KR20190095869A - Pressure sensitive adhesive sheet - Google Patents

Abstract

The present invention relates to an adhesive sheet (1) comprising: a base material (11); and an adhesive layer (12) laminated on one surface of the base material (11), wherein arithmetic mean roughness (Ra) on the surface of the base material (11), on which the adhesive layer (12) is laminated, is 25 nm or less, and the adhesive layer (12) comprises: an addition-reactive silicone resin obtained from a first polydimethylsiloxane having at least two alkenyl groups in one molecule and a second polydimethylsiloxane having at least two hydrosilyl groups in one molecule; a silicone adhesive containing a platinum catalyst; and a silicone type adhesive composition containing a silane coupling agent. The adhesive sheet (1) is also excellent in adhesiveness with respect to the base material which has high smoothness in addition to favorable re-peelabilitye.

Description

Adhesive Sheet {PRESSURE SENSITIVE ADHESIVE SHEET}

This invention relates to the adhesive sheet which can be used suitably as a protective sheet for protecting a device.

Conventionally, in devices, such as an optical member and an electronic member, in order to prevent surface flaw during processes, such as a process, an assembly, and an inspection, the adhesive sheet which consists of a base material and an adhesive layer on the surface of the said device is used as a protective sheet. It may be stuck. This protective sheet is peeled off from the device at the point where the protection is no longer needed.

In recent years, as an optical member, the movement to move from a liquid crystal device to an organic light emitting diode (OLED) device has become active. Furthermore, the examination of the OLED device (henceforth a "flexible OLED device") which has flexibility is also active. Unlike the liquid crystal device and the conventional OLED device, the flexible OLED device is flexible, and thus, when a conventional protective sheet is used, a problem arises that it is difficult to peel from the flexible OLED device. Moreover, in the inspection process of OLED device, since it may be exposed under high temperature conditions, heat resistance is calculated | required by a protective sheet. Under such a background, a silicone pressure sensitive adhesive is preferable as the pressure sensitive adhesive forming the pressure sensitive adhesive layer.

In patent documents 1 and 2, the silicone type adhesive or its use example is disclosed. Patent Literature 1 discloses a room temperature curable silicone pressure sensitive adhesive that is cured by reacting with moisture in air. In particular, in the Example of patent document 1, the composition containing the predetermined polyorganosiloxane and the partial hydrolyzate of an organosilicon compound is poured into a mold, and it cures for 7 days on 23 degreeC and 50% RH conditions, and it is a silicone type adhesive The formation of the sheet which consists of these is disclosed.

Moreover, in patent document 2, it is a surface protection film provided with a base material and the adhesive layer which consists of a silicone pressure sensitive adhesive formed in the single side | surface side of the said base material, The surface protection film in which the antistatic layer is formed in the said adhesive layer side in the said base material is Is disclosed.

Japanese Unexamined Patent Publication No. 2007-321122 Japanese Unexamined Patent Publication No. 2013-107998

The silicone pressure sensitive adhesive disclosed in Patent Document 1 described above is supposed to be used for sealing, adhesion, and coating, and does not exhibit sufficient re-peelability to the adherend. Therefore, the adhesive sheet provided with the adhesive layer comprised from the said silicone type adhesive is not suitable for use as a protective sheet of a device.

In addition, in the light emission inspection of the OLED device, since the inspection is performed at a level more stringent than the light emission inspection of the liquid crystal device, high transparency is required for the protective sheet. However, in the Example of patent document 2, since the base material with comparatively high surface roughness is used, the smoothness of the surface of a base material is comparatively low in the surface protection film provided with the said base material. Due to it, the surface protection film cannot fully acquire the high transparency required by the light emission inspection of OLED device.

Moreover, since the adhesiveness with respect to a base material is low in the conventional silicone type adhesive, there exists a problem that peeling from a base material tends to occur in the adhesive layer comprised from a silicone type adhesive. In particular, the higher the smoothness of the surface on which the pressure-sensitive adhesive layer is formed in the base material, the lower the adhesiveness of the pressure-sensitive adhesive layer to the base material, and the peeling described above is likely to occur.

This invention is made | formed in view of the said real condition, and an object of this invention is to provide the adhesive sheet which is excellent in adhesiveness also with respect to the base material which has the releasability and high smoothness.

In order to achieve the said objective, First, this invention is an adhesive sheet provided with a base material and the adhesive layer laminated | stacked on one surface of the said base material, Comprising: In the surface in which the said adhesive layer in the said base material was laminated | stacked Arithmetic mean roughness Ra is 25 nm or less, and the said adhesive layer is obtained from the 1st polydimethylsiloxane which has at least 2 alkenyl group in 1 molecule, and the 2nd polydimethylsiloxane which has at least 2 hydrosilyl group in 1 molecule. Provided is a pressure sensitive adhesive sheet formed of a silicone pressure sensitive adhesive composition containing an addition reactive silicone resin and a platinum catalyst and a silane coupling agent (Invention 1).

Since the adhesive sheet which concerns on the said invention (invention 1) is a thing comprised from the silicone adhesive containing the above-mentioned addition reaction type silicone resin, favorable re-peelability can be achieved. Moreover, since the said adhesive sheet is a thing comprised from the silicone adhesive containing a silane coupling agent, an adhesive layer can achieve the outstanding adhesiveness also with respect to the base material which has high smoothness.

In the said invention (invention 1), it is preferable that content of the said silane coupling agent is 0.001 mass part or more and 3.0 mass parts or less per 100 mass parts of said addition reaction type silicone resin (invention 2).

In the said invention (invention 1, 2), it is preferable that the said silicone adhesive contains silicone resin (invention 3).

In the said invention (invention 1-3), it is preferable that content of the said silicone resin is 1 mass part or more and 40 mass parts or less per 100 mass parts of said addition reaction type silicone resins (invention 4).

In the said invention (invention 1-4), it is preferable that the haze value of the said base material is 3.5% or less (invention 5).

In the said invention (invention 1-5), it is preferable to be used as a protective sheet for protecting a device (invention 6).

In the said invention (invention 6), it is preferable that the said device is a flexible device (invention 7).

The adhesive sheet which concerns on this invention is excellent in adhesiveness also about the base material which has a high smoothness while re-peelability is favorable.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the adhesive sheet which concerns on one Embodiment of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described.

[Adhesion sheet]

As shown in FIG. 1, the adhesive sheet 1 which concerns on this embodiment is the adhesive layer 12 laminated | stacked on the base material 11, one surface of the base material 11 (lower side in FIG. 1), and an adhesive It consists of the peeling sheet 13 laminated | stacked on the surface on the opposite side (lower side in FIG. 1) from the base material 11 in the layer 12. As shown in FIG. This peeling sheet 13 is for protecting the adhesive layer 12 until the use of the adhesive sheet 1, and is peeled off at the time of use of the adhesive sheet 1. In the adhesive sheet 1 which concerns on this embodiment, the peeling sheet 13 may be abbreviate | omitted.

