TW202108728A - Adhesive tape for vacuum process - Google Patents

Abstract

To provide an adhesive tape used in a vacuum film-formation process which is reduced in a generation amount of out gas causing poor appearance of a functional thin film after film formation. An adhesive tape for a vacuum process includes an adhesive layer having a mass ratio (G)/(R) of a silicone gum (G) to a silicone resin (R) of 35/65 to 100/0, a content of an alkenyl group of 1.0*10<SP>-5</SP> to 1.0*10<SP>-3</SP> mol/g, and storage elastic modulus at 200 DEG C measured in He atmosphere of 1.0*10<SP>5</SP> to 1.0*10<SP>7</SP> Pa, in which the total amount of out gas generated from an adhesive tape when being kept at 200 DEG C for 30 minutes after the temperature has been raised from 23 DEG C to 200 DEG C at a temperature rising rate of 10 DEG C/min in the atmosphere with a degree of vacuum of 1.0*10<SP>-4</SP> Torr or less is 180 mg/m2 or less.

Description

Adhesive tape for vacuum process

The present invention relates to an adhesive tape used in a vacuum process.

In flat panel display devices or touch panel display devices such as smart phones, mobile phones, mobile information terminals PDAs, digital cameras, etc., in order to improve the protection, beauty and design of the display, a thin plate-shaped shield is used The glass is arranged on the front of the display to make a wider area than the image display part. The cover glass is made of chemically strengthened glass.

In recent years, especially in smartphones, a cover glass of 2.5D type, pseudo-3D type, 3D type, etc., which protrudes more from the front than the casing and has curved ends on the end, has been put on the market. . The cover glass is not only a flat part, but also a side part located at the outer periphery of the cover glass is exposed on the surface. Therefore, the side part must be strengthened in the same way as the flat part. The strengthening treatment method of the cover glass processed by such a curved surface is known by the post-reaction sputtering method, or the sputtering method accompanied by the pre-treatment, from which the entire surface of the flat part of the cover glass is set on the outer periphery of the flat part. A processing method of continuously laminating an inorganic film from the surface side to the back side of the side surface of the edge (refer to Patent Document 1).

As a sputtering device for efficiently forming a functional thin film such as a strengthening inorganic film or an anti-reflection film on the above-mentioned cover glass, a carousel type sputtering device is known (refer to Patent Literature 2). The rotating rack type sputtering device is a rotating/batch type sputtering device. It has a polygonal columnar substrate holder (rotating drum) arranged in the chamber, and a magnetron holding a rectangular target is arranged on the inside of the chamber wall The structure of the tube. While rotating the substrate holder on which the substrate is mounted, power is applied to the magnetron, plasma is generated on the upper side of the target, and a specific reaction gas is introduced into the chamber to form a film.

At this time, in general, the cover glass is mounted on a plurality of brackets to form the film, but recently, it has been explored to form a film on a larger number of cover glasses by a batch process. To reduce the damage caused by the cover glass to the bracket installation/removal from the bracket, the plural cover glasses are temporarily fixed to the carrier glass substrate with adhesive tape, etc., and the carrier glass substrate is installed on the bracket to form a film. And the method of peeling/removing the adhesive tape after film formation. When the film is formed by this method, the stent does not directly contact the cover glass, so for example, the functional film can be formed on the entire surface of the side surface of the cover glass of 2.5D~3D type. The temperature of the cover glass at the time of film formation may be set to a high temperature of 150~200℃ from the viewpoint of improving the adhesion of the functional film. In addition, although it also depends on the number of layers or the material of the functional film, the film formation time is usually about 30 to 60 minutes. In addition, the degree of vacuum at the time of film formation is usually 1.0×10 ^-4 Torr or less. Therefore, for the above-mentioned adhesive tape, during the sputtering step, (1) the temporary fixing force that the cover glass does not fall off, (2) the amount of outgas generation is suppressed and controlled to be functional after film formation A grade that does not affect the appearance and characteristics of the film. (3) After the film is formed, the cover glass can be peeled off without damage to the carrier glass substrate, etc., without remaining adhesive.

As an adhesive tape or laminate used in a vacuum environment or at a high temperature, an adhesive tape for a vacuum process is known, which has a substrate and an adhesive layer disposed on at least one side of the substrate. The adhesive layer is polymerized with a substrate. It is composed of an active energy ray-curable adhesive of a photopolymerization initiator, and the 5% weight loss temperature of the photopolymerization initiator in TGA (thermogravimetric analysis) is 160°C or higher (refer to Patent Document 3); or A laminate having a substrate and an adhesive layer laminated on one surface of the substrate, characterized in that the adhesive layer is formed by a silicone adhesive composition. Adhesive composition containing polysilicone rubber containing addition type organopolysiloxane containing siloxane bonds as the main skeleton and alkenyl group as a constituent component, and 0.01 parts by mass or more relative to 100 parts by mass of polysiloxane rubber 3 parts by mass or less of platinum catalyst and 15 parts by mass or more and 100 parts by mass or less of polysilicone resin relative to 100 parts by mass of silicone rubber, and the adhesive layer is heated from 23°C at 5°C/min in an air environment When heated to 200°C, the reduction rate of the mass at 200°C relative to the mass at 40°C is 0.20% by mass or less (refer to Patent Document 4).

In Patent Document 3, specifically, as an example of a vacuum process, there is an example of a process of attaching an adhesive tape as a primer to the semiconductor chip in order to reinforce/protect the bumps of the semiconductor chip during flip-chip packaging. In this process, when the adhesive tape is arranged on the upper side (bump forming surface) of the semiconductor chip, separate airtight spaces are formed above and below the adhesive tape, and the airtight space above and the airtight space below are combined. After decompression, only the airtight space above is returned to atmospheric pressure, and the adhesive tape is attached to the adhered body by using the differential pressure. It records the process in which the airtight space above and the airtight space below are reduced at the same time, which is equivalent to a vacuum process. In the examples, it is recorded in a heated and reduced pressure environment (100°C, 1000Pa=7.5Torr) for 1 hour At that time, the air outflow from the adhesive sheet is in the range of 100~400μg/adhesive sheet 1g.

In Patent Document 4, it is described that a lightly peelable release sheet of an adhesive sheet having an adhesive layer formed of a silicone adhesive composition is peeled off, and the surface of the adhesive layer is attached to an alkali-free glass The main surface of one of the substrates formed by the substrate is then peeled off the re-peeling release release sheet to produce a laminate having a substrate made of an alkali-free glass substrate and an adhesive composition layer. This layer The combined body is put into an oven with an air environment maintained at 240°C, placed in the environment for 60 minutes, then taken out of the oven, and cooled to 23°C in an air environment at 23°C and 50% relative humidity to give resistance to Quality reduction. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2017-171556 A [Patent Document 2] JP 2006-265739 A [Patent Document 3] JP 2017-214528 A [Patent Document 4] JP 2014-195922 A

[The problem to be solved by the invention]

However, the adhesive tape described in Patent Document 3, ^{when used in a high vacuum of 1.0×10 -4} Torr or less, does not sufficiently suppress the outgassing from the adhesive tape. For example, use an inorganic film for strengthening or an anti-reflection film for the cover glass. When the functional film is formed by sputtering, the appearance and characteristics of the functional film may be adversely affected.

In addition, in Patent Document 4, after the production/preparation of the sheet-like laminate, it is placed in an oven at 240°C or higher. After being placed in the environment for 60 minutes, it is necessary to have air at 23°C and a relative humidity of 50%. The long-term annealing treatment step in which the environment is left to cool, so there is room for improvement in workability/productivity. In addition, when the silicone adhesive composition is annealed at 350°C for 60 minutes or more, the adhesive may be denatured or decomposed, and there is a possibility that the adhesive (adhesive residue) may remain on the adherend.

In this way, in order to form a functional thin film on a heat-resistant substrate such as a cover glass, when a vacuum film forming process such as sputtering, vapor deposition, etc. is used, the conventional active energy ray-curable acrylic adhesive or polysiloxane is used. Adhesive tapes based on adhesives are not necessarily the most suitable. In terms of performance or productivity, there is still room for improvement.

The present invention is made in view of the above-mentioned problems, and its purpose is to provide a function of forming a functional film on a thin film substrate such as glass or film by a vacuum film forming process such as sputtering, vapor deposition, etc., which can generate outgassing from the adhesive tape , It is suppressed to the level that does not adversely affect the appearance and characteristics of the functional film, and it is an adhesive tape for vacuum manufacturing that can be produced by a roll-to-roll method. [Means to solve the problem]

Based on this objective, the inventors of the present invention conducted an in-depth study on the adhesive layer of the adhesive tape used in the vacuum process, and found that if (1) is used, a silicone adhesive containing an alkenyl group bonded to a silicon atom can be used. gum) (G) and polysiloxane resin (R) that does not contain alkenyl groups bonded to silicon atoms, blending in the mass ratio (G)/(R) becomes (G)/(R)=35/ The range of 65~100/0, and the content of alkenyl group bonded to silicon atom is set to the range of 1.0×10 ^-5 ~1.0×10 ^-3 mol/g addition reaction type polysiloxane resin mainly Composition, and the addition reaction type polysiloxane resin, (2) is cross-linked by organopolysiloxane having hydrogen atoms (SiH) bonded to silicon atoms and platinum group metal catalysts, by This design is an adhesive composition whose storage modulus at 200°C measured in a He environment is ^{within the range of 1.0×10 5} to 1.0×10 ⁷ Pa, as the adhesive layer, and is aimed at the adhesive layer with the adhesive layer The tape is heated from 23°C to 200°C at a temperature rise rate of 10°C/min under an environment with a vacuum degree of 1.0×10 ^-4 Torr or less, and the total amount of outgas generated when the temperature is maintained at 200°C for 30 minutes is adjusted to 180mg/ m ² or less, if the adhesive tape is used as an adhesive tape for temporary fixation when forming a functional thin film on a heat-resistant substrate by a vacuum film forming process such as sputtering, vapor deposition, etc., the film forming process can be suppressed. The outgassing generated from the adhesive tape will not adversely affect the appearance and characteristics of the functional film obtained, and it has re-peelability (no adhesive residue on the processed adherend, and no damage to the processed adherend during peeling) It is excellent, and can also be produced in a roll-to-roll method, and the present invention has been completed.

In a laminate using a silicone adhesive composition that is not easy to outgas even when placed in a high-temperature environment in the past, the laminate is heated at 200°C or higher for 60 minutes or more by annealing treatment. A method in which the remaining volatile components (solvent or low-molecular siloxane components) inside the adhesive layer of the laminate are removed from the adhesive composition layer. However, with this method, it is extremely difficult to produce the system by a roll-to-roll method like a general adhesive tape, and the workability is also poor. In addition, depending on the treatment temperature or treatment time, the adhesive may decompose and deteriorate, or the decomposed product as a cause of outgassing may increase instead.

The inventors of the present invention have conducted various studies on methods other than high-temperature and long-term annealing treatment to reduce the amount of air generated by the adhesive tape, and focused on the use environment of the adhesive tape not in the air but under high vacuum. this point. That is, the use environment of the adhesive tape is not at the high temperature in the air, but under the special high vacuum, that is, under the high temperature under the airtight. The silicone glue in the silicone adhesive, although it is not easy to cause oxidative decomposition, But on the other hand, when the interaction between silicon atoms in the main chain skeleton and oxygen atoms in other main chain skeletons is strong, a part of the main chain skeleton will be cleaved, which may cause low molecular weight. In addition, polysiloxane resins are also the same, although they are not easy to cause oxidative decomposition, but especially in the case of silanol at the end, the end silanol has a strong interaction between silicon and oxygen atoms in the same main chain skeleton, resulting in formation When it is cyclic, low-molecular-weight components such as linear low-molecular-weight siloxanes or cyclic siloxanes may be produced. As a result, when the adhesive tape is used under high vacuum and high temperature, it can be considered that outgassing is still easily generated from the adhesive layer. From these facts, it is believed that by optimizing the alkenyl content of the silicone rubber, the adhesive layer can be highly cross-linked and structured, so that the silicone adhesive can be stored under high vacuum and high temperature. If the modulus is large, the movement of the molecular chains of silicone rubber and silicone resin is restricted, which can inhibit the interaction between the main chain skeleton or the interaction within the same skeleton, so even in the usual roll-to-roll method The manufactured adhesive tape can also suppress the new generation of low-molecular-weight components as described above. As a result, the generation of outgassing from the adhesive can be suppressed during the vacuum film forming process.

