JPH06234871A - Antistatic laminate and its production - Google Patents

Abstract

PURPOSE:To obtain a laminate retaining stable antistatic effect even at long- term elevated temperatures and humidities, useful for electrical and electronic parts, etc., by coating the surface of a polymeric molded product with an amino group-contg. alkoxysilane, etc., followed by condensation reaction and then treatment under specified conditions. CONSTITUTION:The surface of a polymeric molded product such as a polyethylene terephthalate film is coated with at least one compound selected from amino group-contg. alkoxysilanes, amino group-contg. alkoxytitanium and oligomers thereof followed by condensation reaction of the compound(s) and then treating the surface with a sulfate and/or sulfonate to form a quaternary ammonium salt on the surface layer to bring the surface resistivity to <=10<14>OMEGA/m<2> thus obtaining the objective laminate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate having antistatic ability and a method for producing the same.

[0002]

2. Description of the Related Art Films, sheets, and other polymer moldings are widely used as packaging materials for various articles, electric / electronic parts, and other moldings because of their lightness, heat insulation, and ease of molding. However, they generally have a high electric resistance value, so that they are easily charged with electricity, which hinders the processing work and adsorbs dust and dust to impair the appearance.

As a method of imparting antistatic ability to a polymer molded article, a method of kneading a surfactant into a resin for molding, a method of applying a surfactant to the surface of the molded article, and the like are known. However, these methods cannot suppress the outflow of the surfactant, and the effect cannot be made permanent. Further, in the method of applying a polymer compound containing a polyethylene glycol component such as an acrylic acid ester of polyethylene glycol known as a surfactant in the molecule to the surface of the molded article, since the weather resistance of the polymer compound is low, Hydrolysis occurs at high temperature and high humidity, causing cloudiness,
Phenomena such as film peeling occur.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a laminate having a film capable of always maintaining a stable antistatic effect even under high temperature and high humidity for a long period of time.

[0005]

DISCLOSURE OF THE INVENTION The present invention is derived from at least one compound selected from the group consisting of amino group-containing alkoxysilanes, amino group-containing alkoxytitaniums and oligomers thereof on the surface of a polymer molded article. Formed of a polymer compound containing an amino group, the surface layer of which is coated with a quaternary ammonium salt of sulfuric acid and / or sulfonic acid bound to the polymer compound. Is 10 ¹⁴ Ω / port or less, and a laminate having an antistatic ability is provided.

In the present invention, the surface of a polymer molded article is coated with at least one compound selected from the group consisting of amino group-containing alkoxysilanes, amino group-containing alkoxytitaniums and oligomers thereof, and the compound is subjected to a condensation reaction. After that, the surface of the film is treated with a sulfuric acid ester and / or a sulfonic acid ester to form a quaternary ammonium salt on the surface layer of the film, and the surface resistance value is 10 ¹⁴ Ω /
The present invention provides a method for producing a laminate having an antistatic ability, which is characterized by having a mouth or less.

In the polymer molded article of the present invention, the polymer is not particularly limited, and examples thereof include polyesters and polycarbonates such as polyethylene terephthalate, polyolefins such as polyethylene and polypropylene, polystyrene, polyvinyl chloride and polymethyl. Examples thereof include poly (meth) acrylics such as (meth) acrylate. Examples of the molded products include films, sheets, disk substrates such as optical discs and magnetic discs, and other molded products.

In the present invention, the amino group-containing alkoxysilane has the following general formula (I):

Embedded image (R ¹ O) _4-n Si (CH ₂ CH ₂ CH ₂ NR ² R ³ ) _n (I) (In the formula, R ¹ represents a methyl group, an ethyl group or a propyl group. , R ² and R ³ are each independently a hydrogen atom, an alkyl group or an aminoalkyl group, and n is 1 or 2.

Examples of such compounds include γ-aminopropyltrimethoxysilane, γ-dimethylaminopropyltrimethoxysilane, γ-diethylaminopropyltrimethoxysilane, γ-methylaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Dimethylaminopropyltriethoxysilane, γ-diethylaminopropyltriethoxysilane, γ-methylaminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
A compound such as (aminoethyl) γ-aminopropyltriethoxysilane is preferably used.

Further, the amino group-containing alkoxy titanium is
The following general formula (II)

Embedded image (R ¹ O) _{4 -n} Ti (CH ₂ CH ₂ CH ₂ NR ² R ³ ) _n ... (II) [wherein R ¹ , R ² and R ³ are of the formula (I)] Same definition as above].