1. Each member

(1) mention

In the base material 11 in this embodiment, arithmetic mean roughness Ra in the surface in which the adhesive layer was laminated | stacked is 25 nm or less. Thereby, the adhesive sheet 1 which concerns on this embodiment becomes high transparency, and becomes a thing preferable as a protective sheet of the device in which light emission inspection like a liquid crystal device and an OLED device is performed. From such a viewpoint, the arithmetic mean roughness Ra is preferably 15 nm or less, particularly preferably 9 nm or less, and further preferably 4.5 nm or less. The lower limit of the arithmetic mean roughness Ra is not particularly limited, but is preferably 0.1 nm or more, particularly preferably 0.5 nm or more, and even more preferably 1.0 nm or more. The detail of the measuring method of the said arithmetic mean roughness Ra is as having described in the test example mentioned later.

In the base material 11 in this embodiment, it is preferable that the root mean square height (Rq) in the surface in which the adhesive layer was laminated | stacked is 45 nm or less, It is more preferable that it is 20 nm or less, It is especially 10 nm or less It is preferable that it is further 6 nm or less. When the said root mean square height Rq is the said range, transparency of the adhesive sheet 1 which concerns on this embodiment becomes higher. The lower limit of the root mean square height Rq is not particularly limited, but is preferably at least 0.5 nm, particularly preferably at least 1.0 nm, further preferably at least 2.0 nm. The detail of the measuring method of the said root mean square height Rq is as having described in the test example mentioned later.

In the base material 11 in this embodiment, it is preferable that the maximum height Rz in the surface in which the adhesive layer was laminated | stacked is 400 nm or less, It is more preferable that it is 300 nm or less, It is especially preferable that it is 200 nm or less Furthermore, it is preferable that it is 130 nm or less. When the said maximum height Rz is the said range, transparency of the adhesive sheet 1 which concerns on this embodiment becomes higher. The lower limit of the maximum height Rz is not particularly limited, but is preferably 10 nm or more, particularly preferably 20 nm or more, and more preferably 30 nm or more. The detail of the measuring method of the said maximum height Rz is as having described in the test example mentioned later.

In the base material 11 in this embodiment, it is preferable that the largest cross-sectional height Rt in the surface in which the adhesive layer was laminated | stacked is 500 nm or less, It is especially preferable that it is 400 nm or less, Furthermore, it is 300 nm or less desirable. When the said largest cross-sectional height Rt is the said range, transparency of the adhesive sheet 1 which concerns on this embodiment becomes higher. The lower limit of the maximum cross-sectional height Rt is not particularly limited, but is preferably 10 nm or more, particularly preferably 30 nm or more, and more preferably 50 nm or more. The detail of the measuring method of the said largest cross-sectional height Rt is as having described in the test example mentioned later.

It is preferable that the total light transmittance of the base material 11 in this embodiment is 80% or more, It is especially preferable that it is 85% or more, Furthermore, it is preferable that it is 88% or more. When the total light transmittance is 80% or more, the transparency of the pressure sensitive adhesive sheet 1 according to the present embodiment becomes higher. There is no restriction | limiting in particular about the upper limit of the said total light transmittance, It is preferable that it is 100% or less, It is especially preferable that it is 98% or less, Furthermore, it is preferable that it is 93% or less. In addition, the total light transmittance of the base material 11 was measured according to JISK7361-1: 1997 and ASTM D1003, The detail measuring method is as having described in the test example mentioned later.

It is preferable that the haze value of the base material 11 in this embodiment is 3.5% or less, It is more preferable that it is 2.5% or less, It is especially preferable that it is 2.0% or less, Furthermore, it is preferable that it is 1.3% or less. When the haze value is 3.5% or less, the transparency of the PSA sheet 1 according to the present embodiment becomes higher, and for example, light emission inspection of the OLED device can be performed without a problem. There is no restriction | limiting in particular about the lower limit of the said haze value, It is preferable that it is 0.1% or more, It is especially preferable that it is 0.2% or more, Furthermore, it is preferable that it is 0.3% or more. In addition, the haze value of the base material 11 was measured according to JISK7136: 2000 and ASTMD1003, The detail measuring method is as having described in the test example mentioned later.

The base material 11 is not particularly limited as long as the above-described arithmetic average roughness Ra can be achieved and the pressure-sensitive adhesive layer 12 can be laminated. When using the adhesive sheet 1 which concerns on this embodiment as a protective sheet of a device, it is preferable that the base material 11 has transparency with respect to the light of the wavelength used by the light emission inspection of a device. Moreover, it is preferable that the base material 11 has heat resistance with respect to the high temperature (for example, 90-150 degreeC) applied by the test | inspection of the device which is a protection target.

Specific examples of the base material 11 include polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, cellulose such as diacetyl cellulose, triacetyl cellulose and acetyl cellulose butyrate, polyimide and polyetherimide, The plastic film which consists of resins, such as a polycarbonate, polymethyl pentene, polyphenylene sulfide, and a liquid crystal polymer, is preferable. The plastic film mentioned above may be a film which consists of a single | mono layer, and the film which laminated | stacked the several layer of the same kind or different types may be sufficient. Among the above, a polyester film or a cellulose film is preferable from a viewpoint of transparency and cost, and a polyester film is preferable from a viewpoint of heat resistance, and a polyethylene terephthalate film is especially preferable.

In addition, although the said plastic film may contain additives, such as an antistatic agent, a heat resistance improving agent, and a ultraviolet absorber, when high transparency is calculated | required, it is preferable not to contain a filler.

The base material 11 in this embodiment may be provided with the desired functional layer on the single side | surface or both surfaces as long as the above-mentioned arithmetic mean roughness Ra can be achieved. Examples of the functional layer include an antistatic layer, a hard coat layer, an antireflection layer, an antiglare layer, a slippery layer, a color correction layer, and the like. Among these, it is preferable that the base material 11 is equipped with an antistatic layer. Since the base material 11 is equipped with the antistatic layer, the adhesive sheet 1 of this embodiment will have desired antistatic property. Thereby, peeling charge at the time of peeling the peeling sheet 13 from the adhesive sheet 1, or peeling the adhesive sheet 1 from an adherend is suppressed, and the dust and the particle | grains with respect to the adhesive sheet 1 or a to-be-adhered body are suppressed. Can effectively suppress the adhesion of.

It is preferable that the antistatic layer mentioned above is a layer which consists of a composition for antistatic layers containing a conductive polymer and binder resin, for example. The conductive polymer and binder resin can use a conventionally well-known thing.

When the base material 11 is provided with an antistatic layer on one side or both sides, the thickness of the antistatic layer (the thickness of one antistatic layer in the case of both sides) is 10 nm or more from the viewpoint of easily exhibiting good antistatic properties. It is preferable that it is especially preferable that it is 20 nm or more, Furthermore, it is preferable that it is 30 nm or more. Moreover, it is preferable that it is 200 nm or less from the viewpoint of the intensity | strength and cost of the base material 11, It is preferable that it is especially 150 nm or less, Furthermore, it is preferable that it is 100 nm or less.

