JPH07126598A - Pressure-sensitive adhesive composition - Google Patents

Abstract

PURPOSE:To provide a pressure-sensitive adhesive compsn. which exhibits a strong adhesive force when it is not irradiated with ultraviolet rays and whose adhesive force is decreased remarkably when irradiated with ultraviolet rays. CONSTITUTION:15-200 pts.wt. ultraviolet-curable acrylate, 10-200 pts.wt. tackifier, 1-100 pts.wt. polyisocyanate, 1-30 pts.wt. anhydrous silica powder, and a polymn. initiator are added to 100 pts.wt. elastic polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive composition, and more particularly to a pressure-sensitive adhesive composition capable of reducing its adhesive force by irradiation with ultraviolet rays.

[0002]

2. Description of the Related Art Generally, a pressure-sensitive adhesive sheet or pressure-sensitive adhesive sheet obtained by coating a pressure-sensitive adhesive on a base sheet is used for various purposes in general households and industries. The adhesive sheet has a wide variety of required characteristics, and various functionalities are required depending on the application.

For example, in order to obtain a dice by cutting a silicon wafer into a predetermined size in manufacturing an integrated circuit, that is, dicing, a silicon wafer is placed on a pressure-sensitive adhesive sheet called a so-called dicing film. It is placed, pressure-sensitively adhered and fixed on the dicing film, cut and then picked up, that is, peeled off from the dicing film and taken up. Therefore, in order to accurately dice the silicon wafer, the dicing film has a strong adhesive force to the silicon wafer at the time of dicing, while the dicing film has a strong adhesive force to the silicon wafer when it is picked up from the dicing film. It is necessary that the adhesive strength is weak. For example, when the silicon wafer is diced, the dicing film has a thickness of 100 to 80, although not limited thereto.
It has an adhesive strength of about 0 g / 25 mm, while the dicing film is several tens g / g when picking up the dice.
It is said that it is desirable to have an adhesive force of about 25 mm or less.

However, in this way, after being applied to the adherend,
A pressure-sensitive adhesive composition capable of reducing its adhesive force, if necessary, and a pressure-sensitive adhesive sheet having such properties have not yet been known. On the other hand, for example, generally in the field of adhesives, a UV-crosslinkable adhesive comprising a photopolymerizable oligomer, a photopolymerizable monomer, a photopolymerization initiator and other additives is already known, which is a solventless type, It is a one-component adhesive that is fast-curing and has the advantage that it does not require heating, etc. However, in this adhesive, the UV irradiation inherently gives the adhesive the required adhesive strength. It is done to let you.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive studies, the present inventors have conducted intensive studies to obtain a pressure-sensitive adhesive composition which initially has a strong adhesive force and can reduce the adhesive force as needed. Unexpectedly, a pressure-sensitive adhesive composition comprising a mixture containing an elastic polymer and an ultraviolet-crosslinkable acrylic ester as a main component, when the composition is irradiated with ultraviolet rays, its adhesive force is significantly reduced. I found it.

As a result of further research conducted by the present inventors, a pressure-sensitive adhesive composition obtained by further containing polyisocyanate and anhydrous silica powder as components in the pressure-sensitive adhesive composition is irradiated with ultraviolet rays. The present invention has been completed by finding that the adhesive force is further significantly reduced or substantially disappears when the above is performed. Accordingly, the present invention has an object to provide a pressure-sensitive adhesive composition which has a strong adhesive force when it is not irradiated with ultraviolet rays and which can be significantly reduced in adhesive force by irradiating it with ultraviolet rays. And

[0007]

The pressure-sensitive adhesive composition of the present invention, which can reduce the adhesive force by irradiation with ultraviolet rays, is a UV-crosslinkable acrylic acid ester 15 to 200 per 100 parts by weight of an elastic polymer. It is characterized by containing 10 parts by weight of a tackifier, 10 to 200 parts by weight of a tackifier, 1 to 100 parts by weight of polyisocyanate, and 1 to 30 parts by weight of anhydrous silica powder together with a polymerization initiator.