Such compounds include γ-aminopropyltrimethoxytitanium, γ-dimethylaminopropyltrimethoxytitanium, γ-diethylaminopropyltrimethoxytitanium, γ-methylaminopropyltrimethoxytitanium, γ-aminopropyltriethoxytitanium, γ-
Dimethylaminopropyltriethoxytitanium, γ-diethylaminopropyltriethoxytitanium, γ-methylaminopropyltriethoxytitanium, N-β (aminoethyl) γ-aminopropyltrimethoxytitanium, N-β
Compounds such as (aminoethyl) γ-aminopropyltriethoxytitanium are preferably used.

Further, as oligomers of these compounds, 2 to 20 mer can be mentioned, and 2 to 10 mer can be preferably used.

In the laminate of the present invention, the thickness of the film of the amino group-containing alkoxysilane, amino group-containing alkoxytitanium or a polymer compound containing an amino group derived from an oligomer thereof is preferably 0.0
It is 1 to 100 μm, and more preferably 0.1 to 20 μm.

In the laminate of the present invention, the surface of the polymer molding is first coated with at least one compound selected from the group consisting of amino group-containing alkoxysilanes, amino group-containing alkoxytitaniums and oligomers thereof, and the compound is prepared. Is produced by a condensation reaction.

At least one compound selected from the group consisting of the above-mentioned amino group-containing alkoxysilanes, amino group-containing alkoxytitaniums and oligomers thereof, may be an organic acid such as acetic acid, hydrochloric acid or sulfuric acid, if necessary. It is used for surface coating of a polymer molded product as an alcohol solution containing, for example, 2 to 80% by weight containing a mineral acid. Examples of alcohols that can be used include lower alcohols such as methanol, ethanol and isopropanol.

Examples of the coating means include known spin coating method, dip coating method, doctor knife coating method, bar coater method, spray coating method and the like.

The compound applied to the surface of the polymer molded product is heated, if necessary, at room temperature to the heat distortion temperature of the polymer molded product for several minutes to 1 hour to cause a condensation reaction to cause a silicate having an amino group. It forms a film of a polymer compound of titanate or titanate.

The laminate of the present invention is then coated on its coating surface with a sulfate ester and / or a sulfonate ester (hereinafter referred to as
It may be produced by treating the surface of the surface with a quaternary ammonium salt to form a quaternary ammonium salt at a surface resistance value of 10 ¹⁴ Ω / well or less.

Examples of the sulfuric acid ester that can be used in the present invention include alkyl sulfuric acid esters such as dimethyl sulfuric acid, diethyl sulfuric acid and dipropyl sulfuric acid, and examples of the sulfonic acid ester include aromatic compounds such as methyl p-toluenesulfonic acid and methyl benzenesulfonic acid. Examples thereof include aliphatic sulfonates such as group sulfonates, methyl methanesulfonate, ethyl methanesulfonate, and methyl propanesulfonate. These quaternizing agents can be used alone or in admixture of two or more.

The treatment of the film surface with a sulfuric acid ester and / or a sulfonic acid ester is carried out by dissolving the quaternizing agent in an organic solvent such as ethanol,
It can be carried out by coating the surface of the film formed by condensation of the compound such as amino group-containing alkoxysilane at room temperature, or by dipping the molded product in the solution. From the viewpoint of workability, the concentration of the solution is preferably 10 to 100% by weight, and particularly preferably 20 to 80% by weight. By this treatment, the amino group present in the surface layer portion of the film formed by condensation of a compound such as an amino group-containing alkoxysilane is reacted with a quaternizing agent, and a quaternary ammonium salt is formed only in the surface layer portion of the film. Can be formed. By allowing the polymer compound in which the quaternary ammonium salt is formed to exist only in the surface layer portion, the adhesiveness between the polymer molded product and the amino group-containing polymer compound forming the film can be improved. The reaction for forming the quaternary ammonium salt is generally carried out at room temperature or under heating. Generally lower than the deformation temperature of polymer moldings, eg 150 ° C for polyester film
Hereinafter, in a polycarbonate disc, the reaction can be promoted by heating to 100 ° C. or lower.

Although it is difficult to precisely specify the amount of the sulfuric acid ester and / or the sulfonic acid ester to be used, at least one selected from the group consisting of the above-mentioned amino group-containing alkoxysilanes, alkoxytitaniums and oligomers thereof. It suffices that the amount is such that the surface of the coating film made of a polymer compound containing an amino group derived from the above compound is uniformly covered.