Moreover, when the base material 11 has antistatic property, it is preferable that the surface resistivity is 1x10 <^10> ohm / sq or less, It is especially preferable that it is 1x10 <^9> ohm / sq or less, Furthermore, 1x10 <^8> It is preferable that it is ohm / sq or less. When the surface resistivity is 1 × 10 ¹⁰ Ω / sq or less, it is easy to suppress the peeling electrification voltage of the pressure sensitive adhesive sheet 1 to 0.2 kPa or less, and it is easy to prevent adhesion of dust due to electrostatic action and electrical adverse effects on the device. can do. The lower limit of the surface resistivity is not particularly limited, but is preferably about 1 × 10 ⁵ / sq or more. In addition, the detail of the measuring method of the said surface resistivity and the said peeling electrification voltage is as having described in the test example mentioned later.

Moreover, in the base material 11, as long as the above-mentioned arithmetic mean roughness Ra can be achieved, it is the surface by an oxidation method, an uneven | corrugated method, etc. as desired for the purpose of improving adhesiveness with the adhesive layer 12. Treatment or primer treatment can be performed. Examples of the oxidation method include corona discharge treatment, plasma discharge treatment, chromium oxidation treatment (wet), flame treatment, hot air treatment, ozone, ultraviolet irradiation treatment, and the like. A sand blasting method, a thermal spraying process, etc. are mentioned. These surface treatment methods are suitably selected according to the kind of base material.

It is preferable that the thickness of the base material 11 is 10 micrometers or more, It is preferable that it is especially 25 micrometers or more, Furthermore, it is preferable that it is 38 micrometers or more. Moreover, it is preferable that the thickness of the base material 11 is 200 micrometers or less, It is preferable that it is especially 175 micrometers or less, Furthermore, it is preferable that it is 150 micrometers or less. When the thickness of the base material 11 is the said range, the transparency, heat resistance, and workability of sticking and peeling of the adhesive sheet 1 which concerns on this embodiment become more excellent.

(2) pressure-sensitive adhesive layer

The pressure-sensitive adhesive layer 12 is an addition reaction type silicone resin obtained from a first polydimethylsiloxane having at least two alkenyl groups in one molecule and a second polydimethylsiloxane having at least two hydrosilyl groups in one molecule, and a platinum catalyst. It is formed from the silicone adhesive composition containing the silicone adhesive containing and a silane coupling agent.

In the adhesive sheet 1 which concerns on this embodiment, since the adhesive layer 12 is comprised from the silicone adhesive containing the above addition reaction type silicone resin, favorable re-peelability with respect to a to-be-adhered body can be achieved. have. In addition, since the adhesive layer 12 is formed from the silicone type adhesive composition containing a silane coupling agent, the outstanding adhesiveness with respect to the base material 11 can be achieved. In particular, even when the arithmetic mean roughness Ra in the surface on which the pressure-sensitive adhesive layer in the base material 11 is laminated is in the above-described range, excellent adhesion between the base material 11 and the pressure-sensitive adhesive layer 12 can be ensured. . For this reason, the adhesive sheet 1 which concerns on this embodiment is preferable as a protective sheet of a device, and is especially preferable as a protective sheet which requires high transparency like the protective sheet for OLED devices.

(2-1) silicone adhesive

The silicone pressure sensitive adhesive contains the above-described addition reaction type silicone resin and a platinum catalyst, and the adhesive to the adherend of the pressure sensitive adhesive sheet 1 according to the present embodiment and peeling from the adherend are possible as far as possible. Is not particularly limited. When the adhesive sheet 1 which concerns on this embodiment is used as a protective sheet for protecting the to-be-adhered body exposed to high temperature (for example, 90-150 degreeC) at the time of an inspection or use, a silicone adhesive is this high temperature. It is preferable to exhibit stable adhesive force also under the following. In particular, when the adherend is a flexible device such as a flexible OLED device, it is preferable to select a non-adhesive silicone pressure sensitive adhesive having excellent re-peelability so that the adhesive sheet 1 according to the present embodiment is easily peeled from the flexible device. . Moreover, compared with an acrylic adhesive, a silicone adhesive shows stable adhesive force even at high temperature, and is excellent in heat resistance.

The addition reaction type silicone resin in this embodiment is obtained from the first polydimethylsiloxane having at least two alkenyl groups in one molecule and the second polydimethylsiloxane having at least two hydrosilyl groups in one molecule.

Examples of the alkenyl group contained in the first polydimethylsiloxane include monovalent hydrocarbon groups such as vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, and octenyl group. Vinyl groups are particularly preferred.

It is preferable that content (the ratio of the number of alkenyl groups to the number of methyl groups couple | bonded with a silicon atom) of the alkenyl group in 1st polydimethylsiloxane is 0.005 mol% or more, and it is especially preferable that it is 0.01 mol% or more. Moreover, it is preferable that the said content is 0.1 mol% or less, and it is especially preferable that it is 0.05 mol% or less. It is preferable that 1st polydimethylsiloxane has an alkenyl group in the both terminal of a molecular chain, and may have it in a side chain. Since at least 2 alkenyl groups are contained in 1 molecule of 1st polydimethylsiloxane, and content of an alkenyl group exists in the said range, the crosslinked structure with a high crosslinking density is formed, and the adhesive layer excellent in removability can be obtained. have.

The degree of polymerization (number of siloxane bonds) of the first polydimethylsiloxane is preferably 200 or more, and particularly preferably 500 or more. Moreover, it is preferable that the said polymerization degree is 5,000 or less, and it is especially preferable that it is 3,000 or less.

It is preferable that it is two or more in 1 molecule, and, as for content of the hydrosilyl group in 2nd polydimethylsiloxane, it is especially preferable that it is four or more. Moreover, it is preferable that the said content is 300 or less in 1 molecule, and it is especially preferable that it is 200 or less.

It is preferable that it is 50 or more, and, as for the polymerization degree of 2nd polydimethylsiloxane, it is especially preferable that it is 100 or more. It is preferable that it is 2,000 or less, and, as for the said polymerization degree, it is especially preferable that it is 1,500 or less.

Moreover, it is preferable that the compounding ratio of 2nd polydimethylsiloxane with respect to 100 mass parts of 1st polydimethylsiloxane is 0.01 mass part or more, and it is especially preferable that it is 0.1 mass part or more. Moreover, it is preferable that the said compounding ratio is 20 mass parts or less, and it is especially preferable that it is 10 mass parts or less.

As described above, since the content of each functional group and the blending ratio of the second polydimethylsiloxane to the first polydimethylsiloxane are within the above ranges, the addition reaction of the first polydimethylsiloxane and the second polydimethylsiloxane is preferably generated. It becomes easy to obtain an addition reaction type silicone resin.

Moreover, it is preferable that a 1st polydimethylsiloxane does not have a hydrosilyl group, and it is preferable that a 2nd polydimethylsiloxane does not have an alkenyl group.

