JPS62180384A - Label - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a label having antistatic properties, and in particular, to a label having easy sliding properties and antistatic properties that do not change with humidity.

[Conventional technology]

Conventionally, as a method of imparting antistatic properties and slipping properties to labels made of plastic films, various antistatic agents have been added before film formation, and in addition, various inorganic particles have been added to impart slipping properties. Methods such as kneading metal or forming a thin metal film on the surface of the film using methods such as vapor deposition and sputtering have been used.

[Problem that the invention seeks to solve]

However, when an antistatic agent is mixed in, although it is relatively inexpensive, it has the disadvantages that transparency is impaired due to the antistatic agent bleeding out, the antistatic effect decreases over time, and it is affected by humidity. Moreover, when inorganic particles are kneaded in to impart slipperiness, there is a drawback that transparency deteriorates.

On the other hand, when a metal thin film is formed by a method such as vapor deposition or sputtering, it has drawbacks such as lack of slipperiness and being expensive.

An object of the present invention is to provide an inexpensive label that does not have the above-mentioned drawbacks, that is, has easy slipping properties and does not change its banding resistance due to humidity.

[Means for solving problems]

In the present invention, on at least one surface, interlayer ions with a carbon number of 6
Weight ratio (A/B) of swellable inorganic layered silicate (A) and water-soluble resin (B) with the following aliphatic ammonium, Na %Ll or A12 1/1000 to 2
The present invention relates to a label in which an adhesive layer is provided on the surface of a plastic film having an anti-soldering layer made of a mixture of 1.

As the base material of the plastic film in the invention,
Any known plastic film may be used, whether simple, composite, stretched or unstretched, but typical examples include polyolefin film,
Polystyrene film, polyester film, polycarbonate film, triacetyl cellulose film, cellophane film, polyamide film, polyimide film, polyphenylene sulfide film, polyetherimide film, polyether sulfone film, polysulfone film, polyacrylonitrile film, polyvinyl acetate film, poly Examples include a single substance or a composite such as an ether ether ketone film. Among these, single substances or composites of polyester films (particularly stretched films), polypropylene films, polyphenylene sulfide films, and polyimide films are preferable because of their small thermal dimensional changes and high rigidity. The thickness of the plastic film is not particularly limited, but is usually 0.5 μm or more and 500 μIn.
or less, and from the viewpoint of coating properties, 2μm or more 250
Particularly preferred is one below μm. When using a composite film, the number of layers or method is not particularly limited, but
Usually, when stretching is necessary, it is done by extrusion method, extrusion lamination method on base film, or lamination method using various adhesives, regardless of before or after stretching.
Compounded.

The essence of the present invention is to apply a dispersion liquid of a predetermined composition to the surface of such a plastic film. The first component incorporated into the dispersion is a swellable inorganic layered silicate. Here, the term "swellable" refers to an inorganic layered silicic acid that has the property of "swelling" by coordinating water between its layers. Structurally, the swellable inorganic layered silicate used in the present invention is a phyllosilicate in which the ratio of Si to 0 of Si04 tetrahedrons is theoretically 2:5, and the crystal unit cell is turned around in the thickness direction. It has a structure, and a typical example thereof can be represented by a chemical formula as follows.

Wo, 3-+, + Xl, O40,2 (Si3.5-4
．． 5010) Z+, s-2,2 where W: is an interlayer ion, and is a cationic ion of one or more yuzu.

X: Ion at octahedral position, Mg2+ or Mg2+
Part iLi”, Fe2+, N12+, yl n2+,
An ion substituted with at least one god ion selected from the group consisting of At3+ and F3+.

0: Oxygen.

z: One or two yuzu ions selected from F- or OH-.

In addition, in the present invention, 8+ at the above-mentioned tetrahedral position is Ge
Alternatively, some of these may be replaced with At 2 , Fe, B 2 , etc., and the swellable inorganic layered silicate referred to in the present invention also includes these.

Specific examples of these include clay-based materials such as natural products such as montmorillonite and vermicinilite, and synthetic products such as tetrasilicic mica, taeniolite, and hectorite, which are synthesized by melting or hydrothermally and having the above general formula, and mica. There are minerals.

Among these, synthetic materials are particularly preferred because they contain fewer impurities and have a uniform composition, resulting in uniform crystals.Among these, WX is preferred because it has excellent crystal flatness and a large crystal size. -0,1~X+ 0.1 Mg2B-X-3,x-
xL i) ((S i 3.+5-4.0010)F
l, 8-2.0 or Wx-ol-x+o,t Mg2
．． 8-X-3,2-X L i z (S i 33H
4016) (OH)1. 4th g (where x = 0.
8 to 1.2) are preferred. Also, between layers (however, R
1 is an alkyl group having 1 to 6 carbon atoms, and R4 is hydrogen or an alkyl group having 1 to 3 carbon atoms.