The present invention includes the following constitutions. That is, the adhesive tape for a vacuum process of the present invention is characterized by having a base material and an adhesive layer on at least one side of the base material. The adhesive layer includes a resin composition containing: as a main component Addition reaction type polysiloxane-based resins, organopolysiloxanes having at least two hydrogen atoms (SiH) bonded to silicon atoms in one molecule as a crosslinking agent, and platinum group metals as catalysts Is a catalyst. The above-mentioned addition reaction type polysiloxane resin is a polysiloxane (G) containing an organopolysiloxane containing alkenyl groups bonded to silicon atoms and a polysiloxane (G) containing no silicon atoms bonded The polysiloxane resin (R) of the alkenyl organopolysiloxane is blended in such a way that the mass ratio (G)/(R)=35/65~100/0, and is bonded to the silicon The content of the alkenyl group of atoms is in the range of 1.0×10 ^-5 to 1.0×10 ^-3 mol/g. The storage modulus of the above adhesive layer at 200°C measured in a He environment is 1.0×10 ⁵ to 1.0× In ^{the range of 10 7} Pa, the above-mentioned adhesive tape is heated from 23°C to 200°C at a temperature rise rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total amount of outgas produced is less than ^{180mg/m 2.}

In the above aspect, the substrate is preferably a polyethylene terephthalate film.

In addition, the above-mentioned adhesive tape is an adhesive tape for a vacuum process applied to form a functional film selected from the group consisting of an anti-reflection film, an anti-glare film, an anti-fouling film, and a colored film on a heat-resistant substrate. [Effects of Invention]

According to the present invention, when a functional film is formed on a thin film substrate such as a glass or a film by a vacuum film forming process such as sputtering, vapor deposition, etc., the outgassing from the adhesive tape can be suppressed to the appearance of the functional film, It is a grade that does not cause adverse effects on its characteristics, and it is an adhesive tape for vacuum processes that can be produced by a roll-to-roll method.

Hereinafter, the embodiments of the present invention will be described in detail with reference to the accompanying drawings. (The composition of adhesive tape) FIG. 1 is a diagram showing the structure of a single-sided adhesive tape 10 (hereinafter referred to only as the adhesive tape 10) to which an example of the adhesive tape for a vacuum process of the present embodiment is applied. In addition, FIG. 2 is a diagram showing the structure of a double-sided adhesive tape 20 (only referred to as the adhesive tape 20 hereinafter), which is another example of the adhesive tape for the vacuum process of the present embodiment. The adhesive tapes 10 and 20 of this embodiment are specifically, for example, used in a vacuum process for forming an anti-reflective film on the surface of a cover glass, and are used to pass through a carrier substrate (glass, SUS, etc.) held in a vacuum device. The single-piece cover glass is temporarily fixed.

As shown in FIG. 1, the adhesive tape 10 has a single-sided adhesive tape in which an adhesive layer 2 as an example of an adhesive layer mainly composed of an addition reaction type polysiloxane resin is laminated on one surface of a substrate 1 The composition. In addition, as shown in FIG. 2, the adhesive tape 20 has an adhesive layer 2 and an adhesive layer 2 as an example of an adhesive layer mainly composed of an addition reaction type polysiloxane resin laminated on both sides of the base material 1. The adhesive layer 3 has adhesive tapes on both sides. Here, the adhesive layer 2 and the adhesive layer 3 may be the same or different. Furthermore, although the illustration is omitted, the adhesive tapes 10 and 20 are provided between the base material 1 and the adhesive layer 2, and between the base material 1 and the adhesive layer 3, if necessary, to improve the base material 1. An anchor coat layer for adhesion to the adhesive layer 2 and adhesion to the substrate 1 and the adhesive layer 3. In addition, the surface of the adhesive layer 2 (the surface opposite to the surface opposite to the substrate 1) and the surface of the adhesive layer 3 (the surface opposite to the surface opposite to the substrate 1) may also be provided Peel the film. In addition, in the case of the structure of the single-sided adhesive tape 10, the surface of the base material 1 (the surface opposite to the adhesive layer 2) may be subjected to surface treatment such as releasability improvement treatment.

＜Substrate＞ The substrate 1 of this embodiment is not particularly limited. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, biaxial Stretched polypropylene, polyimide, aliphatic polyimide (transparent polyimide), polycyclic olefin, fluorine-based resin, polyolefin resin and other resin films. In addition, depending on the application, for the substrate 2, for example, a composite film laminated with polyethylene terephthalate and polyolefin resin film can also be used, and the composite film is further laminated with the resin film. Films, resin films that are multi-layered by co-extrusion, etc. Among them, as the base material 1, from the viewpoint of versatility, it is particularly preferable to use a material containing polyethylene terephthalate as the main component. The thickness of the substrate is preferably in the range of 12 to 200 μm, more preferably in the range of 25 to 100 μm.

＜Adhesive layer＞ The adhesive layers 2 and 3 of this embodiment contain addition reaction type silicone resin as a main component. Specifically, the above-mentioned addition reaction type polysiloxane-based resin includes a polysiloxane (G) containing an organopolysiloxane having an alkenyl group bonded to a silicon atom and a polysiloxane (G) that does not have a silicon atom bonded The polysiloxane resin (R) of the alkenyl organopolysiloxane is blended into a resin whose mass ratio (G)/(R) is in the range of 35/65 to 100/0. Hereinafter, each component constituting the adhesive layers 2 and 3 will be described in detail.

[Addition reaction type polysiloxane resin] Addition reaction type polysiloxane resin includes polydimethylsiloxane containing polydimethylsiloxanes containing alkenyl groups bonded to silicon atoms, etc. Silicone rubber (G), and polysiloxane resin (R) containing organopolysiloxanes such as polydimethylsiloxane which does not contain alkenyl groups bonded to silicon atoms, are blended to the mass ratio ( G)/(R) is a resin in the range of 35/65 to 100/0. In addition, the above-mentioned addition reaction type polysiloxane-based resin is designed so that the content of the alkenyl group bonded to the silicon atom is in the range of 1.0×10 ^-5 to 1.0×10 ^-3 mol/g.

When the content of the alkenyl group bonded to the silicon atom is less than 1.0×10 ^-5 mol/g, the cross-linking/hardening of the adhesive layers 2 and 3 is likely to become insufficient, and the cross-linking density also becomes low. As a result, the storage modulus of the adhesive layers 2 and 3 at 200°C under a He environment will decrease, so the amount of outgassing will increase, and the appearance of the film-formed functional film may deteriorate. In addition, the cohesive force of the adhesive layers 2 and 3 is also reduced. Therefore, when the adhesive tapes 10 and 20 are peeled off after film formation, there is a risk of adhesive residue on the film substrate. On the other hand, when the content of the alkenyl group bonded to the silicon atom exceeds 1.0×10 ^-3 mol/g, the crosslinking/hardening of the adhesive layers 2 and 3 is likely to proceed excessively, and the crosslinking density is also excessively increased. As a result, the adhesive force of the adhesive layers 2 and 3 is extremely reduced, so the temporary fixing force of the thin film substrate may be insufficient, and the thin film substrate may fall off during film formation.

In the following, the addition reaction type polysiloxane-based resin contained in the addition reaction type polysiloxane-based resin contains polydimethylsiloxanes containing alkenyl groups bonded to silicon atoms and other organopolysiloxanes (G ), and polysiloxane resin (R) containing organopolysiloxanes such as polydimethylsiloxane that does not contain alkenyl groups bonded to silicon atoms. Furthermore, in the following description, the polysiloxane (G) containing organopolysiloxanes such as polydimethylsiloxanes containing alkenyl groups bonded to silicon atoms is expressed as containing silicon atoms. The alkenyl-based polysilicone (G), or only expressed as polysilicone (G). Similarly, polysiloxane resins (R) containing organopolysiloxanes, such as polydimethylsiloxanes that do not contain alkenyl groups bonded to silicon atoms, are expressed as containing polydimethylsiloxanes, etc. The silicone resin (R) of the organopolysiloxane, or simply the case of the silicone resin (R).

[Polysiloxane gel (G) containing organopolysiloxanes such as polydimethylsiloxane and other alkenyl groups bonded to silicon atoms] This embodiment includes alkenyl groups bonded to silicon atoms Polysiloxane (G) of organopolysiloxane such as polydimethylsiloxane, etc., as long as it is used in addition reaction type polysiloxane adhesive or addition reaction type polysiloxane peeling agent , That is, one molecule containing at least two alkenyl groups bonded to silicon atoms in an average molecule is not particularly limited. Specifically, for the above-mentioned polysilicone (G), the content of the alkenyl group bonded to the silicon atom is in the range of 1.0×10 ^-6 to 1.0×10 ^-1 mol/g. For the adhesive layer 2, From the viewpoint of 3 storage modulus control, it is better to use the range of 2.0×10 ^-6 to 1.0×10 ^-2 mol/g. The above-mentioned silicone rubber (G) can be used alone in such a way that the content of the alkenyl group in the above-mentioned addition reaction type silicone resin is in the range of 1.0×10 ^-5 to 1.0×10 ^{-3 mol/g} Use or combine two or more types.

The above-mentioned molecular structure of organopolysiloxanes such as polydimethylsiloxanes containing alkenyl groups bonded to silicon atoms, for example, include straight-chain structures containing repeating diorganosiloxane units in the main chain , A part of the molecular structure includes a branched chain structure, a branched chain structure, or a ring structure. Among them, from the viewpoint of physical properties such as the mechanical strength of the adhesive, the organic polysiloxane having a linear structure is particularly preferred.

The above-mentioned silicone rubber (G) containing organopolysiloxane containing alkenyl groups bonded to silicon atoms may be in the form of oil or raw rubber, preferably in the form of raw rubber. When the above-mentioned silicone rubber (G) is oily, the viscosity of the silicone rubber (G) containing organopolysiloxane is preferably 1,000 mPa･s or more at 25°C. When the above-mentioned viscosity is less than 1000 mPa·s, the adhesive layers 2 and 3 may not exhibit the desired adhesive properties or physical properties, or the adhesion between the adhesive layers 2 and 3 and the substrate 1 may be poor. When the above-mentioned silicone rubber (G) is in the form of raw rubber, the viscosity when the silicone rubber (G) containing organopolysiloxane is dissolved in toluene in a concentration of 30% by mass, preferably at 25°C Below 100,000mPa･s. When the above-mentioned viscosity exceeds 100,000 mPa･s, it may become difficult to stir when preparing the adhesive composition, or it may become difficult to apply uniformly. Furthermore, the above-mentioned viscosity can be measured using a BM type rotary viscometer.

Polysiloxane (G) containing organopolysiloxane containing alkenyl groups bonded to silicon atoms, for example, those represented by the following general formula (1) or general formula (2), but not limited to these Wait.

Here, in the above general formulas (1) and (2), R ¹ is a monovalent hydrocarbon group having no aliphatic unsaturated bond independently of each other, and X is an alkenyl group-containing organic group. a is an integer of 0~3, m is an integer of 0 or more, and n is an integer of 100 or more, but a and m are not equal to 0 at the same time. m+n is to make the viscosity of the above-mentioned organopolysiloxane at 25°C become 1,000 mPa･s or more.

The above-mentioned R ^{1 is} preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, which does not have an aliphatic unsaturated bond. For example, alkyl groups such as methyl, ethyl, propyl, and butyl groups; cycloalkyl groups such as cyclohexyl groups; and aryl groups such as phenyl groups and tolyl groups. Particularly preferred are methyl groups or phenyl groups.

The above-mentioned X is preferably an alkenyl group-containing organic group having 2 to 10 carbon atoms. For example, vinyl, allyl, hexenyl, octenyl, acryloyl propyl, acryloyl methyl, methacryloyl propyl, acryloyloxypropyl, acryloyloxymethyl Group, methacryloxypropyl, methacryloxymethyl, cyclohexenylethyl, vinyloxypropyl, etc. Among them, lower alkenyl groups such as vinyl, allyl, and hexenyl are particularly preferred. From an industrial viewpoint, vinyl is particularly preferred, and from the viewpoint of crosslinkability, hexenyl is particularly preferred. The bonding position of the aforementioned alkenyl group is not particularly limited, and it may be the end of the molecular chain, the side chain of the molecular chain, or both the end of the molecular chain and the side chain of the molecular chain.

The number of alkenyl groups mentioned above depends on the content or content of polysiloxane resin (R) containing polydimethylsiloxane and other organopolysiloxanes contained in the addition reaction type polysiloxane adhesive. The addition amount of the coupling agent or the balance of other added components may vary in its proper range, so it cannot be generalized. For example, relative to 100 organic groups of organopolysiloxane, the range of 0.02~3.0 is usually better. In addition, it is preferable to adjust the molecular weight in the range of the ratio so as to be in the range of the above-mentioned viscosity, and to adjust the number of the above-mentioned alkenyl groups in 1 molecule of the organopolysiloxane to be at least two on average.