It is preferable that it is 20,000 or more, and, as for the weight average molecular weight of 1st polydimethylsiloxane, it is especially preferable that it is 300,000 or more. It is preferable that it is 1.3 million or less, and, as for the said weight average molecular weight, it is preferable that it is especially 1.2 million or less. In addition, the weight average molecular weight of the second polydimethylsiloxane is preferably 300 or more, and particularly preferably 500 or more. Moreover, it is preferable that the said weight average molecular weight is 1400 or less, and it is especially preferable that it is 1200 or less. In addition, the weight average molecular weight in this specification is a value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.

A platinum catalyst is not specifically limited as long as it can harden an addition reaction type silicone resin (addition reaction of 1st polydimethylsiloxane and 2nd polydimethylsiloxane). Preferred examples of the platinum catalysts are platinum group metal compounds such as particulate platinum, particulate platinum adsorbed on a carbon powder carrier, platinum chloride, alcohol-modified platinum chloride, olefin complexes of platinum chloride, palladium and rhodium.

It is preferable that platinum content is 0.01 mass part or more, and, as for the compounding quantity of the catalyst with respect to 100 mass parts of addition reaction type silicone resin mentioned above, it is especially preferable that it is 0.05 mass part or more. Moreover, it is preferable that platinum powder is 3 mass parts or less, and, as for the said compounding quantity, it is especially preferable that it is 2 mass parts or less.

It is preferable that a silicone adhesive further contains silicone resin. When the silicone adhesive contains silicone resin, the adhesive layer 12 obtained becomes more excellent in a base material adhesiveness. Thereby, even the highly smooth base material can exhibit the outstanding base material adhesiveness. As the silicone resin, for example, an MQ resin composed of an M unit which is a monofunctional siloxane unit [(CH ₃ ) ₃ SiO _1/2 ] and a Q unit which is a tetrafunctional siloxane unit [SiO _4/2 ] is used. It is preferable. In this case, it is preferable that molar ratio of M unit / Q unit is 0.6 or more and 1.7 or less.

When a silicone adhesive contains silicone resin, it is preferable that the compounding quantity of silicone resin with respect to 100 mass parts of addition reaction type silicone resins is 1 mass part or more, It is especially preferable that it is 3 mass parts or more, Furthermore, it is 5 mass parts or more desirable. Moreover, it is preferable that the said compounding quantity is 40 mass parts or less, It is especially preferable that it is 30 mass parts or less, Furthermore, it is preferable that it is 20 mass parts or less. When the compounding quantity of silicone resin is the range mentioned above, recombination of a base material adhesiveness as a pressure sensitive adhesive sheet can be made compatible at a higher level.

(2-2) Silane Coupling Agent

It is preferable that a silane coupling agent is an organosilicon compound which has at least 1 alkoxy group couple | bonded with the silicon atom in the molecule | numerator, and has at least 1 functional group which has reactivity with an organic compound.

Examples of the functional group having reactivity with the organic compound described above include at least one selected from glycidyl group, amino group, vinyl group, isocyanate group, mercapto group, (meth) acryloyl group, styryl group, ureide group, and the like. Can be mentioned. Among these, it is preferable that a silane coupling agent has at least one of a glycidyl group and an amino group from a viewpoint of being easy to achieve the outstanding adhesiveness between the adhesive layer 12 and the base material 11, and it is especially preferable to have an amino group. Do. In addition, from the viewpoint of improving the reactivity of the functional group and improving the compatibility with other components in the silicone-based pressure-sensitive adhesive composition, the general formula C _n H _2n ( n preferably represents a positive integer). In this case, the value of n in the general formula C _n H _2n is preferably 1 or more, and particularly preferably 2 or more. In addition, the value of n is preferably 10 or less, and particularly preferably 8 or less.

Examples of the silane coupling agent having a glycidyl group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane , 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycidoxypropyltrimethoxysilane, and the like. Among these, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propylmethyl diethoxysilane, 2- (from the viewpoint of being easy to achieve the outstanding adhesiveness between the adhesive layer 12 and the base material 11 Preference is given to using at least one of 3,4-epoxycyclohexyl) ethyltrimethoxysilane and 8-glycidoxypropyltrimethoxysilane.

Moreover, the oligomer which uses the material mentioned above as a structural monomer may be sufficient as the silane coupling agent which has glycidyl group. In this case, the epoxy equivalent of the oligomer is preferably 100 g / mol or more, particularly preferably 150 g / mol or more. Moreover, it is preferable that the said epoxy equivalent is 1000 g / mol or less, and it is especially preferable that it is 900 g / mol or less. Moreover, it is preferable that the alkoxy group amount of the said oligomer is 20 mass% or more, and it is especially preferable that it is 30 mass% or more. Moreover, it is preferable that the said alkoxy group amount is 80 mass% or less, and it is especially preferable that it is 70 mass% or less. By using such an oligomer, it becomes easy to achieve the outstanding adhesiveness between the adhesive layer 12 and the base material 11.

Examples of the silane coupling agent having an amino group include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (aminoethyl) -8-aminojade Tyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butyly Den) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, etc. are mentioned. Among them, 3-aminopropyltrimethoxysilane and N-2- (aminoethyl) -3-aminopropyltrimethoxy from the viewpoint of easily achieving excellent adhesion between the pressure-sensitive adhesive layer 12 and the substrate 11. Preference is given to using at least one of silane and N-2- (aminoethyl) -8-aminooctyltrimethoxysilane.

In addition, the silane coupling agent demonstrated above may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that content of the silane coupling agent in a silicone adhesive composition is 0.001 mass part or more with respect to 100 mass parts of addition reaction type silicone resin, It is especially preferable that it is 0.005 mass part or more, Furthermore, it is preferable that it is 0.01 mass part or more. . Moreover, it is preferable that it is 3.0 mass parts or less with respect to 100 mass parts of addition reaction type silicone resin, It is more preferable that it is 2.0 mass parts or less, It is preferable that it is especially 1.0 mass part or less, Furthermore, it is 0.5 mass part or less desirable. When content of a silane coupling agent is 0.001 mass part or more, it becomes easy to achieve the outstanding adhesiveness between the adhesive layer 12 and the base material 11. Moreover, when content of a silane coupling agent is 3.0 mass parts or less, it becomes suppressed that the adhesive force between the adhesive sheet 1 and the to-be-adhered body which concerns on this embodiment excessively increases, and the favorable re-peelability of the adhesive sheet 1 is carried out. It can be secured.

(2-3) Other Ingredients

In addition to the said component, the silicone adhesive composition in this embodiment may contain various additives, such as an antistatic agent, a dispersing agent, a crosslinking agent, a reaction inhibitor, a diffusion filler, a pigment, a dye, and a ultraviolet absorber.

(2-4) thickness of the pressure-sensitive adhesive layer

It is preferable that the thickness of the adhesive layer 12 is 5 micrometers or more, It is preferable that it is especially 10 micrometers or more, Furthermore, it is preferable that it is 15 micrometers or more. Moreover, it is preferable that the thickness of the adhesive layer 12 is 100 micrometers or less, It is preferable that it is especially 75 micrometers or less, Furthermore, it is preferable that it is 50 micrometers or less. When the thickness of the adhesive layer 12 is the said range, it becomes easy for the adhesive sheet 1 which concerns on this embodiment to exhibit suitable adhesive force with respect to a to-be-adhered body. As a result, unintentional peeling of the adhesive sheet 1 from an adherend can be suppressed effectively, and it is easy to achieve favorable re-peelability of the adhesive sheet 1.