Conventionally, various pressure-sensitive adhesive compositions have been disclosed, for example, in "Adhesive Handbook (2nd Edition)" (edited by Japan Adhesive Association,
Nikkan Kogyo Shinyakusha, 1980), known as described on pages 398 to 414, a typical pressure-sensitive adhesive composition contains an elastic polymer as a main component and a It is a mixture obtained by uniformly mixing a tackifier and a plasticizer having good solubility, and further, if necessary, a filler, an antioxidant, a colorant and the like. In the present invention, a saturated copolymerized polyester resin, a polyacrylic acid ester, and a copolymer of acrylic acid ester can be preferably used as the elastic polymer.

First, the saturated copolyester resin is described, for example, in "Industrial Materials" Vol. 25, No. 11, No. 101-106.
As described in the page, it is usually a saturated copolymer resin having a relatively low glass transition point obtained by polycondensing two or more different saturated divalent carboxylic acids and a saturated dihydric alcohol, As the saturated divalent carboxylic acid, an aromatic divalent carboxylic acid and an aliphatic divalent carboxylic acid are used in combination to give a saturated divalent carboxylic acid.
Aliphatic or alicyclic dihydric alcohol as the polyhydric alcohol,
That is, glycol is used. Particularly, in the present invention, the aromatic divalent carboxylic acid / aliphatic divalent carboxylic acid molar ratio is 80/20 to 20/80, preferably 70/30.
A saturated copolyester resin obtained by polycondensing a saturated divalent carboxylic acid mixture of 50 to 50/50 with an equimolar amount is preferably used. In the present invention, terephthalic acid is used as the aromatic divalent carboxylic acid, sebacic acid and adipic acid are used as the aliphatic polycarboxylic acid, and saturated glycols obtained by using ethylene glycol, 1,4-butanediol, propylene glycol, etc. as the glycol are used. Polymerized polyester resin is preferably used. Incidentally, in the production of the saturated copolyester resin, a trivalent or higher polyvalent saturated carboxylic acid or a trivalent or higher polyhydric alcohol may be partially used in combination, if necessary.

Further, as the polyacrylic acid ester or the copolymer of acrylic acid, any of those used as an elastic polymer which is a main component in a pressure-sensitive adhesive conventionally known as an acrylic pressure-sensitive adhesive can be used. Including. The polymer used as the elastic polymer in the acrylic pressure-sensitive adhesive is usually substantially an acrylic acid ester copolymer. This copolymer usually contains an acrylic acid alkyl ester such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, which forms a polymer having a low glass transition point for imparting tackiness, as a main monomer. , A comonomer forming a hard polymer having a high glass transition point for imparting cohesiveness, for example, vinyl acetate, acrylonitrile, styrene, methyl acrylate,
Methyl methacrylate, etc., and a carboxylic acid group, a hydroxyl group, an amide group, a glycidyl group for improving crosslinkability and adhesiveness,
It is a copolymer obtained by copolymerizing monomers having a functional group such as hydroxylmethyl group, for example, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl methacrylate, hydroxylpropyl methacrylate, acrylamide, glycidyl methacrylate, etc. .

The UV-crosslinkable acrylic acid ester used in the pressure-sensitive adhesive composition according to the present invention means an acrylic acid ester or a methacrylic acid ester as an oligomer or a monomer which is crosslinked by irradiation of ultraviolet rays, and has at least 2 in its molecule. It has one acryloyl group or methacryloyl group. Specifically, such oligomers are, for example, oligoester acrylates, and the monomers are, for example, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate. Ester of polyhydric alcohol such as acrylate and acrylic acid, or ester of polyhydric alcohol such as 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol pentamethacrylate and methacrylic acid Can be mentioned.

In the pressure-sensitive adhesive composition according to the present invention, 15 to 200 parts by weight, preferably 50 parts by weight of the above-mentioned UV-crosslinkable acrylic acid ester is used with respect to 100 parts by weight of the elastic polymer.
It is contained in the range of up to 150 parts by weight. Elastic polymer 100
When the amount of the UV-crosslinkable acrylic acid ester is less than 15 parts by weight, the adhesive strength of the obtained adhesive composition does not substantially change even when the adhesive composition is irradiated with ultraviolet rays. When it exceeds the area, the adhesive force can be reduced by UV irradiation, but for example, when the die is picked up after dicing a silicon wafer, the adhesive may remain on the die, which is not preferable. Is.

