end face of the sheet roll of the stretched sheet production example 3. In addition, when these sheets were formed into a food pack in the same manner as in Example 1, and 100 sheets were stacked, the end faces of the food packs obtained from the sheets of Comparative Examples 1 and 2 were brownish, and the sheets of Example 1 and The commercial value was clearly inferior to the food pack obtained from the sheet of Stretched Sheet Production Example 3 (standard color tone comparison sheet: acceptable level color tone). From these results, it can be seen that coating with the water-soluble blue colorant (D) can prevent deterioration of the color tone of sheets and molded articles. It can also be seen that the conventional addition of a dye to a resin has little effect on alleviation of color deterioration caused by the coating. Comparative Example 3 (colorant: 20 μg / m ² coating)
The end face of the sheet roll was apparently bluish green, and was too colored, resulting in inferior commercial value.

[0036]

Examples 2 to 13 The same procedure as in Example 1 was carried out except that the concentration ratio of the liquid supplied to the spray coater was changed to the ratio shown in Table 1. Table 2 shows the physical properties of each sheet. The end face of each sheet roll is milky white to pale greenish white, and has the same color tone as the sheet of Example 1 and the sheet of Sheet Production Example 3, or is more preferable than the sheets of Comparative Examples 1 and 2 (high commercial value). ) Color tone.

[0037]

Comparative Examples 4 to 8 A sheet was obtained in the same manner as in Example 1 except that the concentration ratio of the liquid supplied to the spray coater was adjusted at the ratio shown in Table 3. Table 4 shows the coating amounts of these sheets and the evaluation results of physical properties. Comparative Examples 4 to 8 are cases where the composition ratio of the fatty acid alkanolamide (A) to the POE / POP block polymer (B) and the coating amount of each component are out of the composition range of the present invention. In these examples, it can be seen that the balance between the antistatic property, the transparency of the sheet, the slip property, and the stickiness is poor.

Comparative Examples 9 to 13 The same procedures as in Example 1 were carried out except that the composition of the liquid supplied to the spray coater was as shown in Table 5,
I got a sheet. Table 6 shows the coating amounts of these sheets and the evaluation results of physical properties.

[0038]

[Table 1] (Note) Unit:% by weight, provided that the colorant (D) is ppm.

[0039]

[Table 2] (Note) (A): fatty acid amide, (B): polyoxyethylene-polyoxypropylene block copolymer, (C): silicone oil, (D): blue pigment,

[0040]

[Table 3] (Note) Unit:% by weight, provided that the colorant (D) is ppm.

[0041]

[Table 4] (Note) (A): fatty acid amide, (B): polyoxyethylene-polyoxypropylene block copolymer, (C): silicone oil, (D): blue pigment,

[0042]

[Table 5] (Note) Unit:% by weight, provided that the colorant (D) is ppm.

[0043]

[Table 6] (Note) (A): fatty acid amide, (B): polyoxyethylene-polyoxypropylene block copolymer, (C): silicone oil, (D): blue pigment,

[0044]

The resin sheet or film coated with the antistatic coating composition of the present invention is characterized in that a fatty acid amide is used in combination with a polyoxyethylene polyblock polymer and that a blue colorant is simultaneously coated with silicone oil. There are features. This has an excellent antistatic effect (a good half-life of charged voltage and a reduced effect of frictional charged voltage even under low humidity of 30% RH or less) which could not be realized by itself, and has good slipperiness. , Sheets and molded articles without color tone deterioration. Therefore, it can be suitably used as a transparent resin sheet / film used for various packaging containers, packaging films, envelope window covering films and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F006 AA12 AA15 AA17 AA35 AB35 AB39 AB52 AB65 BA07 CA07 DA04 EA03 4F100 AH03B AH03H AK12A AK52C AK54B AL02B AL05B BA03 BA07 BA10B BA10C CA13C EJ38A GB16 YG03B

Claims (4)

[Claims] 1. An antistatic composition comprising a fatty acid amide (A), a block copolymer (B) comprising polyoxyethylene and polyoxypropylene, a silicone oil (C), and a water-soluble blue colorant (D) Characterized in that at least one surface of the resin sheet or film is coated so as to satisfy the following (1), (2), (3) and (4): . (1): The weight mixing ratio of (A) in the antistatic composition comprising (A) and (B) is 0.90 ≧ (A) / ｛(A) +
(B) The relationship of｝ ≧ 0.40 is satisfied. (2): The coating amount of the antistatic composition comprising (A) and (B) is ² to 30 mg / m ² . (3): The coating amount of the silicone oil (C) is 1 to 25 mg.
/ M ² . (4): The coating amount of the water-soluble blue colorant (D) is 0.05 to 5
μg / m ² . 2. The method according to claim 1, wherein the aliphatic amide (A) is C8 to C1.
The resin sheet or film according to claim 1, wherein the resin sheet or film is a condensation product of a fatty acid of No. 8 and diethanolamine. 3. The water-soluble blue colorant (D) is at least one selected from brilliant blue FCF (edible blue No. 1), indigo carmine (edible blue No. 2) and sodium copper chlorophin. The resin sheet or film according to claim 1 or 2, wherein 4. The resin sheet or film according to claim 1, wherein the resin sheet or film is a biaxially stretched styrene resin sheet or film.