(3) peeling sheet

The release sheet 13 is not particularly limited as long as it does not adversely affect the pressure-sensitive adhesive layer 12. For example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, Polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene (meth) acrylic acid copolymer A film, an ethylene (meth) acrylic acid ester copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, etc. are used. Moreover, these crosslinked films are also used. Moreover, these laminated | multilayer film may be sufficient. Among the above, the polyethylene terephthalate film which is excellent in handling property is preferable.

Peeling process may be given to the surface which contact | connects the adhesive layer 12 of the said peeling sheet 13. As a peeling agent used for a peeling process, the fluorine type, alkyd type, silicone type, unsaturated polyester type, polyolefin type, and wax type peeling agent are mentioned, for example.

The release sheet 13 may be provided with an antistatic layer on one or both surfaces thereof. In addition, while performing the peeling process mentioned above on the same surface side in the peeling sheet 13, you may form an antistatic layer, In this case, after forming an antistatic layer, peeling process is performed on the said antistatic layer. We shall perform. A known antistatic layer may be sufficient as the said antistatic layer, for example, can be formed from the composition for antistatic layers similar to the composition for antistatic layers for forming the antistatic layer in the base material 11. Moreover, although the thickness of the antistatic layer of the peeling sheet 13 is not specifically limited, It may have the same thickness as the antistatic layer in the base material 11.

Moreover, it is also preferable that the peeling sheet 13 is provided with antistatic property by the above method. Thereby, it becomes easy to suppress the peeling electrification voltage of the adhesive sheet 1 low, and to suppress the charging of the adhesive sheet 1 after peeling the peeling sheet 13 to the minimum. From such a viewpoint, it is preferable that the surface resistivity in the surface of the side which contact | connects the adhesive layer of the peeling sheet 13 is 1 * 10 <^12> ohm / sq or less, It is especially preferable that it is 1 * 10 <^11> ohm / sq or less, Furthermore, it is preferable that it is 1 * 10 <^{10> (} ohm) / sq or less. The lower limit of the surface resistivity is not particularly limited, but is preferably about 1 × 10 ⁷ Ω / sq or more. In addition, the detail of the measuring method of the said surface resistivity and the said peeling electrification voltage is as having described in the test example mentioned later.

Although there is no restriction | limiting in particular about the thickness of the peeling sheet 13, Usually, it is preferable that it is 15 micrometers or more, and it is especially preferable that it is 25 micrometers or more. Moreover, it is preferable that the said thickness is 100 micrometers or less normally, and it is especially preferable that it is 75 micrometers or less.

2. Properties of Adhesive Sheet

(1) total light transmittance

In the adhesive sheet 1 in this embodiment, total light transmittance (when the adhesive sheet 1 is equipped with the peeling sheet 13, the total light transmittance with respect to the laminated body formed by peeling and removing the said peeling sheet 13). ) Is preferably 80% or more, particularly preferably 85% or more, and further preferably 90% or more. When the said total light transmittance is 80% or more, the adhesive sheet 1 which concerns on this embodiment becomes easy to achieve excellent transparency, and becomes very preferable as a protective sheet which requires high transparency like the protective sheet for OLED devices. . There is no restriction | limiting in particular about the upper limit of the said total light transmittance, It is preferable that it is 100% or less, It is especially preferable that it is 98% or less, Furthermore, it is preferable that it is 94% or less. In addition, the said total light transmittance is measured according to JISK7361-1: 1997 and ASTMD1003, The detail measuring method is as having described in the test example mentioned later.

(2) haze value

In the adhesive sheet 1 in this embodiment, haze value (when the adhesive sheet 1 is equipped with the peeling sheet 13, haze value with respect to the laminated body formed by peeling and removing the said peeling sheet 13). ) Is preferably 4% or less, more preferably 3% or less, particularly preferably 2% or less, and further preferably 1.5% or less. When the said haze value is 4% or less, the adhesive sheet 1 which concerns on this embodiment can achieve the outstanding transparency, and becomes very preferable as a protective sheet which requires high transparency like the protective sheet for OLED devices. . There is no restriction | limiting in particular about the lower limit of the said haze value, It is preferable that it is 0.1% or more, It is especially preferable that it is 0.2% or more, Furthermore, it is preferable that it is 0.3% or more. In addition, the said haze value was measured according to JISK7136: 2000 and ASTMD1003, The detail measuring method is as having described in the test example mentioned later.

(3) adhesion

In the adhesive sheet 1 which concerns on this embodiment, after attaching the surface on the opposite side to the base material 11 in the adhesive layer 12 (henceforth "adhesive surface") to a soda-lime glass, the said It is preferable that the adhesive force measured when peeling an adhesive sheet from a soda-lime glass at the peeling speed of 0.3 m / min is 10 mN / 25 mm or more, It is especially preferable that it is 20 mN / 25 mm or more, Furthermore, 25 mN / 25 It is preferable that it is mm or more. When the adhesive force is 10 mN / 25 mm or more, it can suppress that the adhesive sheet 1 peels inadvertently from a to-be-adhered body. Moreover, it is preferable that the said adhesive force is 300 mN / 25 mm or less, It is more preferable that it is 200 mN / 25 mm or less, It is especially preferable that it is 100 mN / 25 mm or less, Furthermore, it is preferable that it is 50 mN / 25 mm or less. When the adhesive force is 300 mN / 25 mm or less, the adhesive sheet 1 is easy to achieve the excellent repeelability.

Moreover, in the adhesive sheet 1 which concerns on this embodiment, after affixing an adhesive surface to soda-lime glass, the adhesive force measured when peeling an adhesive sheet from the said soda-lime glass at the peeling rate of 2.0 m / min is 20. It is preferable that it is mN / 25mm or more, It is especially preferable that it is 30mN / 25mm or more, Furthermore, it is preferable that it is 40mN / 25mm or more. Moreover, it is preferable that the said adhesive force is 400 mN / 25 mm or less, It is more preferable that it is 300 mN / 25 mm or less, It is especially preferable that it is 200 mN / 25 mm or less, Furthermore, it is preferable that it is 100 mN / 25 mm or less. When using the adhesive sheet 1 in this embodiment as such a protective sheet, since the adhesive force at the time of peeling at the peeling speed of 2.0 m / min is the said range, it is easy to achieve especially outstanding re-peelability. It becomes.

In addition, these adhesive force was measured according to JISZ0237: 2009, and the detail measuring method is as having described in the test example mentioned later.

