JPH02284979A - Removable tacky body - Google Patents

Abstract

PURPOSE:To obtain the subject tacky body without leaving tacky fine particles on the surface of an adherend even if application and peeling are repeated for the adherend by using a vinylidene chloride resin film or a substrate having the vinylidene chloride resin film on a support. CONSTITUTION:The objective tacky body, obtained by coating or applying plural tacky fine particles (e.g. having 5-100mum average particle diameter) consisting essentially of an acrylic or methacrylic acid ester to a vinylidene chloride resin film containing >=5% vinylidene chloride as a substrate or a substrate prepared by laminating the above-mentioned vinylidene chloride resin film onto a support at 0.1-30g/m<2> (expressed in terms of dry weight coating weight and capable of always sufficiently adhering the tacky fine particles to a smooth surface of the vinylidene chloride resin film and eliminating the need for a primer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an adhesive having good removability, and more specifically, the present invention relates to an adhesive that has good removability, and more specifically, even when repeatedly pasted and peeled from an adherend, the adhesive remains The present invention relates to a removable adhesive body in which no sticky fine particles remain on the surface of the adhered body.

[Prior art and its problems] Reprint female adhesive tapes or sheets using adhesive microparticles as constituent elements are already known, but in conventional removable adhesive tapes, etc., When pasting and peeling are performed, there is a problem in that fine particles, which are adhesive components, remain on the adherend. This problem was particularly noticeable when the adherend was diazocopy paper.

Therefore, in order to solve this problem, in order to fix the microparticles on the base material, it is necessary to
Removable adhesive tapes using a binder of about 175 are known (for example, West German patent tube 2.417
．． (See Japanese Utility Model Application No. 312, Japanese Utility Model Application Publication No. 54-60661, and Japanese Utility Model Application Publication No. 55-42881).

However, even when such a binder is used, the adhesion of the microparticles is not sufficient, and when rapid peeling is performed, there is still a problem that the microparticles remain on the adherend.

Furthermore, in order to more firmly adhere microparticles to a base material, a method has been proposed in which an adhesive such as an acrylic emulsion is used as a binder (see US Pat. No. 3,857,731).

However, even with this method, the adhesion of the microparticles is still insufficient, and a new problem has arisen in that not only the microparticles but also the adhesive used as a binder remains on the adherend.

Furthermore, an invention is also known in which adhesive microparticles having a substantially semispherical shape are adhered onto an undercoat layer formed on a base material without using a binder (see Japanese Utility Model Publication No. 57-57394).

However, in this invention, the adhesive microparticles are limited to a substantially hemispherical shape, and are always fixed to the substrate with the curved surface facing outward, that is, with the contact area between the substrate and the microparticles being larger. It has become necessary to

Therefore, the present inventors used an undercoat layer on the base material that can specifically bind to the adhesive microparticles.
It has been found that a base material and adhesive microparticles can be more firmly bonded without using a binder and even when the contact area is extremely small, and this has already been reported in JP-A-62-143988.

However, when such an undercoat layer is used, the process is complicated, as the undercoat must be dissolved in a solvent, coated on the substrate, heated to evaporate the solvent, and then recovered. Also, if the substrate is porous (especially paper), the primer solution will penetrate not only the surface of the substrate but also to some extent into the substrate, so it is necessary to increase the concentration of the primer solution. I needed to. Furthermore, in the case of porous substrates, the contact area with the spherical adhesive is smaller than in the case of ordinary plastic films, causing the problem that adhesive microparticles are difficult to stick to.

Therefore, an object of the present invention is to solve the above-mentioned problem, that is, when the adherend is repeatedly pasted and peeled off, adhesive microparticles remain on the adherend. This was done as a.

[Means for Solving the Problems] As a result of intensive research to solve the above problems, the present inventors have found that vinylidene chloride resin is used as a base material, or a vinylidene chloride resin film is placed on a support. By configuring the base material with , the adhesive microparticles can always be adhered well to the smooth surface of the vinylidene chloride resin, and since there is no need to use an undercoat, it is completely solvent-free. The present invention was achieved by discovering that the desired removable adhesive can be easily obtained.

That is, the removable adhesive body of the present invention is a removable adhesive body having a plurality of adhesive fine particles containing (meth)acrylic acid ester as a main component on a base material, wherein the base material is made from a vinylidene chloride resin film. It is characterized by having a vinylidene chloride resin film on a support.

Examples of the base material according to the present invention include a base material made of vinylidene chloride resin itself, a base material in which a resin layer made of vinylidene chloride resin is laminated on a support described below, and the like.

The vinylidene chloride resin film according to the present invention is a film containing a copolymer containing vinylidene chloride as a component, and the content of vinylidene chloride in the copolymer is preferably 5% or more, more preferably is 10%
Refers to the above copolymer.