Among them, especially Ag+, L1+ or R1-NH3
'' (where Rt is an alkyl group having 6 or less carbon atoms), more preferably L, R1-NH3'', or a combination of both is preferred because the antistatic effect is significant.

The size of the swellable inorganic layered silicate used in the present invention is not particularly limited, but the average particle size measured by a sedimentation method is 0-OL"m=15μtn, preferably 0.1μ
tn-8prn, more preferably 0.15 μm to 3 μm
When n is in the range, it is preferable because a uniform layer can be obtained. If the thickness of 50mm, preferably 80%, more preferably 90% of all particles is 800λ or less, preferably 4ooX or less, and even more preferably 100X or less, the film surface will be smooth and the product will be more compact. More preferred. A method for obtaining such a thin film is described in Japanese Patent Application No. 58-97557.

In the present invention, the water-soluble resin refers to a resin that exhibits water solubility when forming a dispersion with a silicate and is a polymer (crosslinked polymer or non-crosslinked polymer) in the surface layer of the final antistatic label. Essentially, any one is fine. Structurally, organic polymers or polymer-forming substances having one or more highly hydrophilic polar groups as shown below are preferred.

Nonionic: -OH, -0-1-CN, -CONH
.

Typical water-soluble resins include silane coupling agents, titanium coupling agents, water-soluble acrylic, water-soluble polyester, water-soluble epoxy, water-soluble polyamide, polyvinyl alcohol, polyacrylamide, polyethylene oxide, vinyl acetate copolymer, and polyvinyl. Examples include resins such as pyrrolidone or mixtures thereof.

The water-soluble resin used in the present invention has a softening temperature of 50°C or higher, preferably 80°C or higher, more preferably 120°C or higher after dehydration and drying, and has a softening temperature of 50% by weight or higher, preferably Fl8
It is preferable that it accounts for 0 weight or more, more preferably 90 weight or more. Of course, a curable resin may be used as the water-soluble resin. These resins can be selected appropriately depending on the base film used, but for example, when polyester is used as the base material, silane coupling agents, titanium coupling agents, water bath acrylic,
Water-soluble polyester is preferred from the viewpoint of adhesive properties. Further, when using polyolefin as the base material, titanium coupling, silane coupling agent, and water-soluble acrylic are suitable from the viewpoint of adhesive properties.

't7'c,t! When using phenylene sulfide, polyether ether ketone, polysulfone, polyether sulfone, or polyimide as a base material, a silane coupling agent and titanium coupling agent 1 are suitable.

The silane coupling agent referred to in the present invention is not particularly limited, but representative examples include amino-based silane coupling agent, vinyl-based or methacryloxy-based silane coupling agent, epoxy-based silane coupling agent, and methyl-based silane coupling agent. Examples include chloro-based silane coupling agents, anilino-based silane coupling agents, and mercapto-based silane coupling agents. The silane coupling agent may be selected as appropriate depending on the type of base material, but for example, when applying to a polyester base material such as polyethylene terephthalate or polycarbonate, an epoxy-based silane coupling agent with the following structure or A chloro-based silane coupling agent having the following structure is particularly suitable from the viewpoint of thickening during application or from the viewpoint of adhesion to a substrate.

However, m=Q or 1, n=an integer from 1 to 10, R'=
A hydrocarbon residue selected from an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a cyclohexyl group; ``i'' indicates a hydrocarbon residue selected from hydrogen to an alkyl group having 1 to 10 carbon atoms.

Furthermore, when an imide base material, polyphenylene sulfide, or the like is used as the base material, an epoxy silane coupling agent having the same structure as shown above is suitable.

Typical water-soluble polyesters include polyesters copolymerized with at least 20 moles of polyethylene glycol having a degree of polymerization of 2 to 10 and about 8 moles or more of a sulfonic acid metal salt compound having an ester-forming bifunctional group; In a polyester copolymer consisting of dicarboxylic acid and/or its ester-forming derivative and glycol in which the molar ratio of aromatic dicarboxylic acid component to fatty acid dicarboxylic acid component is 10/1 to 1/10, A. Ester-forming alkali metal sulfonate A salt compound with a composition ratio of 3 to 10 moles B based on the total acid component, a composition ratio of 1,4-bis(hydroxyalkoxy)benzene component among glycol components of 5 to 60 moles, an aromatic dicarboxylic acid component and a methylene group number of 4 to The molar ratio of the saturated linear aliphatic dicarboxylic acid component of 8 is 10/1 to 10
/7.5 in a polyester copolymer consisting of dicarboxylic acid and/or its ester-forming derivative and glycol, A, the ester-forming sulfonic acid alkali metal salt compound is 3.5 to 7.5 to the total acid component. Morti B contains 30% diethylene glycol among the glycol components.
Examples include those having a composition ratio of 100 to 100 molar and containing 20 to 1000 pprn of phosphorus in the phosphorus compound relative to the polyester.