The laminate of the present invention has a surface resistance value of 10
It should be ¹⁴ Ω / mouth or less. Surface resistance value is 1
If it exceeds 0 ¹⁴ Ω / mouth, the antistatic effect is reduced. The surface resistance of the laminate is determined by the film thickness of the polymer compound containing an amino group, the content of at least one compound selected from the group consisting of aminosilane-containing alkoxysilane, alkoxytitanium and their oligomers, It can be adjusted by the amount of grader used.

Unlike the conventional method, the layered product of the present invention has a quaternary ammonium salt effective for antistatic chemically bonded to the film-constituting components of the surface layer thereof, and can maintain a stable effect for a long period of time. Further, the quaternary ammonium salt is stable even in a high temperature and high humidity atmosphere, and even if it is used in such an atmosphere for a long period of time, its surface resistance value hardly increases. Further, the lower layer of the film is composed only of a high molecular compound containing an amino group, and therefore, a laminate having good adhesiveness to a polymer molded article and good antistatic performance as a whole is realized.

[0024]

The present invention will be described in more detail with reference to the following examples. In the examples, “%” and “part” both represent weight standards. The surface resistance value and the weather resistance test were as follows. Surface resistance value: measured according to JIS K-6911. Weather resistance test: Maintained at 80 ° C. in an atmosphere of 85% RH for 500 hours.

Examples 1 to 6 Polyethylene terephthalate (PET) having a thickness of 50 μm
A film and a polycarbonate (PC) disk having a diameter of 130 mm and a thickness of 1.2 mm for an optical disk were prepared, and a bar coater was used to apply the compound of Table 1 (referred to as a primer in Table 1) on each surface. Apply a 5% ethanol solution to a film thickness of about 5 μm and apply at 80 ° C.
It was heated at 60 minutes for condensation. Thereafter, a 30% ethanol solution of diethyl sulfuric acid was applied by a spin coating method so as to have a film thickness of 1 μm, naturally dried, and then heated in a drying oven at 80 ° C. for about 5 minutes.

The surface resistance value of the laminate thus obtained and the surface resistance value after the weather resistance test were measured. The results are shown in Table 1. In Table 1, P1 and P in the primer column
2 and P3 represent oligomers of isopropyltri (N-aminoethylaminoethyl) titanate, γ-aminopropyltriethoxysilane, and γ-aminopropyltriethoxysilane (average degree of polymerization 3), respectively.

[0027]

[Table 1]

Comparative Examples 1 to 8 The same PET films or PC disks as used in Examples 1 to 6 were treated in the same manner as in Examples 1 to 6 except that the ethanol solution of diethylsulfate was not applied. A laminate was obtained, and the surface resistance value of this laminate was measured. The results are shown in Table 2.

[0029]

[Table 2]

[0030]

INDUSTRIAL APPLICABILITY The present invention can provide a laminate having a film capable of maintaining a stable antistatic effect even under high temperature and high humidity for a long period of time.

[Procedure amendment]

[Submission date] August 13, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Examples 1 to 6 Polyethylene terephthalate (PET) having a thickness of 50 μm
A film and a polycarbonate (PC) disk having a diameter of 130 mm and a thickness of 1.2 mm for an optical disk were prepared, and a bar coater and a spin coater were used to coat the surface of each of the compounds listed in Table 1 (with a primer in Table 1 A 5% ethanol solution (described below) was applied so that the film thickness would be about 0.5 μm, and heated at 80 ° C. for 60 minutes for condensation. Thereafter, a 30% ethanol solution of diethyl sulfuric acid was applied by a spin coating method so as to have a film thickness of 1 μm, naturally dried, and then heated in a drying oven at 80 ° C. for about 5 minutes.

Claims (2)

[Claims] 1. A high molecular weight product containing an amino group derived from at least one compound selected from the group consisting of amino group-containing alkoxysilanes, amino group-containing alkoxytitaniums and oligomers thereof on the surface of a polymer molded article. A film made of a molecular compound, on the surface of which a quaternary ammonium salt of sulfuric acid and / or sulfonic acid bound to the polymer compound is laminated, and the surface resistance value is 10 ¹⁴ Ω / mouth or less A laminate having an antistatic ability, which is characterized by being present. 2. The surface of the polymer molded product is coated with at least one compound selected from the group consisting of amino group-containing alkoxysilanes, amino group-containing alkoxytitaniums and oligomers thereof, and the compound is subjected to a condensation reaction. , The surface of the film is treated with a sulfuric acid ester and / or a sulfonic acid ester to form a quaternary ammonium salt on the surface layer of the film, and the surface resistance value is 10 ¹⁴ Ω / mouth or less. A method for producing a laminate having preventive ability.