In addition, in the vinylidene chloride resin, along with the vinylidene chloride, its monomer components include vinyl chloride,
Acrylonitrile, acrylic esters, etc. can be used.

The content of monomer components other than vinylidene chloride described in n'l is 60 to 10% by weight of the entire vinylidene chloride resin.

The physical properties of the vinylidene chloride resin include high strength (
It is preferable that the film has good water resistance and chemical resistance, and that the film is transparent and impermeable to moisture and gas.

Furthermore, the vinylidene chloride resin may contain 50% by weight or less of a colored pigment, an extender pigment, other additives, and the like.

Examples of the material for the support on which the vinylidene chloride resin film is laminated include fibrous base materials such as paper, cloth, and nonwoven fabric, as well as polyethylene, polypropylene, polyester, polyvinyl chloride, cellulose acetate, polycarbonate, cellophane, and polyfluoride. Smooth films or sheets such as vinylidene chloride sheets or films or composites thereof can be mentioned.

The thickness of the vinylidene chloride resin film is 2 to 50 μm.
is preferred.

The method of providing the vinylidene chloride resin film on the support is not particularly limited as long as it can provide the vinylidene chloride resin film with a predetermined thickness (for example, the method of providing the vinylidene chloride resin film processed into the film shape) A method in which vinylidene resin and the support are pasted through hot rolls whose surfaces have been treated to make them non-adhesive; after applying a solvent-free ultraviolet curing adhesive onto the support and pasting the vinylidene chloride resin film, A method of irradiation or a method of laminating an extruded vinylidene chloride resin film on a base material coated with an adhesive can be adopted.

Furthermore, it is also possible to adopt a method in which finely powdered vinylidene chloride is placed on a support and thermocompression bonded to form a film from the finely powdered vinylidene chloride, which is then laminated onto the support.

The removable adhesive of the present invention has a plurality of adhesive fine particles containing (meth)acrylic acid ester as a main component on such a base material.

The adhesive microparticles used in the present invention are (meta)
It can be produced from an acrylic ester by a known suspension polymerization method, for example, as described in US Pat. No. 3,691,140.

As the (meth)acrylic acid ester, in order to obtain microparticles that are sticky at room temperature, those having a glass transition temperature of usually 10° C. or lower, preferably O'C or lower, are preferred. As acid esters, (meth)acrylic esters usually having a linear or branched alkyl group having 2 to 12 carbon atoms, such as butyl (meth)acrylate, isobutyl (meth)acrylate, 5
ec-butyl (meth)acrylate, hexyl (meth)
Acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, inoctyl (meth)acrylate, isononyl (meth)acrylate,
Decyl (meth)acrylate, methyl (meth)acrylate, tetradecyl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, etc. can be mentioned, and these can be used alone or in combination of two or more. 6 In order to increase the cohesive force of microparticles, when these microparticles are used as an adhesive, a stringing phenomenon occurs when peeled from an adherend, so that the adhesive In order to prevent it from remaining on the alkyl ester monomer, vinyl acetate, styrene, acrylonitrile, methacrylonitrile, etc. can be added in an amount of 50% by weight or less based on the alkyl ester monomer.

The fine particles preferably have an average particle diameter of about 5 to 100 μm. Moreover, the shape is preferably spherical for the purpose of enhancing the re-peeling effect.

The adhesive microparticles described above are applied to the surface of the vinylidene chloride resin of the base material.

To apply the microparticles to the vinylidene chloride resin surface, the microparticles are placed in an organic solvent such as n-hexane, n-heptane, toluene, xylene, ethyl acetate, butyl acetate, or 1-1-lichloroethane. After being dispersed, the coating can be carried out by a conventional coating method using a knife coater, a reverse roll coater, a gravure coater, a screen printer, or a spraying method.

In this case, the coating amount is 0.1 to 3 on dry weight basis.
0 g/rn'', preferably 1-10 g/rrlt.

After applying and adhering the adhesive microparticles in this manner, the adhesive body of the present invention can be obtained by drying at 60 to 120°C for 30 to 300 seconds.

[Function] In the removable adhesive body of the present invention, since the base material is a vinylidene chloride resin film or has a vinylidene chloride resin film on a support, there is The particles are strongly bonded to each other without using a binder.

For this reason, it maintains excellent adhesion to the adherend, and at the same time, even when pasting and peeling are repeated, and even when peeling is performed suddenly, the adhesive microparticles will not stick to the adherend. It also has excellent removability with no residue left on the body.

Therefore, when the adherend is a transparent material such as plastic, stains on the surface will not occur (Also, when the adherend is paper such as diazo copy paper, so-called "paper stain" will not occur). do not have.