In the adhesive sheet 1 which concerns on this embodiment, it is preferable that the difference of the adhesive force measured when peeling at the peeling rate of 0.3 m / min, and the adhesive force measured when peeling at the peeling rate of 2.0 m / min is small. Specifically, the absolute value of the difference between the adhesive force at the peeling speed of 2.0 m / min and the adhesive force at the peeling speed of 0.3 m / min is preferably 200 mN / 25 mm or less, particularly preferably 100 mN / 25 mm or less. Furthermore, it is preferable that it is 50 mN / 25 mm or less. When the difference in adhesive force is such a range, the adhesive sheet 1 becomes easy to be firmly fixed to a to-be-adhered body at the time of use, and becomes easy to peel easily after use. In addition, although it does not specifically limit about the lower limit of the absolute value mentioned above, For example, it is preferable that it is 1 mN / 25 mm or more, and it is especially preferable that it is 10 mN / 25 mm or more.

(4) peeling force

In the adhesive sheet 1 which concerns on this embodiment, after affixing an adhesive surface to a polyethylene terephthalate film, the peeling force measured when peeling an adhesive sheet from the said polyethylene terephthalate film at a peeling speed of 0.3 m / min, It is preferable that it is 100 mN / 25 mm or less, It is especially preferable that it is 70 mN / 25 mm or less, Furthermore, it is preferable that it is 50 mN / 25 mm or less. When the said peeling force is 100 mN / 25 mm or less, peeling of the adhesive sheet 1 from an adherend becomes easy, and it becomes easy to achieve the outstanding re peelability. Moreover, it is preferable that the said peeling force is 5 mN / 25 mm or more, It is preferable that it is especially 10 mN / 25 mm or more, Furthermore, it is preferable that it is 15 mN / 25 mm or more. When the peeling force is 5 mN / 25 mm or more, tunneling can be prevented from occurring well.

Moreover, in the adhesive sheet 1 which concerns on this embodiment, after affixing an adhesive surface to a polyethylene terephthalate film, the peeling force measured when peeling an adhesive sheet from the said polyethylene terephthalate film at a peeling speed of 2.0 m / min. This is preferably 200 mN / 25 mm or less, particularly preferably 150 mN / 25 mm or less, and further preferably 100 mN / 25 mm or less. Moreover, it is preferable that the said peeling force is 10 mN / 25 mm or more, It is especially preferable that it is 20 mN / 25 mm or more, Furthermore, it is preferable that it is 30 mN / 25 mm or more. When the peeling force is 10 mN / 25 mm or more, tunneling can be prevented from occurring well. When peeling at the peeling speed of 2.0 m / min is below the said upper limit, when peeling the adhesive sheet 1 in this embodiment from a to-be-adhered body, it is quick to implement without requiring a large force. When using as a protective sheet (for example, the protective sheet for flexible devices) to which a thing is requested | required, it becomes easy to achieve especially the outstanding repeelability.

In addition, these peeling force was measured according to JISZ0237: 2009, and the detail measuring method is as having described in the test example mentioned later.

Moreover, when using the adhesive sheet 1 especially for the to-be-adhered body which is reluctant to the influence of static electricity, or when using it in the environment where dust etc. exist, it is a thing that the adhesive charge of the adhesive sheet 1 was suppressed. desirable. From such a viewpoint, it is preferable that the peeling electrification voltage of the adhesive sheet 1 is 0.2 kPa or less, and it is especially preferable that it is 0.1 kPa or less. In addition, the detail of the measuring method of the said peeling electrification voltage is as having described in the test example mentioned later.

3. Manufacturing method of adhesive sheet

The manufacturing method of the adhesive sheet 1 which concerns on this embodiment is not specifically limited. For example, after apply | coating the silicone adhesive composition mentioned above and the coating liquid containing a diluent as needed to one surface of the base material 11, the obtained coating film is dried and heat-hardened to form the adhesive layer 12. By this, the adhesive sheet 1 can be manufactured.

There is no restriction | limiting in particular as said diluent, Various things can be used. For example, acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and mixtures thereof, as well as hydrocarbon compounds such as toluene, hexane and heptane, are used.

What is necessary is just to apply | coat the coating liquid of a silicone type adhesive composition by a conventional method, for example, if it is carried out by the bar coat method, the knife coat method, the roll coat method, the blade coat method, the die coat method, the gravure coat method. do. When the said coating liquid is apply | coated, it is preferable to heat-dry a coating film.

As conditions of the above-mentioned thermosetting, it is preferable that heating temperature is 80 degreeC or more and 180 degrees C or less, and it is preferable that heating time is 10 seconds or more and 150 seconds or less.

When the adhesive layer 12 was formed as mentioned above, the peeling sheet 13 was bonded to the said adhesive layer 12, and the adhesive sheet 1 can be obtained.

In addition, in the said manufacturing method, although the adhesive layer 12 was formed with respect to the base material 11, you may form with respect to the peeling sheet 13, and after that, you may bond the base material 11 to the adhesive layer 12.

4. Use of Adhesive Sheet

Although the use of the adhesive sheet 1 which concerns on this embodiment is not specifically limited, It is suitable for use as a protective sheet for preventing the surface flaw etc. in a device during processes, such as a process, an assembly, and an inspection of a device. . Moreover, the adhesive sheet 1 which concerns on this embodiment is also suitable as a protective sheet for an end user to affix on the display of electronic devices, such as a smartphone.

In the adhesive sheet 1 which concerns on this embodiment, an adhesive layer is comprised by the silicone adhesive, and can achieve favorable repeelability. Therefore, when peeling the adhesive sheet 1 which completed the role of protection from a device, peeling generate | occur | produces in the interface of the base material 11 and the adhesive layer 12, and a part of adhesive layer 12 remains on a device. It is suppressed. In addition, when peeling the adhesive sheet 1 from a device, generation | occurrence | production of damage or damage of a device is suppressed.

When using the adhesive sheet 1 as a protective sheet of a device, an optical member, an electronic member, etc. are mentioned as an example of the said device. In particular, in the adhesive sheet 1 which concerns on this embodiment, it is preferable that the device used as the object of protection is a flexible device. Moreover, in the adhesive sheet 1 which concerns on this embodiment, it is preferable that the device used as the object of protection is a device for which light emission inspection and high temperature conditions are requested | required in the state which the adhesive sheet 1 affixed. Therefore, it is preferable that the device used as the object of protection by the adhesive sheet 1 which concerns on this embodiment is an OLED device, and it is especially preferable that it is a flexible OLED device.

In the adhesive sheet 1 which concerns on this embodiment, the arithmetic mean roughness Ra of the surface in which the adhesive layer 12 in the base material 11 was laminated | stacked is the range mentioned above, and the adhesive sheet 1 is excellent overall. It is supposed to have transparency. Therefore, the light emission test etc. of a device can be performed favorably in the state which the adhesive sheet 1 affixed. In particular, like the OLED device, the adverse effect on the light emission inspection is suppressed well even for a device in which the light emission inspection is performed at a more stringent level.