When the number of the above-mentioned alkenyl groups is less than 0.02 relative to 100 organic groups of the organopolysiloxane, the crosslinking/hardening of the adhesive layers 2 and 3 is likely to become insufficient, and the crosslinking density also changes low. As a result, the storage modulus of the adhesive layers 2 and 3 at 200°C under the He environment will decrease, so the amount of outgassing will increase, and the cohesive force will decrease. At this time, the appearance of the functional film formed into a film may deteriorate, or the adhesive tape 10 and 20 may be peeled off after the film formation, and the adhesive may remain on the film substrate. On the other hand, when the number of the above-mentioned alkenyl groups exceeds 3.0 relative to 100 organic groups of the organopolysiloxane, the crosslinking/hardening of the adhesive layers 2 and 3 will proceed excessively, and the crosslinking density will also be excessively high. Increase. As a result, the adhesive strength of the adhesive layers 2 and 3 may be extremely reduced. At this time, the temporary fixing force of the film substrate is insufficient, and the film substrate may fall off during film formation.

Specific examples of the above-mentioned polysiloxane (G) containing alkenyl groups bonded to silicon atoms include dimethylpolysiloxane and molecular chain end capped with dimethylvinylsiloxy groups at both ends of the molecular chain. Dimethylsiloxane/methylvinylsiloxane copolymer with both ends blocked by dimethylvinylsiloxane groups, dimethylsiloxane with both ends of the molecular chain blocked by dimethylvinylsiloxane groups Silicone/methyl phenyl siloxane copolymer, methyl phenyl polysiloxane with both ends of the molecular chain blocked by dimethyl vinyl siloxane, and both ends of the molecular chain with trimethyl siloxane End-capped dimethylsiloxane/methylvinylsiloxane copolymer, dimethylsiloxane/methylvinylsiloxane/methanone in which both ends of the molecular chain are blocked by trimethylsiloxy groups Phenylsiloxane copolymer, dimethylsiloxane/methylhexenylsiloxane copolymer with both ends of the molecular chain capped with trimethylsilyloxy, and both ends of the molecular chain with dimethylethylene Dimethylsiloxane/methylhexenylsiloxane copolymer terminated by silyloxy group, dimethylsiloxane/methysiloxane terminated by dimethylhexenylsiloxy group at both ends of the molecular chain Hexenyl siloxane copolymer, etc.

[Polysiloxane resin (R) containing organopolysiloxane such as polydimethylsiloxane] The polysiloxane resin containing organopolysiloxane such as polydimethylsiloxane in this embodiment (R) is an ^{organopolysiloxane having R 2} ₃ SiO _0.5 unit (M unit) and SiO ₂ unit (Q unit), which is called a so-called MQ resin. The polysiloxane resin (R) containing organopolysiloxane such as polydimethylsiloxane basically does not have an alkenyl group in the molecule, and conventionally known ones can be used. R ² is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include those exemplified as R ¹ above. The aforementioned organopolysiloxane preferably ^{contains R 2} ₃ SiO _0.5 unit and SiO ₂ unit so that ^{the molar ratio of R 2} ₃ SiO _0.5 unit/SiO ₂ unit is in the range of 0.5 or more and 1.7 or less. When ^{the molar ratio of R 2} ₃ SiO _0.5 unit/SiO ₂ unit is less than 0.5, the adhesion or tack of the resulting adhesive layer 2 and 3 may decrease, and the temporary fixing force of the film substrate may be insufficient , The thin film substrate may fall off during film formation. On the other hand, ^{when the molar ratio of R 2} ₃ SiO _0.5 unit/SiO ₂ unit exceeds 1.7, the adhesion or retention of the resulting adhesive layer 2 may decrease, and the temporary fixing force of the film substrate may be insufficient, and the result is The thin film substrate in the film may fall off. Furthermore, the organopolysiloxane may have an OH group. In this case, the content of the OH group is preferably 4.0% by mass or less relative to the total mass of the organopolysiloxane. When the content of OH group exceeds 4.0% by mass, low molecular weight components such as low molecular weight silanol or cyclic silicone are likely to be produced. Therefore, the amount of outgas generation increases, and the appearance of the film-forming functional film may deteriorate.

The above-mentioned polysiloxane resin (R) containing organopolysiloxane such as polydimethylsiloxane can be used alone or in combination of two or more. ^{In addition, the aforementioned organopolysiloxane may have R 2} SiO _1.5 units (T units) and/or R ² ₂ SiO units (D units) within a range that does not impair the characteristics of the present invention.

The above-mentioned polysilicone (G) containing organopolysiloxane containing alkenyl groups bonded to silicon atoms, etc., and organopolysiloxane containing polydimethylsiloxane, etc. Polysiloxane resin (R) of alkane can also be used simply by mixing. In addition, the silicone rubber (G) containing organopolysiloxanes such as polydimethylsiloxanes which are bonded to silicon atoms, when containing the organopolysiloxanes represented by the above general formula (2) In the case of alkane, as long as the characteristics of the present invention are not impaired, it is possible to use polysiloxane (G) containing organopolysiloxanes such as polydimethylsiloxanes containing alkenyl groups bonded to silicon atoms and It is used in the form of a (partial) condensation reaction product obtained by pre-reacting polysiloxane resin (R) containing organopolysiloxane such as polydimethylsiloxane.

[The mass ratio (G)/(R) of silicone rubber (G) and silicone resin (R) contained in the adhesive layer of this embodiment] The mass ratio (G)/(R) of polysiloxane (G) to polysiloxane resin (R) in the addition reaction type polysiloxane resin contained in the adhesive layers 2 and 3 of this embodiment , Is in the range of 35/65 to 100/0, preferably in the range of 50/50 to 70/30. Here, when two or more kinds of silicone rubbers (G) are used in combination, the total amount of the respective silicone rubbers is regarded as the polysilicone (G) in the addition reaction type silicone resin quality. Similarly, when two or more types of silicone resins (R) are used in combination, the total amount of the respective silicone resins is also regarded as the silicone resin (R) in the addition reaction type silicone resin. the quality of.

When the mass ratio (G)/(R) of silicone rubber (G) and silicone resin (R) contained in the adhesive layers 2 and 3 of this embodiment does not reach the lower limit of the above range, it is also That is, when the content of polysilicone (G) is small, especially when the content of alkenyl groups bonded to silicon atoms of polysilicone (G) is small, the crosslinking/hardening of adhesive layers 2 and 3 is easy It becomes insufficient, and the crosslink density also becomes lower. As a result, the storage modulus of the adhesive layers 2 and 3 at 200°C under a He environment will decrease, so the amount of outgassing will increase, and the amount of polysiloxane (R) will increase, and the cohesive force will also decrease. At this time, the appearance of the film-formed functional film may deteriorate, or the adhesive may remain on the film substrate when the adhesive tapes 10 and 20 are peeled off after film formation. In addition, even if the content of the alkenyl group bonded to the silicon atom of the silicone rubber (G) is within the preferred range of the present invention, the amount of the silicone resin (R) still increases, so the adhesive force becomes too large. When the adhesive tapes 10 and 20 are peeled off after film formation, the film substrate may be damaged or the adhesive may remain on the film substrate.

In contrast to this, the mass ratio (G) of the polysiloxane (G) to the polysiloxane resin (R) in the addition reaction type polysiloxane resin contained in the adhesive layers 2 and 3 of this embodiment )/(R) is in the above range, and the content of the alkenyl group bonded to the silicon atom of the addition reaction type polysiloxane resin is in the above range of 1.0×10 ^-5 to 1.0×10 ^-3 mol/g , It can be in the adhesive layer. The storage modulus measured at 200℃ under He environment is designed to be 1.0×10 ⁵ ~1.0×10 ⁷ Pa. In the adhesive tape 10 and 20, the vacuum degree is 1.0×10 ^{In an} environment below -4 Torr, after heating up from 23°C to 200°C at a heating rate of 10°C/min, and then maintaining it at 200°C for 30 minutes, it is easy to suppress and control the total amount of outgassed to less ^{than 180mg/m 2} . As a result, the following effects can be achieved. That is, the first effect is the temporary fixing force that can ensure that the film substrate such as cover glass will not fall off during the film formation of the functional film, and it can also suppress the increase of the adhesive force under high vacuum/high temperature. The second effect is that the effect of outgassing can be suppressed, and the appearance and characteristics of the formed functional film, such as an anti-reflection film, can be improved. The third effect is that the film substrate after film formation can be peeled off from the carrier glass substrate or the like without causing damage or adhesive residue.

In addition, the addition reaction type silicone resin of the present invention can also use a commercially available addition reaction type silicone resin which has mixed most of silicone rubber (G) and silicone resin (R). Resin or commercially available silicone rubber (G). Commercially available addition reaction type silicone resins, for example, KR-3700, KR-3701, KR-3704, X-40-3237-1, X-40-3240, KR-3700, KR-3704, KR-3704, X-40-3237-1, X-40-3240, KR-3700 manufactured by Shin-Etsu Chemical Co., Ltd. X-40-3291-1, X-40-3270, X-40-3306, KSN-320A, KSN-3002, KS-776L, KS-841, KS-3601, KS-830E, X-62-2825, X-62-2829, X-92-128 (all trade names), or TSR1512, TSR1516, XR37-B9204, TSE-201, XE-25-511, SL6210, SL6510, SL6562, SL6962 manufactured by Momentive Performance Materials , SL6062, SL6162 (all trade names), or SD4580, SD4584, SD4585, SD4586, SD4587L, SD4560, SD4570, SD4600FC, SD4593, DC7651ADHESIVE, SRX357, BY23-749, SRX211, SD7320, manufactured by Toray Dow Corning Co., Ltd. BY24-312, LTC-310, LTC-450A, LTC-750A, SD7292, BY-15-701A (trade name), etc. As long as these are based on the mass ratio (G)/(R) of the polysilicone (G) to the polysilicone (R) in the addition reaction type polysiloxane resin, and the alkenyl group bonded to the silicon atom As for the content of the above-mentioned aspect of the present invention, one type may be used alone or two or more types may be used in combination. Furthermore, for the addition reaction type polysiloxane-based resin in the form of SD4600FC manufactured by Toray Dow Corning Corporation, etc., without the crosslinking agent described later, it is only necessary to add the crosslinking agent to the adhesive layer afterwards. For use as a combination agent, the storage modulus at 200°C measured in a He environment should be within the range ^{of 1.0×10 5} to 1.0×10 ^{7 Pa.}

[Crosslinking agent] The cross-linking agent in this embodiment is used to cross-link the alkenyl group bonded to the silicon atom of the polysilicone (G) contained in the addition reaction type silicone resin. As the crosslinking agent, an organopolysiloxane (organohydrogenpolysiloxane) having at least two, preferably three or more hydrogen atoms (SiH) bonded to silicon atoms in one molecule is used. In addition, in the following description, the organopolysiloxane having a hydrogen atom (SiH) bonded to a silicon atom may only be expressed as an organohydrogenpolysiloxane.

The molecular structure of the organohydrogenpolysiloxane used as the above-mentioned crosslinking agent includes, for example, a linear shape; a linear shape with a part of branches, a branched chain shape, and a network shape are exemplified. Organohydrogen polysiloxane, the viscosity at 25°C is preferably in the range of 1~5,000mPa･s. Furthermore, the above-mentioned viscosity can be measured using a BM type rotary viscometer.

As the organohydrogenpolysiloxane used as the above-mentioned crosslinking agent, conventionally known ones can be used. For example, the organohydrogenpolysiloxane may include those represented by the following general formula (3) or (4), but it is not limited to these.

Here, in general formula (3) and general formula (4), R ³ is a monovalent hydrocarbon group with a carbon number of 1 to 10, b is 0 or 1, p and q are integers, so that the organohydrogen polysiloxane The viscosity at 25°C becomes 1~5,000mPa･s. r is an integer of 2 or more, s is an integer of 0 or more, and r+s≧3, preferably 8≧r+s≧3. The organohydrogenpolysiloxane can also be a mixture of two or more kinds.

The above-mentioned R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, and butyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl and tolyl; and alkenyl groups such as vinyl and allyl. Particularly preferred is methyl or phenyl.

The content of the organohydrogenpolysiloxane used as the above-mentioned crosslinking agent depends on the content of the alkenyl group bonded to the silicon atom with the polysiloxane (G) and the bonding of the organohydrogenpolysiloxane The proper range of the content of hydrogen atoms in silicon atoms varies, so it cannot be generalized, but usually, for example, compared to organopolysilicon containing polydimethylsiloxanes containing alkenyl groups bonded to silicon atoms, etc. In terms of the total amount of alkenyl groups in the silicone rubber (G) of the oxane, it is preferable to make the molar ratio (SiH) of the total amount of hydrogen atoms (SiH) bonded to the silicon atoms in the organohydrogen polysiloxane The amount in the range of 0.15 to 15.0, more preferably in the range of 0.5 to 10.0, and most preferably in the range of 1.5 to 5.0.