In addition, the removable adhesive body of the present invention can also be bonded directly to a base material by thermocompression of vinylidene chloride resin in the form of a film. There is no need for collection equipment.

Furthermore, when the base material has a vinylidene chloride resin film on the support, even if the support is porous, the solution of the undercoat can be The contact area between the base material and the adhesion method (adhesive microparticles) is increased, and the adhesion becomes stronger, without the inconvenience of being sucked into the material.

A further significant feature of the present invention appears when the vinylidene chloride resin film has a large thickness.

In other words, since vinylidene chloride resin is a thermoplastic resin, it melts when heated, so its properties as a hot melt adhesive can be used.6 For example, by thermally laminating a thick vinylidene chloride resin film on paper, , when sticky microparticles are fixed on top of it,
A removable label can be obtained, but when this label is applied to an adherend and heat is applied, the vinylidene chloride resin melts, covering the sticky microparticles and having an adhesive effect on the adherend. It turns out. Additionally, if the paper base material is thin, the vinylidene chloride resin will penetrate into the paper, and if it spreads throughout the paper, it will become a water-resistant paper base, and if characters, etc. are written on the paper base beforehand, it will become a water-resistant paper base. This means that a label that does not bleed (or swell) even if it gets wet with water can be attached and bonded.In other words, it is an extremely large adhesive that can be used as a removable label as well as a heat-adhesive waterproof label. It has characteristics.

Furthermore, when a general paper-based label is pasted on an adherend with a large curvature, the entire label floats due to the stiffness of the paper. A removable adhesive label has an extremely significant feature in that it does not cause lifting of both ends of the label even when attached to an adherend with a large curvature. Furthermore, no matter how thin the paper is, it has sufficient strength because it is reinforced with vinylidene chloride resin.

Furthermore, if a vinylidene chloride resin is used as the base material itself and adhesive fine particles are adhered to both sides of the base material, a heat-adhesive sheet having removability on both sides can be obtained.

In addition, since the adhesive body of the present invention does not use a binder, it is possible to shorten the manufacturing time and reduce the manufacturing cost.

Hereinafter, the present invention will be explained in further detail with reference to Examples.

[Example 1 Example 1 (1) Production of ion-exchanged water (370 mL) was placed in a 1, 5 β four-loop flask equipped with a thermometer, a reflux condenser, a Wi stirrer, and a nitrogen inlet.
g, isononyl acrylate 108g, acrylic acid 4g
, 2 g of sodium alkylaryl polyethylene oxide sulfonate and 0.37 g of benzoyl peroxide were charged. Next, while stirring the system, nitrogen gas was introduced from a nitrogen inflow device for about 30 minutes to replace the air in the system with nitrogen gas. Then, while further nitrogen gas is introduced,
Heat and stir at 66℃ for 20 hours,! ! ! A dispersion of a cloudy polymer was obtained.

After separating the resulting suspended polymer from the immersion solution, about 500 ml of methanol was added to solidify it, which was then washed with isopropanol. Thereafter, it was dispersed in n-hexane to obtain a dispersion of spherical sticky microparticles (solid content: about 8% by weight).

(2) -] 1st grade - 20cm x 70c+n high quality paper with a thickness of 100μm, and a vinylidene chloride resin (Saran [manufactured by Asahi Dow Co., Ltd. 1] film of the same size and thickness of 12μm) was overlaid. The material was laminated between heated rollers that had been treated with an adhesive surface to obtain a base material with a ridge on one side.

The dispersion containing the adhesive microparticles produced in (1) is applied to the glossy surface of the obtained base material, that is, the surface of the vinylidene chloride resin, and the thickness of the adhesive microparticle layer when dried, that is, the thickness It was coated by a screen coating method so that the thickness as measured by a gauge was 7 μm.

Thereafter, it was dried at 100° C. for 1 minute to obtain an adhesive sheet of the present invention.

The adhesive sheet obtained as above was pasted on a glass slide, and after repeated rubbing with fingers 10 times, it was rapidly peeled off, but no microparticles remained on the glass slide. Furthermore, the surface of the slide glass was not contaminated at all and was completely indistinguishable from the slide glass before the test.

A similar test was also conducted using diazocopy paper. As a result, no fine particles remained at all, and only a portion of the surface layer of the diazocopy paper was slightly peeled off.

Example 2 A 60 μm thick vinylidene chloride resin (Saran F [manufactured by Dow Chemical Co., Ltd. 1] film) was layered on a 20 μm thick high-quality paper, and the film was laminated by passing it between heated rolls with a non-adhesive surface treatment. I got it.

