JPH10204400A - Adhesive sheet for snow-resistant decoration - Google Patents

Abstract

(57) [Summary] [Problem] No delamination occurs even when buried in snow in winter, and the temperature is 0 ° C even in low temperature construction in winter.
The above provides a snow-resistant decorative pressure-sensitive adhesive sheet that can be adhered without preheating the adherend. SOLUTION: One side of a resin sheet has 100 parts by weight of an acrylic pressure-sensitive adhesive and 10 to 40 disproportionated rosin esters.
A snow-resistant decorative pressure-sensitive adhesive sheet on which a pressure-sensitive adhesive layer composed of parts by weight is laminated, wherein the acrylic pressure-sensitive adhesive is a monomer containing n-butyl acrylate, 2-ethylhexyl (meth) acrylate and (meth) acrylic acid It is a copolymer of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a snow-resistant decorative adhesive sheet, and more particularly to a snow-resistant decorative sheet which is constructed outdoors in a cold area and buried in the snow, but does not float or peel off from an adherend after melting. The present invention relates to an adhesive sheet for use.

[0002]

2. Description of the Related Art Conventionally, an adhesive layer is formed on one surface of an opaque, translucent or transparent vinyl chloride resin resin sheet, an acrylic resin sheet, a fluorine resin sheet or the like containing a pigment. A decorative adhesive sheet is used.

[0003] This decorative pressure-sensitive adhesive sheet is applied to an adherend to be decorated by using a pressure-sensitive adhesive, and exerts a decorative effect by the color and pattern of the resin sheet.
Instead of painting, they are used in display fields such as labels and stickers, advertisements and signboards, and fleet marking fields such as vehicle decoration. However, there has been a problem that when the decorative adhesive sheet attached to an adherend such as a signboard is buried in snow during winter, the decorative adhesive sheet comes off from the adherend after the thaw in spring.

One of the causes is that the interfacial adhesive strength between the resin sheet and the pressure-sensitive adhesive layer is insufficient. As a method for improving the interfacial adhesive strength between the resin sheet and the pressure-sensitive adhesive layer, for example, JP-A-2-178377 discloses that
A method of performing a corona treatment on a resin sheet is disclosed.
However, the corona treatment is complicated in the manufacturing process, and further requires explosion-proof measures. Further, when the decorative adhesive sheet is applied at a low temperature in winter, there is another problem that the adherend is heated to some extent in advance by a heating facility such as a heater before the sticking operation is performed, so that there is a problem that it takes time and effort.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method in which, even when buried in snow in winter, the peeling does not occur during thaw,
In addition, it is an object of the present invention to provide a snow-resistant decorative pressure-sensitive adhesive sheet that can be adhered without pre-heating the adherend if the temperature is 0 ° C. or more even in a low-temperature construction in winter.

[0006]

The snow-resistant decorative pressure-sensitive adhesive sheet of the present invention comprises an acrylic pressure-sensitive adhesive on one side of a resin sheet.
A snow-resistant decorative adhesive sheet on which an adhesive layer comprising 00 parts by weight and 10 to 40 parts by weight of a disproportionated rosin ester is laminated, wherein the acrylic adhesive comprises 60 to 80% by weight of n-butyl acrylate, It is a copolymer of a monomer composition containing 15 to 35% by weight of 2-ethylhexyl (meth) acrylate and 1 to 5% by weight of (meth) acrylic acid.

The resin sheet used in the present invention is not particularly limited, but is preferably a resin sheet made of vinyl chloride resin, urethane resin, olefin resin, polyethylene terephthalate (hereinafter referred to as PET), or the like.

[0008] Among them, the vinyl chloride resin sheet is preferably used in view of flexibility, weather resistance and moldability. The vinyl chloride resin sheet is produced by, for example, adding a pigment, a dye, a stabilizer, a plasticizer, and the like to a vinyl chloride resin, and performing casting or calendering.

The thickness of the resin sheet is 50-100 μm.
m is preferred. If the thickness of the resin sheet is less than 50 μm, the sheet may be wrinkled due to its low stiffness at the time of re-attachment.

The pressure-sensitive adhesive layer in the present invention is formed from an acrylic pressure-sensitive adhesive and a disproportionated rosin ester, and the acrylic pressure-sensitive adhesive comprises 60 to 80% by weight of n-butyl acrylate, 2-ethylhexyl (meth) acrylate 15 ~ 3
It is obtained by copolymerizing a monomer composition of 5% by weight and 1 to 5% by weight of (meth) acrylic acid.