The pressure sensitive adhesive composition according to the present invention further comprises
Contains a tackifier. The tackifier used here is not particularly limited, and those conventionally used in the production of pressure-sensitive adhesives can be appropriately used. As such a tackifier, for example, xylene resin, rosin or polymerized rosin, hydrogenated rosin, modified rosin resin such as rosin ester, terpene resin, terpene phenol resin, terpene resin such as rosin phenol resin, aliphatic series , Aromatic and alicyclic petroleum resins, coumarone resins, styrene resins, alkylphenol resins and the like.
The tackifier is usually used in the range of 10 to 200 parts by weight with respect to 100 parts by weight of the saturated copolyester resin. When the blending amount of the tackifier is too small, the adhesive force or tackiness is insufficient, while when it is too large,
The decrease in the adhesive strength after irradiation of the obtained adhesive composition with ultraviolet rays is small, and when such an adhesive composition is applied to a dicing film, it adheres to the dice when the silicon wafer is diced after dicing. This is because the imparting agent may remain, which is not preferable.

The pressure-sensitive adhesive composition according to the present invention further contains a polymerization initiator or a photosensitizer and, if necessary, a polymerization inhibitor. The polymerization initiator is used to accelerate the crosslinking of the above UV-crosslinkable acrylic acid ester by UV irradiation. Such a polymerization initiator is generally well known in the technical field of ultraviolet cross-linking polymerization, and in the present invention, a conventionally known polymerization initiator can be used. Specific examples of such a polymerization initiator include benzoin alkyl ethers such as benzoin methyl ether and benzoin isopropyl ether, and aromatic oxyketones and aromatic ketones such as benzoin, benzyl and benzophenone. It is not limited to.

The thermal polymerization inhibitor is added as necessary in order to prevent the UV-crosslinkable acrylic acid ester from being polymerized by heat, not by UV irradiation, for example. As the inhibitor, a conventionally known ordinary polymerization inhibitor can be used. As such a polymerization inhibitor, for example, picric acid, phenol, hydroquinone, hydolquinone monomethyl ether or the like can be used. The amount of the above-mentioned polymerization initiator and polymerization inhibitor to be blended may be in accordance with a place generally used in the technical field of ultraviolet crosslinking polymerization, for example,
The polymerization initiator is the UV-crosslinkable acrylic ester 1
1 to 20 parts by weight with respect to 00 parts by weight, and the polymerization inhibitor is used in a range of 0.1 to 1 part by weight as needed.

The pressure sensitive adhesive composition according to the present invention further comprises
For 100 parts by weight of the elastic polymer, 1 to 100 parts by weight of polyisocyanate and 1 to 30 parts by weight of anhydrous silica powder are contained. The present inventors have already added the polyisocyanate or anhydrous silica to the pressure-sensitive adhesive composition containing the elastic polymer, the UV-crosslinkable acrylic acid ester, and the polymerization initiator as the main components, respectively. When irradiating with ultraviolet rays, it has been found that the adhesive strength is significantly reduced, but when polyisocyanate and anhydrous silica powder are added together to the pressure-sensitive adhesive composition, polyisocyanate and anhydrous silica powder are added. It has been found that, by virtue of the synergistic effect of (1), the decrease in the adhesive force after ultraviolet irradiation becomes more remarkable as compared with the case where each of them is blended alone. The clear reason is not yet clear, and the present invention is not limited by the reason, but the presence of polyisocyanate does not significantly reduce the adhesive strength of the pressure-sensitive adhesive composition after ultraviolet irradiation. It is considered that the reaction between the polyisocyanate and the functional group of the elastic polymer, for example, in the case of the saturated copolyester resin, is a carboxyl group or a hydroxyl group.