When the content of organohydrogenpolysiloxane does not reach the above lower limit, the cross-linking/hardening of the adhesive layers 2 and 3 is insufficient, and the storage modulus at 200°C under He environment will decrease, so the amount of outgassing will increase. , The cohesive force will also decrease. At this time, the appearance of the functional film formed into a film may deteriorate, or the adhesive may remain on the film substrate when the adhesive tapes 10 and 20 are peeled off after film formation. On the other hand, when the content of organohydrogenpolysiloxane exceeds the above upper limit, there will be residual hydrogen atoms (SiH) bonded to silicon atoms (Si-OH) when the dehydration condensation reaction is carried out during film formation. The generated moisture becomes outgassing, and the appearance of the film-formed functional film may deteriorate. In addition, the adhesion force with the film substrate is increased, and when the adhesive tapes 10 and 20 are peeled off after film formation, the film substrate may be damaged or the adhesive may remain on the film substrate.

The content of the crosslinking agent in the adhesive layers 2 and 3 of this embodiment, as described above, is as long as it is relative to the organopolysiloxane containing polydimethylsiloxane and the like containing alkenyl groups bonded to silicon atoms. In terms of the total amount of alkenyl groups in the silicone rubber (G), the total amount of hydrogen atoms (SiH) bonded to silicon atoms in the organohydrogen silicone is within the range of 0.15 to 15.0 mol equivalents mentioned above You can adjust it in the same way. If the preferred content of the cross-linking agent that satisfies this range is expressed as added mass parts, the appropriate range is based on the balance of the number of hydrogen atoms (SiH) bonded to silicon atoms of the cross-linking agent, etc. It may vary, so it is impossible to generalize, but usually, for example, relative to 100 parts by mass of the solid content of the addition reaction type silicone resin, it is only necessary to add a crosslinking agent so that the solid content is in the range of 0.1 to 15.0 parts by mass. can.

Compared with the addition reaction type silicone resin, by making the content of the crosslinking agent within the above-mentioned range of 0.15 to 15.0 mol equivalents, the alkenyl group of the silicone rubber (G) and the SiH group of the crosslinking agent In the meantime, the hydrosilation reaction, that is, the cross-linking/hardening of the adhesive layers 2 and 3, will proceed sufficiently to make the cohesive force and the storage modulus of 200°C under He environment appropriate. In addition, it can be of a level that the amount of excess remaining SiH groups does not cause adverse effects on the adhesive layers 2 and 3 as described above.

In a preferred aspect, the number of hydrogen atoms bonded to silicon atoms contained in the adhesive layer is adjusted to be more than the number of alkenyl groups bonded to silicon atoms. At this time, the content of the alkenyl group bonded to the silicon atom corresponds to the amount of crosslinking, so it is easy to adjust the storage modulus appropriately.

Therefore, the adhesive tapes 10 and 20 provided with the adhesive layers 2 and 3 containing the crosslinked/hardened addition reaction type polysiloxane resin are used as vacuum film formation by sputtering, vapor deposition, etc. The tape for temporary fixing of the film substrate during the process of forming a functional film on the film substrate can reduce the amount of outgassing from the adhesive tapes 10 and 20, so that the appearance of the film-formed functional film can be improved. In addition, when the adhesive tapes 10 and 20 are peeled off after film formation, it is possible to greatly suppress the occurrence of damage to the film substrate or the residue of the adhesive on the film substrate.

As a cross-linking agent, as long as it is used as a cross-linking agent for addition reaction type polysiloxane resin, that is, an organopolysilicon with at least two hydrogen atoms (SiH) bonded to silicon atoms in a molecule Oxyane (organohydrogen polysiloxane) is sufficient, and it is not particularly limited. Specifically, for example, X-92-122 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., BY24-741 (trade name) manufactured by Toray Dow Corning Co., Ltd., etc. can be cited.

[catalyst] In order to carry out the hydrosilation reaction between the alkenyl group of the silicone rubber (G) in the addition reaction type silicone resin and the SiH group of the crosslinking agent, a platinum group metal catalyst is necessary. The center metal of the catalyst includes, for example, platinum, palladium, iridium, rhodium, osmium, ruthenium, etc., among which platinum is particularly suitable. The platinum-based catalyst is not particularly limited. For example, chloroplatinic acid, an alcohol solution of chloroplatinic acid, a reactant of chloroplatinic acid and alcohol, a reactant of chloroplatinic acid and an alkene compound, and chloroplatinic acid can be mentioned. Reactants with vinyl-containing silicones, etc. For the platinum-based catalysts, commercially available catalysts can also be used. Commercially available catalysts include, for example, CAT-PL-50T manufactured by Shin-Etsu Chemical Co., Ltd., or SRX-212Cat and NC-25 manufactured by Toray Dow Corning Co., Ltd. The content of the platinum group metal-based catalyst is not particularly limited, and it is preferable that the mass of the metal is in the range of 1 to 500 ppm relative to the mass of the silicone rubber (G). When the metal mass is less than 1ppm, the reaction is slow, the crosslinking/hardening of the adhesive layer 2, 3 is insufficient, the storage modulus at 200°C under He environment will decrease, so the amount of outgassing will increase, and the cohesive force will also decrease. . At this time, the appearance of the film-formed functional film may deteriorate, or the adhesive may remain on the film substrate when the adhesive tape 10 is peeled off after the film is formed. On the other hand, when the metal mass exceeds 500 ppm, the solution containing the resin composition of the addition reaction type polysiloxane resin may increase viscosity or gel. In addition, the cost becomes high and uneconomical.

[Reaction Delay Agent] In the resin composition containing the addition reaction type silicone resin of this embodiment, a reaction retarder can be optionally added. The reaction retarder is an optional component added to the resin composition in order to prevent the addition reaction from starting the addition reaction before heating and hardening and the solution to thicken or gel when the solution of the above-mentioned resin composition is prepared or applied to the substrate. In the solution of the substance, the platinum group metal is coordinated in the addition reaction catalyst to inhibit the addition reaction. When heating is used to harden the coated adhesive layer, the coordination is removed and the catalyst activity is exhibited. The hydrosilation reaction proceeds. The above-mentioned reaction retarder can be used as a reaction retarder such as 1-ethynylcyclohexanol which has been used in addition reaction type silicone adhesives. As the above-mentioned retarder, a commercially available reaction retarder may also be used. Examples of commercially available reaction delay agents include CAT PLR-2 manufactured by Shin-Etsu Chemical Co., Ltd., BY24-808 manufactured by Toray Dow Corning Co., Ltd., and the like. The content of the reaction delay agent is not particularly limited, and it is preferably in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of the silicone rubber (G). When the addition amount of the reaction delay agent is less than 0.01 parts by mass, the reaction cannot be suppressed, and the solution containing the resin composition of the addition reaction type polysiloxane resin may increase viscosity or gel. On the other hand, when the addition amount of the reaction delay agent exceeds 5 parts by mass, the reaction may become slower and the crosslinking/curing may be insufficient.

[Thickness] The thickness of the adhesive layers 2 and 3 is not particularly limited, but when the thickness of the adhesive layers 2 and 3 is increased, of course, the amount of outgassing under high vacuum and high temperature tends to increase. Therefore, in an environment with a vacuum degree of 1.0×10 ^-4 Torr or less, the adhesive tapes 10 and 20 are heated from 23°C to 200°C at a heating rate of 10°C/min, and then maintained at 200°C for 30 minutes. The total amount of outgassing must be set below ^{180mg/m 2.} Depending on the balance of the storage modulus of the adhesive layers 2 and 3 at 200°C in a He environment, the appropriate range of the thickness of the adhesive layers 2 and 3 will vary, so it is impossible to generalize, but for example, usually the above-mentioned thickness The lower limit is preferably 3 μm or more, more preferably 10 μm or more from the viewpoint of securing temporary fixing power. On the other hand, the upper limit of the above-mentioned thickness is preferably 200μm from the viewpoints of suppression of the total amount of outgassing, suppression of uniform coating properties of the adhesive layer and residual solvent amount, and easy peelability of the adhesive tapes 10 and 20 Or less, more preferably 100 μm or less.

(Adhesive tape) The adhesive tape of this embodiment has a single-sided adhesive tape 10 with an adhesive layer 2 on one side of the substrate 1, and an adhesive layer 2 and an adhesive layer 3 on both sides of the substrate 1. Any form of the adhesive tape 20 is outgassed when the temperature is increased from 23°C to 200°C at a temperature rise rate of 10°C/min under a ^{vacuum of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total amount is 180 mg/m ² or less, more preferably 100 mg/m ² or less. When the total amount of outgas above exceeds 180mg/m ² , the existence of this outgas will hinder the original movement of atoms during the process of transporting or accumulating atoms from the target material of the film-forming material to the film-forming film substrate. The deposition of the flexible thin film affects the appearance and characteristics of the functional thin film formed on the thin film substrate by the vacuum process may deteriorate.

(Method of manufacturing adhesive tape) Next, taking the structure of the single-sided adhesive tape 10 illustrated in FIG. 1 as an example, an example of its manufacturing method will be described. The single-sided adhesive tape 10 can be manufactured in a roll shape in the same way as the conventional silicone adhesive tape, such as the silicone adhesive tape for plastic lens molding described in JP 2012-107125 A, etc. It is produced by laminating an adhesive layer 2 on one surface of the base material 1 and winding it into a roll-like original film.

＜Formation of Adhesive Layer＞ Firstly coat one side of the substrate 1 with a tackifier coating agent to improve the adhesion to the adhesive layer 2 and dry to form a tackifier coating, and then coat the tackifier coating for an addition reaction The resin composition (adhesive composition) for the adhesive layer 2 whose main component is silicone resin is solution and dried to form the adhesive layer 2. Then, the other side of the substrate 1 is coated with a releasability improvement treatment agent for the adhesive layer 2 and dried to form a releasable treatment layer, which is wound into a roll-shaped original adhesive tape film. Furthermore, it is not necessary to form the above-mentioned peeling treatment layer, that is, a peeling film is attached to the adhesive layer 2 and wound into a roll-shaped adhesive tape original film. To explain the formation of the adhesive layer 2 in more detail, firstly, a silicone resin (G) containing an alkenyl group and a silicone resin (R) not containing an alkenyl group bonded to silicon atoms are the main components. The adhesive is dissolved in a solution obtained by dissolving an organic solvent such as toluene and xylene, and a crosslinking agent, a catalyst, etc. are added to produce and prepare a resin composition solution for the adhesive layer 2. Then, the resin composition solution is applied to the adhesion-promoting coating of the substrate 1 with a Comma coater (registered trademark) or a lip coater to make the thickness after drying uniform. After that, by heating/drying the applied adhesive composition at a specific temperature, an adhesive layer 2 is formed on the substrate 1 with an adhesion-promoting coating layer therebetween. Through the above steps, the single-sided adhesive tape 10 shown in FIG. 1 is obtained. Furthermore, the adhesion-promoting coating and the peeling treatment layer are not shown in FIG. 1.