[0011] The glass transition point (T
g) is preferably in the range of -30 to 0 ° C. If the glass transition point (Tg) is lower than -30 ° C, the acrylic pressure-sensitive adhesive may become sticky in autumn or early spring, and if it exceeds 0 ° C, the adhesiveness at low temperature in winter decreases.

In the above-mentioned pressure-sensitive adhesive layer, the disproportionated rosin ester is used as a tackifier resin.
For example, "Super Ester A-12" manufactured by Arakawa Chemical Company
5 "," Superester A-115 "and the like.

If the amount of the disproportionated rosin ester is too small, no effect is exhibited, and if it is too large, the adhesiveness at low temperature is reduced. Therefore, 10 to 40 parts by weight to 100 parts by weight of the acrylic pressure-sensitive adhesive is used. Is limited to

The thickness of the pressure-sensitive adhesive layer is preferably from 10 to 50 μm, more preferably from 20 to 30 μm. If the thickness of the pressure-sensitive adhesive layer is less than 10 μm, the anchoring property with the resin sheet may be deteriorated. If the thickness exceeds 50 μm, the initial adhesive strength becomes too high, so that re-attachment during construction becomes difficult.

The pressure-sensitive adhesive layer may be added with, for example, an isocyanate-based crosslinking agent (“Coronate L-28” manufactured by Nippon Polyurethane Co., Ltd.) in order to increase the cohesive strength.

As a method for forming the pressure-sensitive adhesive layer on the resin sheet (substrate), for example, a pressure-sensitive adhesive comprising a predetermined amount of the acrylic pressure-sensitive adhesive, disproportionated rosin ester, organic solvent and isocyanate-based crosslinking agent A method of applying the agent composition on a resin sheet (substrate) and then drying it to evaporate the organic solvent.

In addition to the method of directly forming the pressure-sensitive adhesive layer on the resin sheet (substrate), the pressure-sensitive adhesive composition is applied to release paper once and dried to form the pressure-sensitive adhesive layer. A transfer method in which a resin sheet (substrate) is stuck on the pressure-sensitive adhesive layer may be adopted.

The coating machine for the pressure-sensitive adhesive composition is not particularly limited as long as it is used for ordinary pressure-sensitive adhesive coating. Preferably, the thickness can be adjusted with high accuracy and the productivity can be improved. Examples thereof include a knife coater, a comma roll coater, and a roll coater that can be applied.

The snow-resistant decorative pressure-sensitive adhesive sheet produced by the above method is usually produced as a laminate in which a release sheet is bonded to an adhesive layer, and the release sheet is peeled from the pressure-sensitive adhesive layer when used. To use.

The release sheet has a supporting force,
It is not particularly limited as long as it has a release layer capable of releasing the acrylic pressure-sensitive adhesive layer on its surface, and for example, nonwoven fabric, synthetic fiber, net, paper, resin sheet, olefin resin film and paper For various sheet materials such as laminates,
One coated with a material for forming a release layer is used. Specific examples of such a release sheet include, for example, paper or PET film coated with a silicone resin.

[0021]

DETAILED DESCRIPTION OF THE INVENTION Preparation of Acrylic Adhesive Solution (A) In a separable flask equipped with a cooling tube, a thermometer, and a stirrer, 80 parts by weight of n-butyl acrylate, 15 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of an acid and 0.05 parts by weight of n-dodecanethiol were added, and 100 parts by weight of an ethyl acetate solvent was further added and mixed. The mixture was heated to reflux under a nitrogen gas atmosphere,
After holding for one minute, 0.3 parts by weight of a polymerization initiator benzoyl peroxide was added dropwise to start the reaction, thereby performing boiling point polymerization. After completion of the reaction, 157 parts by weight of an ethyl acetate solvent was stirred and mixed to obtain an acrylic pressure-sensitive adhesive solution (A) having a viscosity of 6700 cps (solid content: 28% by weight).

Preparation of Acrylic Adhesive Solution (B) In a separable flask equipped with a cooling tube, a thermometer, and a stirrer, 60 parts by weight of n-butyl acrylate, 35 parts by weight of 2-ethylhexyl acrylate, and 5 parts by weight of acrylic acid And 0.05 parts by weight of n-dodecanethiol, and 100 parts by weight of ethyl acetate were further added and mixed. The mixture was heated to reflux under a nitrogen gas atmosphere and kept for 20 minutes, after which 0.3 part by weight of a thermal polymerization initiator, benzoyl peroxide, was added dropwise to initiate a reaction and perform boiling point polymerization. After completion of the reaction, 157 parts by weight of an ethyl acetate solvent was stirred and mixed to obtain an acrylic pressure-sensitive adhesive solution (B) having a viscosity of 6900 cps (solid content: 28% by weight).