However, when the amount of the polyisocyanate compounded is less than 1 part by weight per 100 parts by weight of the elastic polymer, the effect of lowering the adhesive force after irradiation with ultraviolet rays is not sufficient, while it is more than 100 parts by weight. In this case, the adhesive force of the resulting pressure-sensitive adhesive composition before irradiation with ultraviolet rays decreases with time. A particularly preferable range of the compounding amount is the elastic polymer 100.
The amount is 1 to 50 parts by weight, and particularly preferably 1 to 20 parts by weight.

The polyisocyanate is not particularly limited, but in the present invention, diisocyanate and triisocyanate are preferable. Examples of the diisocyanate include 2,4-toluene diisocyanate, m-phenylene diisocyanate, m-xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate. , Isophorone diisocyanate, dianisidine diisocyanate hexamethylene diisocyanate, and the like. Also, various triisocyanates are commercially available, for example, trimethylolpropane toluene diisocyanate marketed as "Sumidijule L" from Sumitomo Chemical Co., Ltd. is preferably used as a polyisocyanate in the present invention. It is an example of a triisocyanate capable of producing.

Further, a so-called urethane prepolymer of a terminal isocyanate obtained by reacting a diisocyanate and a polyol in the presence of an excess amount of the diisocyanate can also be used as the polyisocyanate.

The content of anhydrous silica in the pressure-sensitive adhesive composition is 1 to 3 parts by weight with respect to 100 parts by weight of the elastic polymer.
It is in the range of 0 parts by weight. However, when the compounding amount is less than 1 part by weight with respect to 100 parts by weight of the elastic polymer, the effect of lowering the adhesive strength after ultraviolet irradiation is poor, while
When the amount is more than 30 parts by weight, the pressure-sensitive adhesive composition obtained is remarkably thickened to form a gel and, for example, the coating operation becomes difficult. A preferable blending amount range is 100% of the elastic polymer.
The amount is in the range of 1 to 20 parts by weight, particularly preferably 1 to 15 parts by weight. The anhydrous silica powder is not particularly limited, but is preferably fine particles in the present invention. Therefore, for example, "Aerosil" by Degussa Co. can be preferably used.

The pressure-sensitive adhesive composition according to the present invention contains the elastic polymer, the UV-crosslinkable acrylic ester, the tackifier, the polymerization initiator, the polyisocyanate and the anhydrous silica powder in the above-mentioned blending amounts, if necessary. And a polymerization inhibitor, a filler, an antioxidant, a colorant, etc., and an appropriate organic solvent that dissolves the organic components other than anhydrous silica powder, such as an aromatic hydrocarbon, a ketone, or a mixture thereof. By dispersing the anhydrous silica powder, a uniform liquid composition can be obtained. As the solvent, for example,
Specifically, a mixed solvent of toluene and methyl ethyl ketone is preferably used, however, it is not limited to this. Further, the content of the elastic polymer in the adhesive composition is appropriately selected depending on the application etc., but is usually 1
It is in the range of 0 to 50% by weight. However, it is not limited to this.

The method for preparing the pressure-sensitive adhesive composition as described above is not particularly limited, but the elastic polymer and the tackifier are usually commercially available in the form of a solution, and these are used. Since it is convenient to do so, for example, these solutions are mixed, and then UV-crosslinkable acrylic acid ester, polymerization initiator, polyisocyanate and anhydrous silica powder, and if necessary, a polymerization inhibitor, filler, aging An inhibitor, a colorant, etc. may be added and mixed uniformly.

Furthermore, the pressure-sensitive adhesive composition according to the present invention comprises
If necessary, a liquid polyacrylic ester, a liquid polybutene, a mineral oil, a plasticizer such as lanolin, or a filler,
You may contain antiaging agents etc. suitably. The pressure-sensitive adhesive composition according to the present invention, as a pressure-sensitive adhesive sheet formed by forming a layer on a substrate sheet capable of transmitting ultraviolet rays,
It is used to advantage. For example, a pressure-sensitive adhesive composition as a solution composition as described above is applied on a substrate sheet,
Such a pressure-sensitive adhesive sheet can be obtained by drying. Such a pressure-sensitive adhesive sheet is particularly advantageously used for applications in which the adhesive force can be reduced, if necessary, after being applied to the adherend surface.