For the heating/drying conditions of the above-mentioned adhesive composition, for example, the conditions disclosed in the above-mentioned Japanese Patent Application Publication No. 2012-107125 can be referred to. Specifically, for example, the resin composition solution for coating the adhesive layer 2 on the substrate 1 through the adhesion-promoting coating is performed by gradually increasing the temperature in the first half of the drying oven at a temperature of 40 to 90°C. After the initial drying, heat and dry at the temperature range of 130~200℃ for 1~5 minutes in the rear half of the drying furnace, and then wind it into a roll-shaped original film. In particular, due to the heating and drying treatment of the half area after the drying furnace, the low molecular weight dimethylpolysiloxane contained in the material of the addition reaction type silicone resin from the beginning is processed according to the drying process. Under conditions, the self-adhesive layer 2 volatilizes and reduces, and promotes the hydrosilylation reaction of the polysilicone (G) in the addition reaction type silicone resin, so that the adhesive layer 2 is cross-linked/hardened. Here, the adhesive layer 2 of the single-sided adhesive tape 10 of the present embodiment is used as a vacuum process as described above to realize the alkenyl group of the polysilicone (G) in the addition reaction type silicone resin. And the optimization of the content of silicone rubber (G). Therefore, by the above heating and drying, compared with the conventional general silicone adhesive tape, the adhesive layer 2 can be highly cross-linked and structured. Increase the storage modulus of the adhesive layer 2 under high vacuum and high temperature, in other words, the storage modulus at 200°C measured in a He environment to the range of 1.0×10 ⁵ to 1.0×10 ⁷ Pa. That is, as described above, the movement of the molecular chains of silicone rubber (G) and silicone resin (R) is restricted by a high degree of cross-linking structure, which can inhibit the interaction between the main chain skeleton or the The interaction within the same framework can greatly suppress the new generation of low-molecular-weight components that are the cause of outgassing in the vacuum film forming process. As a result, even if the high-temperature and long-term annealing process of the adhesive sheet is not carried out as in the prior art, the single-sided adhesive tape 10 can be designed to have a vacuum degree of 1.0×10 ^-4 Torr easily by a roll-to-roll method. After heating up from 23°C to 200°C at a heating rate of 10°C/min in the following environment, and then maintaining at 200°C for 30 minutes, the total amount of outgas generated will be 180mg/m ² or less. Use this adhesive tape 10 as When the adhesive tape for temporary fixation when forming a functional thin film on a heat-resistant substrate by a vacuum film forming process such as sputtering, vapor deposition, etc., the outgassing from the adhesive tape 10 generated during the vacuum film forming process can be suppressed, and the The appearance of the obtained functional film became good. In addition, under the temporary fixing force that ensures that the film substrate will not fall off during the vacuum film formation, when the adhesive tape 10 is peeled off after film formation, the film substrate is greatly prevented from being damaged or the adhesive remains on the film substrate.

Next, taking the structure of the double-sided adhesive tape 20 illustrated in FIG. 2 as an example, an example of its manufacturing method will be described. Coat one side (1 side) of the substrate 1 with an adhesion promoter coating agent for improving the adhesion to the adhesive layer 3 and dry to form an adhesion promoter coating, and then apply on the adhesion promoter coating The resin composition solution for the adhesive layer 3 mainly composed of addition reaction type silicone resin is applied and dried to form the adhesive layer 3. Next, the first release film is attached to the surface of the adhesive layer 3 and wound into a roll-shaped original film. Further, in the same manner as the above method, on the other side (the second side) of the substrate 1 on which the adhesive layer 3 is formed, an adhesion-promoting coating layer and an adhesive layer 2 are formed, and the adhesive layer 2 is attached to the surface of the adhesive layer 2. 2. Peel off the film and wind it into a roll-shaped original film. Through the above steps, the double-sided adhesive tape 20 shown in FIG. 2 is obtained. The conditions for coating and drying may be set in the same manner as the above-mentioned conditions. In addition, in FIG. 2, the first and second release films are not shown.

(Temporary fixing method of film substrate to carrier substrate with adhesive tape) As described above, the adhesive tapes 10 and 20 of the present embodiment are applied on a thin film substrate represented by the cover glass of a smart phone in a vacuum film forming process using, for example, a rotating rack type sputtering device. When forming a functional thin film such as an anti-reflective film by the method, as shown in Figures 3 and 4, it is used to temporarily fix a plurality of cover glasses on a carrier substrate 11 made of glass, SUS, etc. Etc. of the film substrate 12. When the functional thin film is formed, the carrier substrate 11 temporarily fixed with the plurality of thin film substrates 12 is mounted on the rotating support of the rotating rack type sputtering device, and a film is formed on the surface of each thin film substrate 12 to form a resist Functional film such as reflective film. Next, an example of the temporary fixing method of the film substrate 11 using the single-sided adhesive tape 10 of this embodiment is demonstrated.

＜Temporary fixing method with single-sided adhesive tape 10＞ FIG. 5 is a diagram showing an outline 50 of an example of a temporary fixing method of the carrier substrate 11 using the single-sided adhesive tape 10 according to one embodiment of the present embodiment. First, on the carrier substrate 11, the release film of the single-sided adhesive tape 10 is peeled off, the single-sided adhesive tape 10 is placed so that the adhesive layer 2 becomes the upper side, and both ends of the single-sided adhesive tape 10 are placed. The strip-shaped single-sided adhesive tape 10 ′ (which can be the same as or different from the single-sided adhesive tape 10) of this embodiment is used to attach to the carrier substrate 11 to fix the carrier substrate 11 and the single-sided adhesive tape 10. Then, on the surface of the adhesive layer 2 of the single-sided adhesive tape 10, a plurality of thin film substrates 12 (temporarily fixed) are placed and attached at equal intervals to form a film in a vacuum process.

FIG. 6 is a diagram showing an outline 60 of another example of the temporary fixing method of the film substrate using the single-sided adhesive tape 10 of the embodiment. First, the second release film on the side of the adhesive layer 3 is peeled off, and on the carrier substrate 11, two strip-shaped double-sided adhesive tapes 20 of this embodiment are attached in parallel. Next, peel off the first release film on the adhesive layer 2 side of the double-sided adhesive tape 20, and apply the adhesive layer 2 of the single-sided adhesive tape 10 (with release film) on the side of the adhesive layer 2 of the double-sided adhesive tape 20 The single-sided adhesive tape 10 is attached so as to be the upper side. Next, peel off the release film on the adhesive layer 2 side of the single-sided adhesive tape 10, and place and attach a plurality of film substrates 12 at equal intervals on the surface of the adhesive layer 2 of the single-sided adhesive tape 10 (temporary fixation) , Carry out the film formation of the vacuum process.

＜Temporary fixing method with adhesive tape 20 on both sides＞ FIG. 7 is a diagram showing an outline 70 of an example of a temporary fixing method of the film substrate 11 using the double-sided adhesive tape 20 of another aspect of the present embodiment. First, the first release film on the side of the adhesive layer 3 is peeled off, and the double-sided adhesive tape 20 is attached on the carrier substrate 11. Then, peel off the second release film on the adhesive layer 2 side of the double-sided adhesive tape 20, place and attach a plurality of film substrates 12 (temporarily fixed) at equal intervals on the surface of the adhesive layer 2 of the double-sided adhesive tape 20, Carry out vacuum process for film formation.

FIG. 8 is a diagram showing an outline 80 of another example of the temporary fixing method of the film substrate 11 using the double-sided adhesive tape 20 of another aspect of the present embodiment. First, the double-sided adhesive tape 20 is punched into the same size as the film substrate 11. Then, the second release film on the side of the adhesive layer 3 is peeled off, and the double-sided adhesive tape 20 that has been stamped is attached to the carrier substrate 11 at equal intervals. Then, peel off the first release film on the adhesive layer 2 side of the double-sided adhesive tape 20, and attach a plurality of film substrates 12 (temporarily fixed) to the adhesive layer 2 side of the double-sided adhesive tape 20, and perform the vacuum process The film formation.

(Film formation of functional thin film by vacuum process) There are no special restrictions on the film formation method of functional thin film such as anti-reflective film by vacuum process. For example, vacuum vapor deposition method, ion beam assisted vapor deposition method, ion Plating method, sputtering method, etc. Among these, the sputtering method is particularly suitable from the viewpoint of the hardness or adhesion of the functional film obtained. In a sputtering method using a rotating rack type sputtering device, etc., the carrier substrate 11 temporarily fixed with a plurality of thin film substrates 12 as illustrated in FIGS. 5 to 8 is placed in the vertical position as shown in FIGS. 3 and 4 30, 40 After mounting/placement on the substrate holder arranged on the rotating drum of the rotating rack type sputtering device, the carrier substrate 11 (thin film substrate 12) is heated to a temperature of, for example, 150 to 200°C, and the chamber becomes The pressure is around 10 ^-5 ~10 ^{-6 Torr.} Next, the chamber is directed toward the thin film substrate 12 maintaining the vertical posture rotating along the circular orbit, and the material of the functional thin film (atoms constituting the target) is scattered by sputtering from the target disposed on the outer side of the circular orbit. On the surface and side surfaces of the film substrate 12 facing the outer side of the circular orbit, a material as a functional thin film is deposited to form a desired functional thin film. The above functional film, in addition to the anti-reflection film, includes an anti-glare film, an anti-fouling film, a colored film, a wear resistance imparting film, a corrosion resistance imparting film, a conductivity imparting film, a reinforcing film, an infrared reflective film, etc. A thin film formed by a vacuum process.

(How to peel off the adhesive tape after film formation) Next, the peeling method of the adhesive tape after film formation is explained. After cooling the chamber and returning the pressure to atmospheric pressure, the carrier substrate 11 temporarily holding the film-forming substrate 12 is removed from the substrate holder. When the film substrate 12 is temporarily fixed by the single-sided adhesive tape 10 as shown in Figure 5, first, peel off the single-sided adhesive tape 10' at both ends of the single-sided adhesive tape 10, and temporarily fix the film with the film-forming process. With the substrate 12 in the state, the single-sided adhesive tape 10 is removed from the carrier substrate 11. Finally, while taking care not to damage the film substrate 12, the single-sided adhesive tape 10 is peeled off from the film substrate 12 subjected to the film forming process. At this time, the film-forming processing surface of the film substrate 12 may be vacuum sucked on a clean platform, and the single-sided adhesive tape 10 may be peeled off from the film-forming processing surface of the film substrate 12. Through the above, a thin film substrate 12 on which an organic thin film is formed is obtained.

When the film substrate 12 is temporarily fixed by the single-sided adhesive tape 10 as shown in FIG. 6, first, the single-sided adhesive tape 10 is removed from the double-sided adhesive tape 20 with the film substrate 12 temporarily fixed to the film-forming process. Peel slowly. Finally, while taking care not to damage the film substrate 12, the single-sided adhesive tape 10 is peeled off from the film substrate 12 subjected to the film forming process. At this time, the film-forming processing surface of the film substrate 12 may be vacuum sucked on a clean platform, and the single-sided adhesive tape 10 may be peeled off from the film-forming processing surface of the film substrate 12. Through the above, a thin film substrate 12 on which an organic thin film is formed is obtained.

As shown in Figures 7 and 8, when the film substrate 12 is temporarily fixed by the adhesive tape 20 on both sides, the carrier substrate 11 is vacuum-adsorbed on the clean platform and placed on the corners of the film substrate 12 after the film formation process. Between the adhesive layer 2 of the double-sided adhesive tape 20, a sharp stainless steel knife is slowly inserted to impart a peeling force between the film substrate 12 and the adhesive layer 2. Next, using a vacuum suction pad, slowly pull up from the corner of the film substrate 12 to peel off the film substrate 12 after the film formation process from the adhesive layer 2. Even if the power for peeling is not provided, the case where peeling can be performed using only a vacuum suction pad is not limited to this. Through the above, a thin film substrate 12 on which an organic thin film is formed is obtained. [Example]

Next, examples and comparative examples are used to explain the present invention more specifically. In addition, the present invention is not limited to the following examples. Hereinafter, each embodiment and each comparative example will be described in detail.

In order to prepare the various adhesives used in the present examples and comparative examples, the following polysiloxane resins (A) to (D), which are the main components of the adhesive, and the following crosslinking agents, are bonded to The organopolysiloxane (organohydrogenpolysiloxane) of the hydrogen atom (SiH) of the silicon atom. Silicone resins (A) and (B) are a mixture of silicone rubber (G) and silicone resin (R) [(G)/(R) mass ratio=40/60], the silicone Glue (G) is a dimethylsiloxane/methylvinylsiloxane copolymer in which both ends of the molecular chain with a polymerization average molecular weight (Mw) of about 500,000 are terminated by dimethylvinylsiloxane groups; this Polysiloxane resin (R) is an organopolysiloxane (MQ resin) ^{with R 2} ₃ SiO _0.5 unit (M unit) and SiO ₂ unit (Q unit) with a polymerization average molecular weight (Mw) of about 5000. In addition, silicone resins (C) and (D) are separate resins of silicone rubber (G), and silicone resin (G) of silicone resin (C) uses a polymer average molecular weight ( Mw) Dimethylsiloxane/methylhexenylsiloxane copolymer of approximately 200,000 molecular chains terminated by dimethylhexenylsiloxy; polysiloxane resin (D) Polysilicone (G), using dimethyl siloxane/methyl hexenyl silicon with a polymer average molecular weight (Mw) of about 600,000 molecular chains terminated by dimethyl hexenyl silalkoxy at both ends Oxyalkylene copolymers. Furthermore, the silicone resin (E) is a single resin of the silicone resin (R), and the silicone resin (R) uses a polymer average molecular weight (Mw) of about 5000 with R ² ₃ SiO _0.5 unit (M unit) and SiO ₂ unit (Q unit) of organopolysiloxane (MQ resin).