When polyester is used as a base material, from the viewpoint of coating properties and adhesive properties, it is necessary to form a dicarboxylic acid and/or its ester in which the molar ratio of the aromatic dicarboxylic acid component and the aliphatic dicarboxylic acid component is 10/1 to 1/10. In a polyester copolymer consisting of a chemical derivative and glycol, A: 3 to 10 mol of an ester-forming alkali metal sulfonic acid salt compound to the total acid component; A composition having a composition ratio of 60 molti or an aromatic dicarboxylic acid component and a methylene group number of 4 to 8
The molar ratio of the aliphatic dicarboxylic acid component is 1
In a polyester copolymer consisting of dicarboxylic acid and/or its ester-forming derivative and glycol consisting of 0/1 to 10/7.5, A, an ester-forming sulfonic acid alkali metal salt compound is added at a ratio of 3% to the total acid component. .5 to 7.5 mole B6 Of the glycol components, diethylene glycol has a composition ratio of 30 to 100 mole and preferably contains 20-xoooppm of phosphorus in the phosphorus compound relative to the polyester.

Typical examples of water-soluble epoxy resins include glycidyl ether epoxy resins, heterocyclic epoxy resins, glycidylamine epoxy resins, and aliphatic epoxy resins.

Further, it is preferable to add a small amount of various surfactants, particularly nonionic and anionic surfactants, usually 10 tres or less, preferably 5 tres or more, to improve transparency. Further, it is more preferable to add a small amount of polyvinyl alcohol (usually 10% or less, preferably 5% or less, preferably 111% or less, 0.01% or more) because the surface gloss or transparency is further improved.

In the present invention, the mixing ratio (B/A) of the swellable inorganic layered silicate (A) and the water-soluble resin (B) is from 1/1000 to
It is necessary to set it to 2/1, preferably 11500 to 1/3, more preferably 1/200 to 1/10. This is 1/1
If it is less than 000, the band'1 prevention effect is lost, which is undesirable. On the other hand, if it is more than 2/1, creases will relatively easily occur within the film surface layer, which is undesirable.

The sticky layer in the present invention is not particularly limited, but includes (1) polymeric materials such as natural rubber, styrene-butadiene rubber, polyimbutylene, polychloroprene, polyacrylate rubber, and polyvinyl ether rubber; Vinyl chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl butyral, chlorinated rubber, m-compounds of plasticizers with polymeric substances such as rubber chloride, (3) rosin, rosin ester, coumaron resin, terpene resin, Tackifiers such as hydrocarbon resins and oil-soluble phenolic resins, (4) various additives such as fillers, pigments, anti-aging agents, and stabilizers;
) to (4) can be cited as representative examples.

Usually, the swellable inorganic layered silicate (A) is dispersed in water or a water-soluble organic solvent to create a dispersion system of fine particles in a non-agglomerated state, and then a water-soluble resin is added to the dispersion system to satisfy the above ratio.
The dispersion thus obtained is coated on at least one surface of a plastic film. As the solvent, water, alcohol, or a mixture thereof is preferable.

The base film may be subjected to corona discharge treatment in air or other various atmospheres, if necessary. Anchor treatment may be performed using a known anchor treatment agent such as urethane resin or epoxy resin, but this is usually not necessary. Coating is performed using known methods such as gravure coating, reverse coating, and spray coating, and then
Dry at ~250°C for about 1 second to 15 minutes. It should be noted that other components may be appropriately mixed into the dispersion within a range that does not impair the characteristics of the present invention. The coating may be applied to one or both sides of the plastic film, either over the entire surface, in stripes, or in sections.

The thickness of the coating layer is not particularly limited, but is usually 10 μm or less, preferably 5 μm or less, =V preferably 1 μm or less, particularly preferably 0.5 μm or less, and 0.01 μm or more.