The base sheet is not particularly limited as long as it can transmit ultraviolet rays, and various types of sheets can be used, but a transparent or translucent synthetic resin sheet is usually used. For example, vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer resin, vinyl chloride-
A resin sheet made of vinyl acetate copolymer resin, vinylidene chloride resin, polyolefin, acetyl cellulose, polyvinyl alcohol, polyamide, polyester, polycarbonate or the like is preferably used.

Among the above-mentioned various base resin sheets, the resin sheet made of polyvinyl chloride or a copolymer of vinyl chloride containing a plasticizer is flexible and inexpensive, and therefore, in the present invention. It can be used particularly preferably. In addition to the vinyl chloride resin sheet, there is a substrate sheet that can be suitably used as a base material sheet containing a plasticizer. For example, vinyl chloride-vinylidene chloride copolymer resin, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acrylic acid ester copolymer resin, polyvinylidene chloride, acetyl cellulose and the like can be mentioned.

The plasticizer is not particularly limited, but examples thereof include phthalic acid diesters such as dibutyl phthalate, dioctyl phthalate, didecyl phthalate, ditridecyl phthalate and butylbenzyl phthalate, and tricresyl phosphate. , Trioctyl phosphate, triphenyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, and other phosphate esters, dioctyl adipate,
Dioctyl sebacate, dioctyl azelate, fatty acid diester such as tri-2-ethylhexyl acetyl citrate, polyester adipate, polyester plasticizer such as polypropylene sebacate, epoxy plasticizer such as epoxidized soybean oil, chlorinated paraffin, chlorine Examples thereof include chlorine-based plasticizers such as modified fatty acid ester.

However, when a resin sheet containing a plasticizer is used as the base sheet of the pressure-sensitive adhesive sheet, the plasticizer migrates from the resin sheet into the pressure-sensitive adhesive composition, Further, usually, since the plasticizer and the UV-crosslinkable acrylic ester have good compatibility, the UV-crosslinkable acrylic ester contained in the pressure-sensitive adhesive composition migrates into the resin sheet, and such mutual migration occurs. As a result, the effect of reducing the adhesive strength of the pressure-sensitive adhesive sheet after irradiation with ultraviolet rays is significantly reduced.

Therefore, when a resin sheet containing a plasticizer is used as the base sheet of the pressure-sensitive adhesive sheet, the plasticizer and the UV-crosslinkable acrylic resin are interposed between the base sheet and the pressure-sensitive adhesive sheet. It is preferable to interpose a barrier layer made of a resin layer that does not allow the acid ester to pass therethrough. However,
This barrier layer should not interfere with the transmission of UV light.

That is, this barrier layer does not hinder the transmission of ultraviolet rays at all, but prevents the plasticizer contained in the base resin sheet from migrating into the pressure-sensitive adhesive composition.
The UV-crosslinkable acrylic acid ester contained in the pressure-sensitive adhesive composition is prevented from migrating to the base resin sheet, and thus the plasticizer contained in the base resin sheet is added to the base resin sheet. The inside of the pressure-sensitive adhesive composition contains the UV-crosslinkable acrylic ester contained in the pressure-sensitive adhesive composition, so that the adhesive strength of the pressure-sensitive adhesive sheet decreases with time due to UV irradiation. To prevent.

As the barrier layer, polyethylene,
A film of poly-α-olefin such as polypropylene or polyalkylene terephthalate such as polyethylene terephthalate, or a resin coating film, for example, a resin coating layer such as a modified polyacrylic resin is preferably used. Therefore, the barrier layer is formed by pressing a film made of the above-exemplified resin on the base resin sheet, or by applying a melt of the resin and cooling, or by applying a solution of the above resin and drying. Therefore, it can be formed. The barrier layer can also be obtained by, for example, applying a modified polyacrylic resin solution, heating and drying it as necessary to form a coating film.