・Polysiloxane resin (A), polysiloxane glue (G)/polysiloxane resin (R) = 40% by mass/60% by mass, alkenyl (vinyl) content: 2.0×10 ^-5 mol/g

・Polysiloxane resin (B), polysiloxane glue (G)/polysiloxane resin (R)=40% by mass/60% by mass, alkenyl (vinyl) content: 2.0×10 ^-6 mol/g

・Polysiloxane resin (C) Polysiloxane glue (G) Alkenyl (hexenyl) content: 2.0×10 ^-4 mol/g

・Polysiloxane resin (D) Polysiloxane glue (G) Alkenyl (hexenyl) content: 1.0×10 ^-2 mol/g

・Polysiloxane resin (E) Silicone resin (R)

・Crosslinking agent (A) Organic hydrogen polysiloxane SiH group content: 1.0×10 ^-2 mol/g

・Crosslinking agent (B) Organic hydrogen polysiloxane SiH group content: 4.0×10 ^-2 mol/g

1. The production of adhesive tape and the formation of a functional film (anti-reflection film) on the film substrate 12 (Example 1) The silicone resin (A) and the silicone resin (C) are mixed to form the The addition reaction type polysiloxane resin (S1) with a mass ratio (A)/(C) of 83/17 is diluted with toluene and stirred to prepare an addition reaction type polysiloxane resin solution (solid content concentration 30 mass %). The addition reaction type silicone resin (S1), the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is 50/50, and the content of alkenyl group is 5.0× 10 ^-5 mol/g. Incidentally, the content of alkenyl groups in the silicone rubber (G) is 1.0×10 ^-4 mol/g.

Next, 333 parts by mass of the addition reaction type silicone resin solution (100 parts by mass in terms of solid content) was blended with 1.01 parts by mass of the crosslinking agent (A) (SiH group/alkenyl group) with a disperser. Ear ratio=2.02), stir/mix evenly. Next, 1.0 part by mass of platinum-based catalyst "NC-25" (trade name) manufactured by Toray Dow Corning Co., Ltd. was blended with a disperser, and uniformly stirred/mixed to prepare an adhesive solution for coating.

Next, the adhesive solution for coating was applied to the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 2 became 20 μm, in the first half of the drying oven , The initial drying step by step at a temperature of 40 ~ 90 ℃. After that, the adhesive layer 2 was heated/cured by drying for 2 minutes in a region where the maximum temperature of the heat treatment set in the second half of the drying furnace was 180° C., and the release film was attached to obtain a single-sided adhesive tape 10 with a total thickness of 95 μm. In the same way, a single-sided adhesive tape 10' with a total thickness of 58 m with only the thickness of the base material 1 changed to 38 m was produced.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200°C measured in a He environment is 2.2×10 ⁵ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 72.5mg/m ² .

Next, use the single-sided adhesive tape 10 (size 310 mm × 340 mm) and single-sided adhesive tape 10' (size 20 mm × 360 mm), as shown in Figure 4. First, the single-sided adhesive tape 10 of the peeled off film The adhesive layer 2 is fixed on the carrier substrate 11 (SUS, size 370mm×380mm, thickness 2mm) with a single-sided adhesive tape 10' so that the adhesive layer 2 becomes the upper side. Next, six film substrates 12 (cover glass, size 140mm×70mm, thickness 0.4mm) are placed on the adhesive layer 2 of the single-sided adhesive tape 10 at equal intervals and temporarily fixed. In this way, prepare a total of 8 sets of carrier substrates 11 (thin film substrates 12: 48 sheets in total per batch) with 6 thin film substrates 12 temporarily fixed by a single-sided adhesive tape 10 to provide functional thin films (anti-reflective films) The film formation.

Next, the above-mentioned carrier substrates were installed in the vertical position on the substrate holders arranged on the rotating drum of the rotating rack-type radical assisted sputtering device, and the carrier substrates (thin film substrates) were heated to 200°C while being discharged by a vacuum pump. The pressure inside the device becomes 10 ^-6 Torr. Next, using silicon (Si) as a target, while rotating the rotating drum, a film was formed on the surface of the thin film substrate 12 (cover glass) by the post-reactive sputtering method under the following conditions to form a high refractive index layer (nitrogen). A total of 6 anti-reflective layers consisting of alternate layers of silicon: SiNx) and low refractive index layers (silicon oxide: SiO _{2 ).}

・Sputtering conditions High refractive index layer (silicon nitride: SiNx) N ₂ gas: 10 sccm Ar gas: 10 sccm Sputtering power: 2.0KW Low refractive index layer (silicon oxide: SiO ₂ ) O ₂ gas: 10 sccm Ar gas: 10 sccm Sputtering power: 1.5KW

・Anti-reflective film (//thin film substrate) SiO ₂ (110nm)/SiNx(60nm)/SiO ₂ (43nm)/SiNx(33nm)/SiO ₂ (50nm) /SiNx(140nm)(//thin film substrate)

(Example 2) Except for using polysiloxane resin (A) and polysiloxane resin (C) to mix the mass ratio (A)/(C) to 50/50 addition reaction type polysiloxane The resin (S2) is substituted for the addition reaction type silicone resin (S1), and the blending amount of the crosslinking agent (A) is changed to 2.20 parts by mass (SiH group/alkenyl group molar ratio = 2.00) Except this, it was the same as that of Example 1, and the adhesive solution for coating was prepared. The addition reaction type silicone resin (S2), the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is 70/30, and the content of alkenyl group is 1.1× 10 ^-4 mol/g. Incidentally, the content of alkenyl groups in the silicone rubber (G) is 1.5×10 ^-4 mol/g.

Next, the adhesive solution for coating was applied to the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 2 became 50 μm, in the first half of the drying oven , Is the initial drying step by step at a temperature of 40~90℃. After that, the area where the highest temperature of the heat treatment in the second half of the drying furnace becomes 160°C is dried for 1 minute to heat/harden the adhesive layer 2, and the release film is attached to the adhesive layer 2 to obtain a total thickness of 125 μm. Single-sided adhesive tape 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200°C measured in a He environment is 5.9×10 ⁵ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 65.1mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Example 3) Except for mixing polysiloxane resin (A), polysiloxane resin (B), and polysiloxane resin (E) into the mass ratio (A)/(B)/(E) Become a 50/42/8 addition reaction type silicone resin (S3) to replace the addition reaction type silicone resin (S1), and change the blending amount of the crosslinking agent (A) to 0.22 Parts by mass (molar ratio of SiH group/alkenyl group=2.17), except that the blending amount of the platinum-based catalyst "NC-25" is changed to 0.5 parts by mass, the same as in Example 1 was used for coating Adhesive solution. The addition reaction type silicone resin (S2), the mass ratio of silicone rubber (G) to silicone resin (R) (G)/(R) is 35/65, and the content of alkenyl group is 1.0× 10 ^-5 mol/g. Incidentally, the content of alkenyl groups in the silicone rubber (G) is 2.9×10 ^-5 mol/g.

Next, the adhesive solution for coating was applied to the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 2 became 30 μm, in the first half of the drying oven , Is the initial drying step by step at a temperature of 40~90℃. After that, the area where the highest temperature of the heat treatment in the second half of the drying furnace becomes 180°C is dried for 1 minute to heat/harden the adhesive layer 2, and the release film is attached to the adhesive layer 2 to obtain a total thickness of 105 μm. Single-sided adhesive tape 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200°C measured in a He environment is 1.0×10 ⁵ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 159.8mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Example 4) Except for using a mixture of silicone resin (C) and silicone resin (D), the mass ratio (C)/(D) is an addition reaction type silicone resin of 92/8 (S4) Substitute addition reaction type silicone resin (S1), and change 1.01 parts by mass of crosslinking agent (A) to 4.90 parts by mass of crosslinking agent (B) (SiH group/alkenyl mol Ratio=1.97), except that the blending amount of the platinum-based catalyst "NC-25" was changed to 3.0 parts by mass, in the same manner as in Example 1, an adhesive solution for coating was prepared. The addition reaction type silicone resin (S2), the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is 100/0, and the content of alkenyl group is 1.0× 10 ^-3 mol/g.

Next, the adhesive solution for coating was applied to the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 2 became 75 μm, in the first half of the drying oven , Is the initial drying step by step at a temperature of 40~90℃. After that, the area where the highest temperature of the heat treatment in the second half of the drying furnace becomes 200°C is dried for 3 minutes to heat/harden the adhesive layer 2, and the release film is attached to the adhesive layer 2 to obtain a total thickness of 150 μm. Single-sided adhesive tape 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200° C. measured in a He environment is 7.2×10 ⁶ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 31.2mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Example 5) A single-sided adhesive tape 10 with a total thickness of 125 μm was obtained in the same manner as in Example 2 except that the blending amount of the crosslinking agent (A) was changed to 0.55 parts by mass (molar ratio of SiH group/alkenyl group=0.50).

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200° C. measured in a He environment is 1.5×10 ⁵ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 122.3mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Example 6) Except that the blending amount of the crosslinking agent (A) was changed to 1.65 parts by mass (the molar ratio of SiH group/alkenyl group=1.50), in the same manner as in Example 2, a single-sided adhesive tape with a total thickness of 125 μm was obtained 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200°C measured in a He environment is 4.7×10 ⁵ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 70.3mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Example 7) Except that the blending amount of the crosslinking agent (A) was changed to 5.55 parts by mass (the molar ratio of SiH group/alkenyl group = 5.00), in the same manner as in Example 2, a single-sided adhesive tape with a total thickness of 125 μm was obtained 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200°C measured in a He environment is 6.0×10 ⁵ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 84.2mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Example 8) Except that 5.55 parts by mass of the crosslinking agent (A) was changed to 2.80 parts by mass of the crosslinking agent (B) (the molar ratio of SiH group/alkenyl group = 10.00), it was the same as in Example 2 to obtain a total thickness of 125 μm The single-sided adhesive tape 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200°C measured in a He environment is 6.7×10 ⁵ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 105.7mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Example 9) First, as an adhesive solution for coating for the adhesive layer 3, an adhesive solution for coating containing the same composition as in Example 1 (using an addition reaction type silicone resin (S1)) was prepared. Next, the adhesive solution for coating was applied to one side of the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 3 became 30 μm, and then dried. The first half of the furnace is initially dried in stages at a temperature of 40~90℃. After that, the area where the highest temperature of the heat treatment in the second half of the drying furnace becomes 180°C is dried for 2 minutes to heat/harden the adhesive layer 3, and the first release film is bonded to the adhesive layer 3 to obtain the total thickness 105μm middle laminate.

Next, as an adhesive solution for coating for the adhesive layer 2, an adhesive solution for coating containing the same composition as in Example 2 (using an addition reaction type silicone resin (S2)) was prepared. Next, the adhesive solution for coating was applied to the surface opposite to the surface on which the adhesive layer 3 of the intermediate laminate was formed so that the dry thickness of the adhesive layer 2 became 30 μm (base material 2 Face side), in the first half of the drying furnace, the initial drying stepwise at a temperature of 40~90℃. After that, the area where the maximum temperature of the heat treatment in the second half of the drying furnace becomes 160°C is dried for 1 minute to heat/harden the adhesive layer 2, and the second release film is bonded to the adhesive layer 2 to obtain the total thickness Adhesive tape 20 on both sides of 135μm.

The storage modulus of the adhesive layer 2 and the adhesive layer 3 of the double-sided adhesive tape 20 at 200°C measured in a He environment are 5.9×10 ⁵ Pa and 2.5×10 ⁵ Pa, respectively. In addition, the double-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0 × 10 -4 Torr and then maintained at 200°C for 30 minutes.} The total amount of outgassing is 128.3mg/m ² .

Then, using the double-sided adhesive tape 20 (size 310mm × 340mm), as shown in FIG. 6, first, peel off the first release film on the adhesive layer 3 side of the double-sided adhesive tape 20, and affix the adhesive layer 3 side to The carrier substrate 11 (SUS, size 370mm×380mm, thickness 2mm) is fixed with adhesive tape 20 on both sides. Next, peel off the second release film on the adhesive layer 2 side of the double-sided adhesive tape 20, and place 6 film substrates 12 (cover glass, size 140 mm×70 mm, thickness 0.4 mm) on both sides at equal intervals. On the adhesive layer 2 of the adhesive tape 20. In this way, a total of 8 sets of carrier substrates 11 (thin film substrates 12: 48 sheets in total per batch) in which 6 film substrates 12 are temporarily fixed by adhesive tapes 20 on both sides are prepared for the functional film (anti-reflection film) Film formation.