Moreover, as mentioned above, in the adhesive sheet 1 which concerns on this embodiment, the surface in which the adhesive layer 12 of the base material 11 was laminated | stacked shows the arithmetic mean roughness Ra mentioned above, and is relatively smooth. This is a high side. Nevertheless, the pressure-sensitive adhesive layer 12 is formed of a silicone pressure-sensitive adhesive composition containing a silane coupling agent, thereby providing excellent adhesion at the interface between the base material 11 and the pressure-sensitive adhesive layer 12. Therefore, in the adhesive sheet 1 which concerns on this embodiment, unintentional peeling in the interface of the base material 11 and the adhesive layer 12 can be suppressed, and the adhesive sheet 1 is peeled from a to-be-adhered body. When doing so, it is suppressed that only the adhesive layer 12 remains on the adherend. Moreover, also when winding up the adhesive sheet 1 which concerns on this embodiment to make a roll, generation | occurrence | production of tunneling which peeling of the interface of the base material 11 and the adhesive layer 12 generate | occur | produces is suppressed.

[Flexible device with protective sheet]

In the flexible device with a protective sheet according to the present embodiment, the PSA sheet 1 according to the present embodiment is affixed on at least one side of the flexible device as a protective sheet. As a flexible device in this embodiment, the optical member, electronic member, etc. which have flexibility are mentioned, It is preferable that it is especially a flexible OLED device.

The embodiments described above are described for facilitating the understanding of the present invention, and are not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

For example, another layer (for example, an antistatic layer) may be interposed between the base material 11 and the pressure sensitive adhesive layer 12 in the pressure sensitive adhesive sheet 1, and the pressure sensitive adhesive layer in the base material 11 ( 12) Another layer (for example, antistatic layer) may be laminated | stacked on the surface on the opposite side to the side.

Example

Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples.

EXAMPLE 1

1. Preparation of coating liquid of silicone pressure-sensitive adhesive composition

100 parts by mass of an addition-response silicone resin (Shin-Etsu Chemical Co., Ltd., product name "KS-847H") as a main ingredient of a silicone adhesive, 2 parts by mass of a platinum catalyst (Toray Dow Corning Company, product name "SRX 212 CATALYST") 0.25 parts by mass of 3-glycidoxypropyltrimethoxysilane as a coupling agent and 15 parts by mass of silicone resin (Toray Dow Corning, product name "SD-4584") were mixed, diluted with methyl ethyl ketone, and this was a silicone pressure sensitive adhesive. It was set as the coating liquid of the composition.

2. Preparation of Adhesive Sheet

After apply | coating the coating liquid of the silicone adhesive composition obtained at the said process by the knife coater to one surface in the base material A shown in Table 1, it heat-processed at 130 degreeC for 2 minutes, and formed the adhesive layer of thickness 25micrometer. . Next, the polyethylene terephthalate (PET) film (Toray Corporation make, product name "Lumirror T60", no peeling agent layer, thickness: 50 micrometers) was bonded together to this adhesive layer, and the adhesive sheet was obtained.

[Examples 2 to 14 and Comparative Examples 1 to 5]

The adhesive sheet was produced like Example 1 except having changed the kind and compounding quantity of a silane coupling agent, the kind of base material, and the kind of release sheet as shown in Table 2. In addition, in the example using the base material C or E in which the easily bonding layer exists only in single side | surface, the adhesive layer was formed in the surface in which the said easily bonding layer exists.

In addition, in Table 1, about the used base materials A-E and 2 types of base materials (product name "T100F38" and "T100J") as a reference, the kind of the coating layer which each base material has, and it measured by the test example mentioned later It shows various physical properties.

In addition, the details, such as the symbol of Table 2, are as follows.

[Peel sheet]

Lumirror T-60: Polyethylene terephthalate film (Toray Corporation make, product name "Lumir T60", no release agent layer, thickness: 50 micrometers)

PET25T-100 (WJ): Polyethylene terephthalate film with antistatic layer formed on both surfaces (Mitsubishi Resin Co., Ltd. product name "PET25T-100 (WJ)", thickness: 25 micrometers, surface resistivity measured by the test example mentioned later: 2.4 × 10 ⁹ Ω / sq)

[Test Example 1] (Measurement of Surface Roughness of Substrate)

About the base material shown in Table 1, various surface roughness was measured. Specifically, about the base material in which an easily bonding layer or an antistatic layer exists, the arithmetic mean surface roughness (Ra; unit nm) of one surface of the surface of those layer side with respect to the base material which does not have an easily bonding layer and an antistatic layer. ), The root mean square height (Rq; unit nm), the maximum height (Rz; unit nm), and the maximum cross-sectional height (Rt; unit nm) in accordance with JIS B601: 2001, and an optical interference microscope (manufactured by Veeco, product name) It measured using "surface shape measuring apparatus WYKO NT110". At this time, measurement conditions PSI were made into 50 times the magnification, and the average value of 5 measurement points was made into the value of surface roughness. The results are shown in Table 1.

[Test Example 2] (Measurement of Surface Resistivity, such as Substrate)

The surface resistivity (Ω / sq) was measured about the base material shown in Table 1, and the peeling sheet of the product name "PET25T-100 (WJ)" mentioned above. Specifically, in the base material in which an easily bonding layer or an antistatic layer exists, with respect to the surface of those layer side, in the base material in which an easily bonding layer and an antistatic layer do not exist, with respect to one surface, in a peeling sheet, with respect to the one side surface, In an environment of 23 ° C. and 50% relative humidity, a resistivity measuring instrument (manufactured by Mitsubishi Chemical Analytical Co., Ltd., product name “Hysterster UP MCP-HT450 type”) was used to provide a substrate and a release sheet in accordance with JIS K6911: 2006. The surface resistivity (Ω / sq) after applying a voltage of 100 V for 10 seconds was measured. Table 1 shows the measurement results for the substrate. In addition, the measurement result about a peeling sheet is as above-mentioned.

[Test Example 3] (Measurement of total light transmittance and haze value of substrate)

About the base material shown in Table 1, while measuring the total light transmittance (%) according to JISK7361-1: 1997 and ASTMD1003 using the haze meter (made by Nippon Denshoku Industries Co., Ltd., NDH7000), JISK7136: 2000 And haze value (%) was measured according to ASTMD1003. These results are shown in Table 1.

[Test Example 4] (Evaluation of substrate adhesion)

After peeling the adhesive sheet manufactured by the Example and the comparative example for 1 day on 23 degreeC and 50% RH conditions, the peeling sheet was peeled off. Subsequently, a cross notch (50 mm x 50 mm) was put in the cutter knife with respect to the exposed pressure-sensitive adhesive layer. And the adhesive layer of the site | part into which the notch was put was rubbed inside a finger, the dropping degree of the adhesive layer was confirmed, and the base material adhesiveness was evaluated on the following references | standards. The results are shown in Table 3.

○…. The pressure-sensitive adhesive layer was not detached from the substrate, and good adhesiveness could be maintained.

Δ. Although a part of adhesive layer was detached from a base material, some adhesiveness was able to be maintained.

×… The whole adhesive layer was desorbed from the base material, and adhesiveness became inadequate.

Moreover, the adhesive sheet manufactured by the Example and the comparative example was left still for seven days on 85 degreeC and 85% RH conditions, and the adhesive sheet manufactured by the Example and the comparative example was changed to 7 degreeC under the conditions of 60 degreeC and 90% RH. Also about the thing left still for days, base material adhesiveness was evaluated similarly to the above. These results are also shown in Table 3.