Various types of modified polyacrylic resins have been known so far, but generally they are excellent in solvent resistance, and accordingly, they are plasticizers contained in the UV-crosslinkable acrylic ester or the base resin sheet. An alkyd-modified polyacrylic resin that does not dissolve and swell in water and a thermosetting polyacrylic resin are preferable. As the thermosetting polyacrylic resin, for example, acid type, hydroxyl group type, epoxy type, amide type and the like are preferably used.

However, as described above, this barrier layer is particularly preferable as long as it does not substantially permeate the UV-crosslinkable acrylic ester contained in the pressure-sensitive adhesive composition and the plasticizer contained in the base resin sheet. However, it is easily understood that the material is not limited, and the selection is made according to each specific UV-crosslinkable acrylic ester and plasticizer.

The means and method for irradiating the pressure-sensitive adhesive composition according to the present invention with ultraviolet rays are not particularly limited, and in the technical field of ultraviolet-curable resin coatings and ultraviolet-curable adhesives,
It is possible to use means and methods that have been conventionally performed conventionally. For example, as the irradiation means, a xenon lamp,
Irradiation may be performed for a few seconds to a few minutes using an ultraviolet ray source such as a low pressure, medium pressure, high pressure or ultra high pressure mercury lamp.

[0034]

As described above, the pressure-sensitive adhesive composition according to the present invention comprises an elastic polymer and a predetermined amount of ultraviolet-crosslinkable acrylic ester, tackifier, polyisocyanate and anhydrous silica to the elastic polymer. The main component is powder, and these are contained together with a polymerization initiator. The reason is not always clear, but the adhesive force can be remarkably reduced or substantially eliminated by irradiation with ultraviolet rays. .

Accordingly, a layer of such a pressure-sensitive adhesive composition is formed on a suitable base sheet which can transmit ultraviolet rays,
If a pressure-sensitive adhesive sheet is used, it can be easily peeled off from the adhered surface by applying ultraviolet rays from the base material sheet side after applying it to the wearing surface. You can Therefore, such a pressure-sensitive adhesive sheet can be suitably used, for example, as a film for dicing a silicon wafer, as described above.

[0036]

EXAMPLES Examples will be shown below, but the present invention is not limited to these examples. In the examples, "parts" means "parts by weight".

Example 1 A pressure-sensitive adhesive having the composition shown in Table 1 was coated on a release paper, and
Dry for 1 minute at 0 ° C. and apply 1 layer of pressure sensitive adhesive as solids.
It was formed to a thickness of 0 μm. Here, as the saturated copolyester resin, a terephthalic acid / sebacic acid molar ratio of 70
A resin having a glass transition point of about 10 ° C., which was obtained by polycondensing a 30/30 saturated divalent carboxylic acid mixture and ethylene glycol in an equimolar amount, was used.

Next, 100 parts of polyvinyl chloride having an average degree of polymerization of 1300, 35 parts of dioctyl phthalate or polyester plasticizer as a plasticizer and a vinyl chloride resin composition comprising an appropriate amount of a stabilizer and having a thickness of 0.1 mm. Apply the modified acrylic resin solution on the sheet, dry it,
A barrier layer was formed. Then, the pressure-sensitive adhesive layer was laminated on the surface of the barrier layer of the base resin sheet to obtain a pressure-sensitive adhesive sheet.

Each pressure-sensitive adhesive sheet thus obtained was allowed to stand at a predetermined temperature for a predetermined time, the release paper was peeled off, the adhesive strength was measured as it was, and another vinyl chloride resin was used. Main wavelength from sheet side 365 mμ, 120 W
After irradiating with ultraviolet rays for 7 seconds at / cm, the adhesive strength was measured. The results are shown in Table 1.

According to the pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition according to the present invention, the decrease in the adhesive force due to the irradiation of ultraviolet rays is particularly remarkable even after a long period of time. Since it has an adhesive force of 100 g / 25 mm, and can be reduced to about several tens of g / 25 mm after being irradiated with ultraviolet rays, or can be substantially eliminated, as described above, it can be used for dicing a silicon wafer. It can be preferably used.