Preparation of vinyl chloride resin sheet Composition comprising 100 parts by weight of vinyl chloride resin, 15 parts by weight of plasticizer, 4 parts by weight of epoxidized soybean oil, 5 parts by weight of barium-tin stabilizer and 1 part by weight of ultraviolet absorber Was supplied to a calendering machine to obtain a vinyl chloride resin sheet having a thickness of 50 μm.

(Examples 1 to 6 and Comparative Examples 1 to 6) A predetermined amount of an acrylic pressure-sensitive adhesive solution [(A) or (B)] and a disproportionated rosin ester (manufactured by Arakawa Chemical Co., Ltd.) shown in Table 1. , Trade name "Super Ester A-115" and / or trade name "Super Ester A-125"), and further mixed with 100 parts by weight of this mixture, an isocyanate-based crosslinking agent ("Coronate L" manufactured by Nippon Polyurethane Co., Ltd.) -2
8 ") After stirring and mixing 2 parts by weight, the mixture was coated and dried on the vinyl chloride resin sheet (substrate), and the film thickness after drying was 30 μm.
m having a pressure-sensitive adhesive layer of m.

(Comparative Examples 7 and 8) A predetermined amount of an acrylic pressure-sensitive adhesive solution [(A) or (B)] and a polymerized rosin ester (trade name "Pencel D" manufactured by Arakawa Chemical Co., Ltd.) shown in Table 2
-160 ") with stirring.
After stirring and mixing 2 parts by weight of an isocyanate-based cross-linking agent (“Coronate L-28” manufactured by Nippon Polyurethane Co., Ltd.) with respect to 0 part by weight, coating and drying on the vinyl chloride resin sheet (substrate), and then drying To obtain a snow-resistant decorative pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a thickness of 30 μm.

The following evaluations were performed on the snow-resistant decorative adhesive sheets obtained in the above Examples and Comparative Examples, and the results are shown in Tables 1 and 2. (1) 180 degree peeling force Nippon Shokubai Co., Ltd. primer "NK-
350 "so as to have a thickness of 1 μm, and the snow-resistant decorative pressure-sensitive adhesive sheet was
At 2 ° C under a pressure of 2 ° C, the pressure was applied and applied.
The sample was cured in an oven at a temperature of 1 ° C. for one hour. Next, this sample was immersed in a container filled with water,
After putting in a freezer at 12 ° C. for 12 hours, taking out and leaving it in a refrigerator at 5 ° C. for 12 hours as one cycle, a total of 7 cycles were performed, and then a 180 ° peeling test was immediately performed at a tensile speed of 300 mm / min. The force was measured. It was determined that the greater the 180 degree peeling force, the better the interfacial adhesion and the better the snow resistance.

(2) Evaluation of low-temperature workability After the above-mentioned pressure-sensitive adhesive sheet for decoration with snow resistance was allowed to stand at 0 ° C. for 1 hour or more, a stainless steel plate which was set up vertically was adhered as an adherend, and adhered. The condition was evaluated according to the following evaluation criteria. ：: firmly adhered to the adherend and no peeling occurred. Δ: Barely adhered to adherend and peeled off with slight external force. X: It did not adhere to the adherend at all.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

The pressure-sensitive adhesive sheet for decorative snow of the present invention has the above-mentioned structure, and may be buried in snow during winter by improving the interfacial adhesion between the resin sheet and the pressure-sensitive adhesive layer. However, peeling does not occur from the adherend. Also,
If the temperature is 0 ° C. or more when the work is performed at a low temperature in winter, the application can be performed without particularly heating the adherend.

Claims (1)

[Claims] 1. One side of a resin sheet is provided with 100 parts by weight of an acrylic pressure-sensitive adhesive and 10 to 40 disproportionated rosin esters.
A snow-resistant decorative pressure-sensitive adhesive sheet on which a pressure-sensitive adhesive layer composed of parts by weight is laminated, wherein the acrylic pressure-sensitive adhesive comprises 60 to 80% by weight of n-butyl acrylate and 15 to 35% by weight of 2-ethylhexyl (meth) acrylate. And a monomer composition containing 1 to 5% by weight of (meth) acrylic acid.