Furthermore, the adhesive layer is usually 0.2 to 20 μm, preferably 0.
．． It is assumed that the thickness is 5 to 5 μm. Further, if necessary, a release layer may be further provided on the adhesive layer side or a release treatment may be performed on the opposite side before use. In addition, before forming the antistatic layer, printing may be performed regardless of #, a resin layer may be provided for providing gas barrier properties, coloring, or other purposes, bonding with metal foil, vapor deposition, sputtering, etc. It may also be used after forming a metal thin film. Further, double boss processing may be applied.

The antistatic property of the film thus obtained can be varied depending on the application, but usually the surface resistivity is 10 12 Ω or less, more 10 11 or less, and even 10' or less, regardless of whether it is dried or not.

The slipperiness can also be changed as appropriate, but the static friction coefficient of the surface is usually 0.5 or less, more preferably 0.45 or less.

For antistatic labels such as those of the present invention, Table 111j
Roughness Ra) is 0.4 μrn or less, preferably 0.05 μrn
A value of rn or less is particularly suitable because it provides a film with improved transparency and gloss.

Application #1c of the label of the present invention is not particularly limited, but it is suitable for use as a label for displaying name, price, quality, etc., for sealing various stickers on cans, for surface protection, or for pasting paper or film.

[Action/effect of the invention]

In the present invention, since a swellable inorganic layered silicate is used, good quality can be obtained just by providing an extremely thin layer, and the following effects are exhibited.

(υ It is possible to obtain a stable antistatic effect that does not change with time or humidity.

■ It is transparent.

(3) Easy to slip.

[Characteristics measurement method, evaluation criteria]

The force method and i'F value standard for measuring properties in the present invention are as follows.

(1) Surface resistivity: Measured using a super megohmmeter for a sample left in a room at 20°C and 65SRH for 8 hours (shown as room temperature) and sample C dried in a vacuum dryer at 120°C (shown as after drying). did.

(2) Peel the coating layer mainly composed of inorganic layered silicate onto a commercially available cellophane adhesive tape by 90° from K. If the adhesion strength to the base material is less than 1, the adhesive strength to the base material is "○", and if the adhesive strength is 40 or more, it is rated "○".
×”.

(2) Static friction coefficient μs: Measured using a slip tester according to ASTM-D-1894B-63.

(4) WD-No.: 1 sample 90tWI” in the room
After leaving it for several months, I sprinkled 100 Me white morundum on it, and the weight of white morundum stuck to it due to static electricity! (2) was designated as the measurement WD-No.

Next, embodiments of the present invention will be described based on Examples.

Examples 1 to 4, Comparative Examples 1 to 2 After corona discharge treatment was performed on a base film made of a polyethylene terephthalate biaxially stretched film having a thickness of 100 μm, an antistatic layer having the following composition was applied for 10 times. % sol and applied to both sides to a thickness of 0.1 μm after drying. However, drying was performed in hot air at 150° C. for 2 minutes.

[Antistatic composition]

Silicate (A): W MgzLi (814()1
6) F2W: CH3-(CH2)3-MH3 (abbreviated as phtheramine TN) Watertight resin (B): polyester copolymer, but as acid components 80 mol of terephthal, 20 mol of 5-sulfondium inphthalic acid Ethylene glycol was used as the glycol component, but the mixing ratio is shown in the table.

Afterwards, as an adhesive layer, acrylic ester (Soken Chemical Co., Ltd.)
l! 8! 3μ of SK Dyne 1501B) was applied and its physical properties were evaluated. As shown in the table, in the case of the range of the present invention, the slipperiness is excellent, and at the same time, it has an effect of preventing sagging, and it is difficult for dirt to adhere. - If the strength of the strength bar is not within the invention range, the antistatic property will be insufficient (Comparative Example 1) or the adhesive strength will be insufficient (Comparative Example 2).

Example 5, Comparative Examples 3 to 4 As the silicate (A) of Example 1, a non-swelling silicate (Dimonite POM-7 manufactured by Topie Lai) (Comparative Example 3.4) and Li 34Mgz V3Li y3(5
i40to ) Fz structure layered silicate (Li-
(abbreviated as klT) (Example 5) and its physical properties were investigated. The swollen type silicate described in the present invention exhibits antistatic properties, but the non-swelled silicate exhibits no antistatic property and is therefore unsuitable for use as a label.

Claims (1)

[Claims] At least on one surface, the interlayer ions are aliphatic ammonium having 6 or less carbon atoms, Na^+, Li^+ or Ag^+.
A swellable inorganic layered silicate (A) and a water-soluble resin (B
) A label comprising an adhesive layer provided on one surface of a plastic film having an antistatic layer made of a mixture of A/B at a weight ratio (A/B) of 1/1000 to 2/1.