[Test Example 5] (Measurement of total light transmittance and haze value of the adhesive sheet)

About peeling a peeling sheet from the adhesive sheet manufactured by the Example and the comparative example, total light transmittance (%) according to JISK7361-1: 1997 and ASTMD1003 using haze meter (NDH7000 by Nippon Denshoku Industries Co., Ltd.). ), And the haze value (%) was measured according to JIS K7136: 2000 and ASTM D 1003. These results are shown in Table 3.

In addition, as a base material, using the product names "T100F38" and "T100J", respectively, it carried out similarly to Example 1, and produced two types of adhesive sheets, and measured their haze value (%), and all exceeded 4%. It was.

[Test Example 6] (Measurement of Adhesive Force)

The adhesive sheet manufactured by the Example and the comparative example was cut out to length 100mm and width 25mm. Subsequently, the peeling sheet was peeled from the said adhesive sheet, and the exposed surface of the exposed adhesive layer was pressurized at 0.5 Mpa and 50 degreeC with respect to soda-lime glass for 20 minutes, and affixed. Then, the sample for adhesive force measurement was obtained by leaving to stand on standard environment (23 degreeC, 50% RH) for 24 hours.

About the said adhesive force measurement sample, in accordance with JISZ0237: 2009, using a tensile tester (Orientech company make, product name "Tensilon UTM-4-100") in standard environment (23 degreeC, 50% RH). , At a peel angle of 180 ° and a peel rate of 0.3 m / min, the force at the time of peeling the adhesive sheet from the soda lime glass was measured, and this was set as the adhesive force (mN / 25 mm). The results are shown in Table 3.

Moreover, about the sample for adhesive force measurement obtained similarly to the above, the tensile tester (Orientech Co., Ltd. make, product name "Tensilon UTM-4-", under standard environment (23 degreeC, 50% RH) based on JISZ0237: 2009. 100 ”), the force at the time of peeling an adhesive sheet from soda-lime glass at the peeling angle of 180 degrees and the peeling speed of 2.0 m / min was measured, and this was made into adhesive force (mN / 25mm). This result is also shown in Table 3.

Test Example 7 (Measurement of Peeling Force)

The adhesive sheet manufactured by the Example and the comparative example was cut out to length 100mm and width 25mm. Next, the sample for peeling force measurement was obtained by fixing the surface of the base material side of the said adhesive sheet to a stainless steel plate.

About the said sample for peeling force measurement, the tensile tester (Orientec company make, product name "Tensilon UTM-4-100") is used in standard environment (23 degreeC, 50% RH) according to JISZ0237: 2009. The force at the time of peeling a peeling sheet from an adhesive sheet was measured at the peeling angle of 180 degrees, and the peeling speed of 0.3 m / min, and this was made into peeling force (mN / 25mm). The results are shown in Table 3.

Moreover, about the sample for peeling force measurement obtained similarly to the above, the tensile tester (Orien Tech Co., Ltd. make, product name "Tensilon UTM-4") by standard environment (23 degreeC, 50% RH) based on JISZ0237: 2009. -100 "), the force at the time of peeling a peeling sheet from an adhesive sheet was measured at the peeling angle of 180 degrees, and the peeling speed of 2.0 m / min, and this was made into peeling force (mN / 25mm). This result is also shown in Table 3.

[Test Example 8] (Evaluation of Tunneling)

The adhesive sheet manufactured by the Example and the comparative example was wound up to the cylindrical plastic pipe of diameter 7.62 cm, and the roll of the adhesive sheet was obtained. At this time, it wound up so that the surface on the base material side in an adhesive sheet might become an inner side, and the adhesive sheet was wound up until the diameter of the roll obtained becomes 50 cm.

The roll of the adhesive sheet obtained as mentioned above was left to stand for 1 week on condition of 23 degreeC and 65% RH in the state which an adhesive sheet does not touch the ground. Then, the interface state of an adhesive layer and a peeling sheet was confirmed, and tunneling was evaluated based on the following criteria. The results are shown in Table 3.

○…. Peeling did not arise in the interface of an adhesive layer and a peeling sheet.

×… Peeling occurred at the interface between the pressure-sensitive adhesive layer and the release sheet.

[Test Example 9] (Evaluation of Peeling Chargeability)

The adhesive sheet manufactured by the Example and the comparative example was cut out to 25 mm x 100 mm, and this was made into the sample. Under 23 ° C and 50% RH environment, the peeling sheet was peeled from the sample at a peeling speed of 2.0 m / min by hand, and after 5 seconds of peeling, an electrostatic measuring instrument (manufactured by Simco Japan, product name "FMX-003") Using the method, the electrostatic potential (peelable charge voltage; V) at the position of 2.0 cm from the exposed surface of the pressure-sensitive adhesive layer was measured. From the measurement result, the peeling electrification voltage in the adhesive layer surface was evaluated based on the following criteria. The results are shown in Table 3.

○…. Peeling electrification voltage is 0.1 kPa or less.

Δ. Peeling electrification voltage is more than 0.1 kV and 0.2 kPa or less.

×… Peeling electrification voltage is more than 0.2 kPa.

As is apparent from Table 3, the pressure-sensitive adhesive sheet produced in the example was excellent in re-peelability and was also excellent in substrate adhesion of the pressure-sensitive adhesive layer.

The adhesive sheet which concerns on this invention is suitable as a protective sheet used at the process of processing, assembly, an inspection, etc. of OLED device which has flexibility, for example.

1: adhesive sheet
11: description
12: pressure-sensitive adhesive layer
13: peeling sheet

Claims (7)

As an adhesive sheet provided with a base material and the adhesive layer laminated | stacked on one surface of the said base material,
Arithmetic mean roughness Ra in the surface in which the said adhesive layer in the said base material was laminated | stacked is 25 nm or less,
The pressure-sensitive adhesive layer contains an addition reaction type silicone resin obtained from a first polydimethylsiloxane having at least two alkenyl groups in one molecule and a second polydimethylsiloxane having at least two hydrosilyl groups in one molecule, and a platinum catalyst. The adhesive sheet formed from the silicone adhesive composition containing a silicone adhesive and a silane coupling agent. The method of claim 1,
Content of the said silane coupling agent is 0.001 mass part or more and 3.0 mass parts or less per 100 mass parts of said addition reaction type silicone resin, The adhesive sheet characterized by the above-mentioned. The method of claim 1,
Said silicone adhesive contains silicone resin, The adhesive sheet characterized by the above-mentioned. The method of claim 1,
Content of the said silicone resin is 1 mass part or more and 40 mass parts or less per 100 mass parts of said addition reaction type silicone resins, The adhesive sheet characterized by the above-mentioned. The method of claim 1,
Haze value of the said base material is 3.5% or less, The adhesive sheet characterized by the above-mentioned. The method of claim 1,
The adhesive sheet used as a protective sheet for protecting a device. The method of claim 6,
The said device is a flexible device, The adhesive sheet characterized by the above-mentioned.

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