Next, in the same manner as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Comparative Example 1) Except for the addition reaction type polysiloxane which mixed polysiloxane resin (A) and polysiloxane resin (B) into the mass ratio (A)/(B) to 40/60 The resin (S5) is substituted for the addition reaction type polysiloxane resin (S1), and the blending amount of the crosslinking agent (A) is changed to 0.18 parts by mass (SiH group/alkenyl group molar ratio = 2.00) Except this, it was the same as that of Example 1, and the adhesive solution for coating was prepared. The addition reaction type silicone resin (S5), the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is 40/60, and the content of alkenyl group is 9.2× 10 ^-6 mol/g. Incidentally, the content of alkenyl groups in the silicone rubber (G) is 2.3×10 ^-5 mol/g.

Next, the adhesive solution for coating was applied to the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 2 became 20 μm, in the first half of the drying oven , Is the initial drying step by step at a temperature of 40~90℃. After that, the area where the highest temperature of the heat treatment in the second half of the drying furnace becomes 180°C is dried for 2 minutes to heat/harden the adhesive layer 2, and the release film is attached to the adhesive layer 2 to obtain a total thickness of 95 μm. Single-sided adhesive tape 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200°C measured in a He environment is 7.4×10 ⁴ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 193.3mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Comparative Example 2) Except for using a mixture of silicone resin (C) and silicone resin (D), the mass ratio (C)/(D) becomes 70/30 addition reaction type silicone resin (S6) Substitute addition reaction type silicone resin (S1), and change 1.01 parts by mass of crosslinking agent (A) to 15.7 parts by mass of crosslinking agent (B) (SiH group/alkenyl mol Except for ratio=2.09), it was the same as in Example 1, and the adhesive solution for coating was prepared. The addition reaction type silicone resin (S6), the mass ratio of silicone rubber (G) to silicone resin (R) (G)/(R) is 100/0, and the alkenyl content is 3.0× 10 ^-3 mol/g.

Next, the adhesive solution for coating was applied to the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 2 became 40 μm, in the first half of the drying oven , Is the initial drying step by step at a temperature of 40~90℃. After that, the area where the highest temperature of the heat treatment in the second half of the drying furnace becomes 180°C is dried for 1 minute to heat/harden the adhesive layer 2, and the release film is attached to the adhesive layer 2, to obtain a total thickness of 115 μm Single-sided adhesive tape 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200°C measured in a He environment is 1.9×10 ⁷ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 33.6mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Comparative Example 3) Except for using mixed silicone resin (A), silicone resin (C) and silicone resin (E), the mass ratio (A)/(C)/(E) becomes 63/5/32 addition reaction type silicone resin (S7), to replace addition reaction type silicone resin (S1), and the blending amount of crosslinking agent (A) is changed to 0.45 mass Except that the molar ratio of SiH group/alkenyl group=1.97, the same as in Example 1 was used to prepare an adhesive solution for coating. The addition reaction type silicone resin (S6), the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is 30/70, and the content of alkenyl group is 2.3× 10 ^-5 mol/g. Incidentally, the content of alkenyl groups in the silicone rubber (G) is 7.3×10 ^-5 mol/g.

Next, the adhesive solution for coating was applied to the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 2 became 15 μm, in the first half of the drying oven , Is the initial drying step by step at a temperature of 40~90℃. After that, the area where the maximum temperature of the heat treatment in the second half of the drying furnace becomes 180°C is dried for 1 minute to heat/harden the adhesive layer 2, and the release film is attached to the adhesive layer 2 to obtain a total thickness of 90 μm. Single-sided adhesive tape 10.

The storage modulus of the adhesive layer 2 of the single-sided adhesive tape 10 at 200° C. measured in a He environment is 1.5×10 ⁵ Pa. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The total gas output is 135.7mg/m ² .

Next, using the single-sided adhesive tape 10 and the single-sided adhesive tape 10' produced in Example 1, as in Example 1, a film was formed on the surface of the film substrate 12 (cover glass) to form an anti-reflection film.

(Comparative example 4) Except not adding the crosslinking agent (A), it was made into the adhesive solution for coating in the same manner as in Example 2. The addition reaction type silicone resin (S2), the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is 70/30, and the content of alkenyl group is 1.1× 10 ^-4 mol/g.

Next, the adhesive solution for coating was applied to the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 2 became 50 μm, in the first half of the drying oven , Is the initial drying step by step at a temperature of 40~90℃. After that, the area where the maximum temperature of the heat treatment in the second half of the drying furnace becomes 200°C is dried for 2 minutes to heat/dry the adhesive layer 2 to obtain a single-sided adhesive tape 10 with a total thickness of 125 μm, but the adhesive layer The adhesiveness of 2 is too high, which causes problems such as sticking to the conveying roller. Therefore, a good single-sided adhesive tape 10 cannot be manufactured.

Similar to the above drying conditions, for the single-sided adhesive tape 10 made of a sheet, after evaluating the storage modulus of the adhesive layer 2 at 200°C in a He environment, as the temperature rises, it can be seen that the elastic modulus drops sharply, and it cannot be confirmed. To the storage modulus near 200℃. In addition, the single-sided adhesive tape 10 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr and then maintained at 200°C for 30 minutes.} The amount is 251.1mg/m ² .

(Comparative Example 5) First, as the adhesive solution for coating for the adhesive layer 3, an adhesive solution for coating containing the same composition as in Example 3 (using an addition reaction type silicone resin (S3)) was prepared. Next, the adhesive solution for coating was applied to one side of the polyester film substrate 1 (thickness 75 μm) made by Toray Co., Ltd. so that the dry thickness of the adhesive layer 3 became 30 μm, and then dried. The first half of the furnace is initially dried in stages at a temperature of 40~90℃. After that, the area where the highest temperature of the heat treatment in the second half of the drying furnace becomes 180°C is dried for 1 minute to heat/harden the adhesive layer 3, and the first release film is bonded to the adhesive layer 3 to obtain the total thickness 105μm middle laminate.

Next, as an adhesive solution for coating for the adhesive layer 2, an adhesive solution for coating containing the same composition as in Example 1 (using an addition reaction type silicone resin (S1)) was prepared. Next, the adhesive solution for coating was applied to the surface opposite to the surface on which the adhesive layer 3 of the intermediate laminate was formed so that the dry thickness of the adhesive layer 2 became 20 μm (base material 2 Face side), in the first half of the drying furnace, the initial drying stepwise at a temperature of 40~90℃. After that, the area where the highest temperature of the heat treatment in the second half of the drying furnace becomes 180°C is dried for 2 minutes to heat/harden the adhesive layer 2, and the second release film is attached to the adhesive layer 2 to obtain the total thickness Adhesive tape 20 on both sides of 125μm.

The storage modulus of the adhesive layer 2 and the adhesive layer 3 of the double-sided adhesive tape 20 at 200°C measured in a He environment are 2.2×10 ⁵ Pa and 1.3×10 ⁵ Pa, respectively. In addition, the double-sided adhesive tape 20 is heated from 23°C to 200°C at a temperature increase rate of 10°C/min under an environment ^{with a vacuum degree of 1.0×10 -4 Torr or less, and then maintained at 200°C for 30 minutes.} The total amount of outgassing is 201.2mg/m ² .

Next, using the double-sided adhesive tape 20 (size 310 mm×340 mm), in the same manner as in Example 9, a film was formed on the surface of the film substrate 12 (cover glass) temporarily fixed to the adhesive layer 2 to form an anti-reflection film.

2. Evaluation method (1) Quantitative determination of the content of alkenyl groups in polysiloxane resins and the content of SiH groups in crosslinking agents The polysilicone gel of the present invention containing organopolysiloxanes containing alkenyl groups bonded to silicon atoms (G) It is blended with polysiloxane resin (R) containing organopolysiloxane that does not contain alkenyl groups bonded to silicon atoms at the mass ratio (G)/(R)=35/65~100/ The content of alkenyl groups in the addition reaction type polysiloxane resin in the range of 0 is ^{calculated by measuring the 1} H-NMR spectrum at 500 MHz. Specifically, the non-volatile components of the above-mentioned addition reaction type polysiloxane-based resin are sufficiently dissolved in deuterium chloroform containing dimethyl sulfoxide as an internal standard sample, and NMR manufactured by JEOL Ltd. is used. The device "JNM･ECA500" (product name) measures the ¹ H-NMR spectrum. Next, obtain the resonance signal area (integrated value) of the internal standard sample in the measurement spectrum and the resonance signal area (integrated value) of the alkenyl group, and calculate from the ratio per 1g of addition reaction polysilicon The content of the alkenyl group of the oxygen-based resin. Also, for the crosslinking agent ^{containing organohydrogen polysiloxane, the 1} H-NMR spectrum was measured to obtain the resonance signal area (integrated value) of the internal standard sample in the measurement spectrum. ) The area of resonance signal with SiH group (integrated value), and calculate the content of SiH group per 1g of crosslinking agent from the ratio. In addition, when the crosslinking agent is internally added to the addition reaction type silicone resin from the beginning, it is sufficient to calculate the content of the alkenyl group and the SiH group at the same time ^{from the 1 H-NMR spectrum.}

(2) Storage modulus of the adhesive layer For the adhesive tapes 10 and 20 of Examples 1 to 9 and Comparative Examples 1 to 5, the storage modulus of the adhesive layers 2 and 3 was measured by the following method. First, the adhesive solutions for coating prepared in the respective examples and comparative examples were respectively coated on the first release film, dried and cured under the same conditions as in the respective examples and comparative examples, and the second release film was laminated to obtain Adhesive tape (no substrate). Next, each of the obtained adhesive tapes was cut into small pieces, and the release film was peeled off to prepare a sample in which only the adhesive layer was laminated so as to have a thickness of about 500 μm. For these samples, a viscoelasticity measuring device "DMA6100" (product name) manufactured by Hitachi High-Tech Science Co., Ltd. was used to measure the dynamic viscoelasticity to obtain the storage modulus of the adhesive layer. The measurement conditions were in a He environment, while applying a shear strain with a frequency of 1 Hz, while changing the temperature from 30°C to 280°C at a heating rate of 2°C/min, the dynamic viscoelastic spectrum was measured. The value of the storage modulus of the obtained spectrum at 200° C. was used as the storage modulus of the adhesive layer at 200° C. measured in a He environment.

(3) The total amount of outgas generated by the adhesive tape For the adhesive tapes 10 and 20 of Examples 1-9 and Comparative Examples 1 to 5, the temperature programmed desorption gas-phase mass spectrometry (TPD-MS) was used to determine the total amount of gas produced by the adhesive tape 10, 20 The total amount of gas produced. First, prepare a sample (excluding the release film) by cutting the adhesive tapes 10 and 20 into a size of 4 mm×20 mm. Next, put the respective adhesive tape samples into the quartz sample tube of the horizontal differential type differential thermal balance "MB6" (product name) manufactured by Rigaku Co., Ltd. with an infrared heating furnace, and exhaust with a vacuum pump. Adjust the pressure in the sample tube to 1.0×10 ^-5 ~ 1.0×10 ^{-6 Torr.} Next, the sample tube was heated from room temperature to 200°C at a temperature increase rate of 10°C/min, and kept at 200°C for 30 minutes. For the gas components generated from the sample at this time, the mass spectrometer "Q" manufactured by Hewlett Packard was used. -MS5973A" (product name) was analyzed by mass spectrometry, and MS total ion current (TIC) chromatogram was obtained. Furthermore, as a standard sample, CO ₂ (carbon dioxide gas) generated when calcium oxalate is heated is used. The calibration curve is made by adjusting the concentration and the peak area. The gas composition generated by the calibration curve and the self-adhesive tape sample The total peak area of the TIC _{is calculated by CO 2} conversion. After the adhesive tape is heated from 23°C to 200°C at a heating rate of 10°C/min under an environment with a vacuum degree of 1.0×10 ^{-4 Torr or less, the temperature is further increased to 200°C.} When the temperature is maintained for 30 minutes, the total amount of outgassed by the adhesive tape.

(4) Evaluation in the vacuum film forming process Regarding the adhesive tapes 10 and 20 of Examples 1 to 9 and Comparative Examples 1 to 5, on the surface of the film substrate 12 (cover glass) temporarily fixed on the adhesive layer 2 of the respective adhesive tapes 10 and 20, When using a rotating rack type free radical-assisted sputtering device to form an anti-reflective film by the post-reactive sputtering method, the following four items are evaluated based on the three-stage A~C standard.

＜Temporary fixing force to film substrate＞ After the formation of the anti-reflective film is completed, the 48 thin film substrates in the vertical position are checked for peeling. A: The number of peeled film substrates is 0. B: The number of thin film substrates that fell off is one piece. C: Two or more thin film substrates peeled off.