A dispersion containing the same adhesive microparticles as that produced in f1+ of Example 1 was applied to the glossy surface of the obtained base material, that is, the surface of the vinylodene chloride resin, so that the thickness as measured by a thickness gauge was 5 μm. Coating and coating in the same manner as in Example 1 so that
After drying, the viscosity of the present invention was obtained (this sheet was obtained).

The rubbed adhesive sheet was punched out into a size of 24+nn x 50n+m to obtain a removable label.

This label was subjected to the same test as in Example 1, and as in Example 1, the removability was good.

Next, I attached this label to the cover of a commercially available notebook, and when I applied pressure and heat for about 1 second with a TSO'C iron, it adhered to the notebook and could no longer be removed from the cover. When the label was attached to the cover of the notebook without applying any heat, the letter J) was written in ink, and then the label was pressed and heated for 3 to 5 seconds with an iron at 180℃, and at the same time the label was adhered to the cover of the notebook. Vinylidene chloride resin also penetrated the cover of the label. After that, even when I dripped water on it, the letters did not smear with the water.

Furthermore, this removable label is 12mm x 24mm.
When the label was cut out to size and wrapped around a glass test tube with a diameter of 18 mm, the edges of the label did not float at all and the entire surface was stuck to the test tube.

Example 3 A dispersion of the adhesive microparticles obtained in Example 1 dispersed in ethyl acetate (solid content: 5
% by weight) was applied to the front and back sides of the film using a spray gun and dried to obtain a double-sided removable sheet.4 This was placed on drawing paper, and a release paper was applied from above and pressed lightly. After removing the release paper, I pasted and peeled off the colored paper cut out in various shapes, but the colored paper did not tear and the adhesive did not stick to the colored paper.

Example 4 Vinylidene chloride resin (Zeon 200[
Nippon Zeon (Structure) vinylidene chloride resin content 70
The adhesive microparticles obtained in Example 1 (1) are coated on a film (having a composition of 30 parts by weight and 30 parts by weight of white pigment) using a knife coater, and dried, and the adhesive microparticles are measured using a thickness gauge. A removable sheet with a layer thickness of 41 tm was obtained.

This seat was extremely flexible with almost no waist.

Next, this sheet was cut out into a size of 6 mm x 1.2 mm to obtain a label. Even when this was pasted on a plastic ABS sheet with a diameter of 4 openings, the edges did not lift at all6.Also, when the same label was pasted on the cover of a notebook and heated and pressed with an iron at 180℃, it was Similar to example 2,
It adhered to the surface of the notebook and could not be removed. Also,
After that, when I rubbed it with my fingers, the corners of the label came off and I couldn't feel the thickness.

Comparative Example 1 The adhesive microparticles obtained in (1) of Example 1 were coated on a saturated polyester film with a thickness of 50 μm using a knife coater, and the thickness of the adhesive microparticle layer was 7 μm using a thickness gauge. A transparent removable sheet was obtained. When this was pasted on the cover of a notebook and removed, a considerable amount of adhesive remained.

Comparative Example 2 5% vinylidene chloride resin/(toluene/MEK) was coated on -F paper with a thickness of LOOum using a knife coater so as to form a vinylidene chloride resin layer with a thickness of 0.5 μm. The adhesive microparticles obtained in step +11 of Example 1 were coated on the surface with a knife caulk to a thickness of 4 um and dried to obtain a removable adhesive sheet. This is 12mm x 24mm
A removable label was obtained by cutting it out to the size of . When this label was wrapped around a glass test tube with a diameter of 18 mm, both ends of the label peeled off from the test tube, leaving the label stuck to the test tube with its four corners floating.

[Effects of the Invention] In the removable adhesive body of the present invention, the part where the adhesive microparticles come into contact with the base material is a smooth surface of vinylidene chloride resin, so the adhesive microparticles are reliably and firmly attached to the base. Adhesive and fixed to the material, no adhesive microparticles remain on the adherend, and can function as a high-quality removable adhesive.

Furthermore, in the case where the base material has a vinylidene chloride resin film on the support, even if the support is porous, the surface of the vinylidene chloride resin that the adhesive microparticles come into contact with is Therefore, moisture permeability is eliminated, that is, water resistance is imparted. Furthermore, if the adhesive of the present invention is applied to an adherend and then heated, the vinylidene chloride resin melts and acts as a hot-melt adhesive between the adhesive base material and the adherend, that is, it is not an adhesive but an adhesive. Can be used as an agent,
It also has the following advantages.

Claims (1)

[Scope of Claims] A removable adhesive body having a plurality of adhesive fine particles containing (meth)acrylic acid ester as a main component on a base material, wherein the base material is made of a vinylidene chloride resin film, or A removable adhesive comprising a vinylidene chloride resin film on a support.