The measuring method of the adhesive force is as follows. That is, a pressure-sensitive adhesive sheet having a width of 25 mm and a length of 100
After cutting into a test piece by cutting it into mm, the test piece was placed on a stainless steel plate as an adherend and reciprocated 5 times with a 3 kg roller and then pressed with a hopper at a pulling speed of 300 mm / min.
An 80 ° peel test was conducted.

Comparative Example 1 For comparison, a representative example of a pressure-sensitive adhesive composition having the same composition as in Example 1 except that one of polyisocyanate and anhydrous silica powder was not contained was prepared and the same as in Example 1. Then, a pressure-sensitive adhesive sheet was prepared. The results are shown in Table 1. According to these pressure-sensitive adhesive sheets, as compared with the pressure-sensitive adhesive sheets according to the above-described examples, the degree of decrease in the adhesive force after ultraviolet irradiation with respect to the adhesive force before ultraviolet irradiation is small. Furthermore, for comparison, a pressure-sensitive adhesive composition containing neither polyisocyanate nor anhydrous silica was prepared, and a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1. It is apparent that the adhesive force of these pressure-sensitive adhesive sheets does not substantially change even when irradiated with ultraviolet rays.

[0043]

[Table 1]

Example 2 Acrylic pressure-sensitive adhesive solution containing polyacrylic acid ester or copolymer of acrylic acid ester as an elastic polymer (manufactured by Sanyo Kasei Kogyo Co., Ltd., Poly 610SA, polyacrylic acid ester or acrylic acid ester copolymerization) The combined content of about 40% by weight) was dissolved in 100 parts by weight of dipentaerythritol hexaacrylate and benzoin isopropyl ether, and the same polyisocyanate as used in Example 1 was added and mixed. A pressure sensitive adhesive composition was prepared.

This pressure-sensitive adhesive composition was applied on a release paper and dried at 120 ° C. for 1 minute to form a layer of the pressure-sensitive adhesive as a solid content having a thickness of 10 μm. Next, the same modified acrylic resin solution as in Example 1 was applied onto the sheet having the same thickness as in Example 1 and dried to form a barrier layer, and then the barrier layer of the base resin sheet was formed. The pressure-sensitive adhesive layer was laminated on the surface and laminated to obtain a pressure-sensitive adhesive sheet according to the present invention. With respect to the pressure-sensitive adhesive sheet thus obtained, the adhesive force after ultraviolet irradiation was measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2 For comparison, a representative example of a pressure-sensitive adhesive composition having the same composition as in Example 2 except that one of polyisocyanate and anhydrous silica powder was not contained was prepared and the same as in Example 1. Then, a pressure-sensitive adhesive sheet was prepared. The results are shown in Table 2. According to these pressure-sensitive adhesive sheets, as compared with the pressure-sensitive adhesive sheets according to the above-described examples, the degree of decrease in the adhesive force after ultraviolet irradiation with respect to the adhesive force before ultraviolet irradiation is small. Further, for comparison, a pressure-sensitive adhesive composition containing neither polyisocyanate nor anhydrous silica was prepared, and a pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1. It is apparent that the adhesive force of these pressure-sensitive adhesive sheets does not substantially change even when irradiated with ultraviolet rays.

[0047]

[Table 2]

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C09J 7/02 JKK 11/04 JAT 11/06 JAX

Claims (3)

[Claims] 1. To 100 parts by weight of an elastic polymer, 15 to 200 parts by weight of a UV-crosslinkable acrylic ester, 10 to 200 parts by weight of a tackifier, and 1 to 10 of polyisocyanate.
A pressure-sensitive adhesive composition containing 0 part by weight and 1 to 30 parts by weight of anhydrous silica powder together with a polymerization initiator, the adhesive force of which can be reduced by ultraviolet irradiation. 2. The pressure-sensitive adhesive composition according to claim 1, wherein the elastic polymer is a saturated copolyester resin. 3. The pressure-sensitive adhesive composition according to claim 1, wherein the elastic polymer is a polyacrylic acid ester or a copolymer of acrylic acid ester.