＜Removability of film substrate＞ After forming the anti-reflective film, evaluate whether the adhesive tape can be peeled off the film substrate by the above-mentioned method or the film substrate can be peeled off without the film substrate being damaged. A: The number of film substrates damaged during peeling is 0, and all of them can be peeled off again. B: The number of film substrates damaged during peeling is one, and the others can be peeled again. C: Two or more film substrates were damaged during peeling.

＜Generation of Adhesive Residue＞ After forming the anti-reflective film, visually confirm the average state of the adhesive remaining on the film substrate when the adhesive tape is peeled from the film substrate by the above method, or when the film substrate is peeled by the adhesive tape. A: No clear adhesive residue is observed. B: A little adhesive residue is observed, but it is a grade that can be easily removed by washing. C: Definite adhesive residue is observed.

＜Appearance of anti-reflective film＞ Visually observe the average state of the appearance of the anti-reflection film formed on the film substrate. A: No clear uneven film formation is observed. B: Depending on the viewing angle, a slight unevenness in film formation was observed, but it was of an inconspicuous level. C: Clear uneven film formation is observed. In all items, the evaluation system of A or B is judged to be a level that has no practical problems.

3. Test results The composition and evaluation results of the adhesive tapes 10 and 20 of Examples 1 to 9 and Comparative Examples 1 to 5 are shown in Tables 1 to 4.

As shown in Tables 1 to 3, the single-sided adhesive tape 10 of Examples 1 to 8 and the double-sided adhesive tape 20 of Example 9 manufactured by the roll-to-roll method, the adhesive measured at 200°C under He environment The storage modulus of the layer is in the range of 1.0×10 ⁵ ~1.0×10 ⁷ Pa. Under an environment with a vacuum degree of 1.0×10 ^-4 Torr, the temperature is increased from 23°C to 200°C at a heating rate of 10°C/min. when maintained at 200 ℃ 30 minutes, and the total amount of air is generated 180mg / m ² or less, the adhesive tape known as applications, etc. by using this carousel type sputtering vacuum deposition apparatus of the plating process, the film When the adhesive tape for temporary fixation when forming an anti-reflective film on the substrate, even in the vertical position, the temporary fixation force of the film substrate is sufficient, which can suppress the outgassing from the adhesive tape during the film formation process, and the The appearance of the anti-reflective film will not cause adverse effects, and the film substrate and the adhesive tape can be peeled off after the film is formed (there is no adhesive residue on the film substrate, and the film substrate is not damaged during peeling). In addition, the visible light reflectance necessary for the characteristics of the anti-reflection film is also 1.0% or less, and there is no particular problem in practical use.

In terms of the appearance of the anti-reflective film on the film substrate, the less the total amount of outgassing produced by the adhesive tape, the better the tendency to get good results. Among them, the total amount of outgassing is less than 100mg/m ² in Example 1 ~2. The single-sided adhesive tape 10 of Example 4 and Examples 6-7 is particularly good.

In addition, the same adhesive layer was used in the comparison of Example 2 and Examples 5 to 8, except for the molar ratio of the SiH group of the crosslinking agent and the alkenyl group of the addition reaction type silicone resin. When the SiH-based/alkenyl-based molar ratio is in the range of 1.5 to 5.0 in Example 2, when the single-sided adhesive tape 10 of Examples 6 to 7, the temporary fixing force on the film substrate, the re-peelability of the film substrate, and the film Good results were obtained in all evaluations of the adhesive residue on the substrate and the appearance of the anti-reflection film on the thin film substrate. When using the single-sided adhesive tape 10 of Example 5 with the SiH-based/alkenyl-based molar ratio of 0.5, the crosslinking/hardening of the adhesive layer is slightly insufficient, and the storage modulus is slightly smaller, so the total amount of outgassing is slightly larger, and the film The appearance of the anti-reflection film on the substrate is slightly poor. In addition, the adhesive force of the adhesive layer is slightly larger, and the re-peelability of the film substrate is also slightly poor. However, they are all practically problem-free grades. In addition, when the single-sided adhesive tape 10 of Example 8 with a molar ratio of SiH group/alkenyl group of 10.0 was used, the amount of remaining SiH group was slightly higher, and the SiH was silanolated to become SiOH, which was carried out during heating/film formation The moisture generated during the dehydration condensation reaction becomes outgassing, so the total amount of outgassing is slightly increased, and the appearance of the anti-reflection film on the film substrate is slightly poor. Moreover, the adhesive force of the adhesive layer is slightly larger, and the re-peelability of the film substrate is also slightly poor. However, they are all practically problem-free grades.

Furthermore, when the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is used, the single-sided adhesive tape 10 of Example 3 where the lower limit of the present invention is 35/65, The storage modulus of the adhesive layer has also become the lower limit of the present invention, and the total amount of outgassing is slightly higher, so the appearance of the anti-reflection film on the film substrate is slightly poor. In addition, the ratio of polysiloxane resin (R) is a relatively high 65% by mass, and the adhesive force of the adhesive layer is also slightly larger. Therefore, the re-peelability of the film substrate and the adhesive residue on the film substrate are also slightly poor. However, they are all practically problem-free grades.

Furthermore, when the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is used as the upper limit of the present invention, the single-sided adhesive tape 10 of Example 4 is 100/0 , The storage modulus of the adhesive layer has also become the upper limit of the present invention. The adhesive layer is slightly harder, and the adhesive force is slightly lower, so only the temporary fixing force of the film substrate is slightly poor. However, it is a practically problem-free level.

Furthermore, when using the double-sided adhesive tape 20 of Example 9 in which the adhesive layer of Example 1 is provided on one side of the substrate and the adhesive layer of Example 2 is provided on the second side of the substrate, the adhesive The total thickness of the agent layer becomes thicker, and the total amount of air out of the double-sided adhesive tape 20 is slightly increased by a corresponding amount. Therefore, although the appearance of the anti-reflection film on the film substrate is slightly poor, other evaluations are good, which are practical. No problem level.

By this, it is confirmed that the use of "the polysilicone rubber (G) containing alkenyl groups and the polysilicone resin (R) not containing alkenyl groups will be blended to a mass ratio (G)/(R)=35/65~ The range of 100/0, and the content of the alkenyl group becomes 1.0×10 ^-5 ~1.0×10 ^-3 mol/g addition reaction type polysiloxane resin, through the organic polysiloxane with SiH group The resin composition obtained by heating/hardening an alkane and platinum group metal catalyst" is used as the adhesive layer, and is designed as "the storage modulus of the adhesive layer at 200°C measured in a He environment is 1.0×10 ⁵ ~ In the range of 1.0×10 ⁷ Pa, and in an environment with a vacuum degree of 1.0×10 ^-4 Torr or less, the temperature is increased from 23°C to 200°C at a heating rate of 10°C/min, and then maintained at 200°C for 30 minutes. The single-sided adhesive tape 10 of Examples 1 to 8 and the double-sided adhesive tape 20 of Example 9 in which the total amount of outgas generated by the adhesive tape is ^{less than 180 mg/m 2 are suitable as adhesive tapes for vacuum processes.}

On the other hand, as shown in Tables 3 to 4, it can be seen that when the single-sided adhesive tape of Comparative Examples 1 to 4 and the double-sided adhesive tape 20 of Comparative Example 5 are used, the structure of the present invention is not satisfied, so the temporary fixing force of the film substrate The evaluation results of at least one of the re-peelability of the film substrate, the adhesive residue on the film substrate, and the appearance of the anti-reflection film on the film substrate are inferior to Examples 1-9.

Specifically, the single-sided adhesive tape 10 of Comparative Example 1 has a small content of alkenyl groups in the addition reaction type silicone resin, and the storage modulus of the adhesive layer after crosslinking/hardening is small, so the total amount of outgassing The appearance of the anti-reflection film on the film substrate is worse than that of the embodiment. In addition, the adhesive force of the adhesive layer is also large, so the re-peelability of the film substrate is also inferior to the embodiment.

In addition, the single-sided adhesive tape 10 of Comparative Example 2 has a high content of alkenyl groups in the addition reaction type polysiloxane resin, and the storage modulus of the adhesive layer after cross-linking/hardening is too large. Therefore, the adhesion of the adhesive layer When the force becomes too small, the thin film substrate cannot be sufficiently temporarily fixed, and the thin film substrate falls off during the film forming process, and the film cannot be formed to form an anti-reflective film.

Furthermore, in the single-sided adhesive tape 10 of Comparative Example 3, since the mass ratio (G)/(R) of silicone rubber (G) to silicone resin (R) is 30/70, silicone resin (R) If the ratio of) is too large, the adhesive force of the adhesive layer becomes too large. Therefore, the re-peelability of the film substrate and the adhesive residue on the film substrate are inferior to the embodiment.

Furthermore, since the single-sided adhesive tape 10 of Comparative Example 4 is not blended with a crosslinking agent, the crosslinking/hardening of the adhesive layer has not proceeded, so the cohesive force is small, and a good adhesive tape cannot be produced by a roll-to-roll method. Furthermore, the amount of air outflow of the adhesive tape made from the sheet is still large.

Furthermore, in the double-sided adhesive tape 20 of Comparative Example 5, although the adhesive layer of Example 3 is provided on one side of the substrate, the adhesive layer of Example 1 is provided on both sides of the substrate. Adhesive tape, but since the amount of air outflow from the adhesive layer on the one side of the substrate is slightly larger, the total amount of air outflow from the adhesive layer on the two sides of the substrate is added as the total amount of air out of the double-sided adhesive tape 20 Therefore, the appearance of the anti-reflective film on the thin film substrate is worse than that of the embodiment.

1: Substrate 2,3: Adhesive layer 10,10’: Single-sided adhesive tape 11: Carrier substrate 12: Thin film substrate 20: Adhesive tape on both sides 30, 40: Schematic diagram of the vertical posture of the carrier substrate with the film substrate temporarily fixed 50, 60, 70, 80: Schematic diagram of the carrier substrate with the film substrate temporarily fixed

[Fig. 1] A diagram showing an example of the structure of the single-sided adhesive tape to which this embodiment is applied. [Fig. 2] A diagram showing an example of the structure to which the double-sided adhesive tape of this embodiment is applied. [FIG. 3] A diagram showing an example of a state in which a plurality of film substrates are temporarily fixed to a carrier substrate by applying the double-sided adhesive tape of this embodiment in the vertical position. [FIG. 4] A diagram showing another example of a state in which a plurality of film substrates are temporarily fixed to a carrier substrate in the vertical position by applying the double-sided adhesive tape of this embodiment. [Fig. 5] A diagram showing an example of a method of temporarily fixing a film substrate to a carrier substrate by applying the single-sided adhesive tape of this embodiment. [FIG. 6] A diagram showing another example of the temporary fixing method of the film substrate to the carrier substrate by applying the single-sided adhesive tape of this embodiment. [FIG. 7] A diagram showing an example of the temporary fixing method of the film substrate to the carrier substrate by applying the double-sided adhesive tape of this embodiment. [Fig. 8] A diagram showing another example of the temporary fixing method of the film substrate to the carrier substrate by applying the double-sided adhesive tape of this embodiment.

1: Substrate

2: Adhesive layer

10: Single-sided adhesive tape

Claims (3)

An adhesive tape for a vacuum process, which is provided with a substrate and an adhesive layer on at least one side of the substrate, wherein the adhesive layer includes a resin composition, and the resin composition contains: as a main component The addition reaction type polysiloxane-based resin, the organopolysiloxane having at least two hydrogen atoms (SiH) bonded to the silicon atom in one molecule as a crosslinking agent, and the platinum group as a catalyst Metal catalysts, the aforementioned addition reaction type polysiloxane resins are polysiloxane gels (G) containing organopolysiloxanes containing alkenyl groups bonded to silicon atoms and those containing no silicon atoms bonded The polysiloxane resin (R) of the alkenyl organopolysiloxane, in the mass ratio (G)/(R), (G)/(R)=35/65~100/0 The method is blended, and the content of alkenyl groups bonded to silicon atoms is in the range of 1.0×10 ^-5 to 1.0×10 ^-3 mol/g. The aforementioned adhesive layer is stored at 200 ℃ under He environment. The modulus is in the range of 1.0×10 ⁵ ~1.0×10 ⁷ Pa. After the aforementioned adhesive tape is heated from 23°C to 200°C at a temperature rise rate of 10°C/min under an environment with a vacuum degree of 1.0×10 ^{-4 Torr or less,} When the temperature is further maintained at 200°C for 30 minutes, the total amount of outgas generated is 180 mg/m ² or less. The adhesive tape for a vacuum process of claim 1, wherein the aforementioned substrate is a polyethylene terephthalate film. For example, the adhesive tape for the vacuum process of claim 1 or 2, which is applied to form a functional film selected from the group of anti-reflective film, anti-glare film, anti-fouling film, and colored film on a heat-resistant substrate.

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