TW202035635A - Adhesive composition and adhesive tape - Google Patents

Abstract

The present invention makes it possible to provide an adhesive composition capable of suppressing adhesion enhancement even when subjected to a high-temperature heat treatment step while having high adhesive strength at the time of application, and an adhesive tape having an adhesive layer composed of the adhesive composition. The present invention is an adhesive composition that contains an adhesive component and a silicone-based graft copolymer having a functional group capable of crosslinking with the adhesive component.

Description

Adhesive composition and adhesive tape

The present invention relates to an adhesive composition and an adhesive tape having an adhesive layer composed of the adhesive composition.

In recent years, adhesive tapes have been used in various industrial fields. In the construction field, double-sided adhesive tape is used for the temporary fixing of protective sheets and the lamination of interior materials; in the automotive field, it is used for fixing, side moldings, and side trims of interior parts such as sheets and sensors. Double-sided adhesive tape is used when fixing exterior parts such as window visors; in the electrical and electronic fields, double-sided adhesive tape is used when assembling modules and attaching modules to shells. Specifically, for example, in portable electronic devices (such as mobile phones, mobile information terminals, etc.) equipped with image display devices or input devices, double-sided adhesive tapes are used for assembly. More specifically, for example, in order to bond the cover for protecting the surface of the portable electronic machine to the touch panel module or the display panel module, or to bond the touch panel module and the display panel module , And use double-sided adhesive tape. Such a double-sided adhesive tape is used, for example, by punching it into a frame shape or the like and arranging it on the periphery of the display screen (for example, Patent Literature 1 and 2). In addition, double-sided adhesive tapes are also used for fixing vehicle parts (such as automotive panels) to the vehicle body. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2009-242541 Patent Document 2: Japanese Patent Application Publication No. 2009-258274

[The problem to be solved by the invention]

According to the purpose of the adhesive tape, a high-temperature heat treatment step is carried out while the adhesive tape is attached to the adherend, and then the adhesive tape needs to be peeled off. For example, in the manufacturing steps of electronic parts such as semiconductor chips, various high-temperature heat treatment steps are performed in a state where the semiconductor wafer is bonded to a support plate via a double-sided adhesive tape for reinforcement, and then the semiconductor wafer is peeled from the support plate. Here, if the adhesion of the adhesive tape increases due to the high-temperature heat treatment step, it may become difficult to peel the semiconductor wafer from the support plate, or the paste may remain on the surface of the semiconductor wafer during the peeling. In response to this, polysiloxane compound is blended into the adhesive layer as a peeling aid. By blending the silicone compound, the silicone compound exuded from the adhesive layer can be used to suppress the subsequent increase.

However, depending on the type of the adherend, the conventional silicone compound has a situation where it is difficult to sufficiently suppress the adhesion enhancement. Conventional polysiloxane compounds have low affinity with highly polar substances due to their low polarity. When the adherend is a semiconductor wafer with high polarity, it will ooze out to the surface of the adhesive tape. The polysiloxane cannot stay on the surface, but diffuses from the interface with the adherend. Therefore, sometimes the polysiloxane present at the interface between the adhesive tape and the adherend decreases, and the subsequent increase cannot be sufficiently suppressed.

In addition, the adhesive tape needs to suppress the subsequent hyperplasia on the one hand, and on the other hand, it also needs to have a high adhesive force during attachment (hereinafter, the adhesive force during attachment is referred to as the initial adhesive force). However, the conventional polysiloxane also has a problem that the adhesion cannot be suppressed if it is not used in a large amount, and the initial adhesion is lowered if the polysiloxane is used in a large amount.

The object of the present invention is to provide an adhesive composition that can suppress the subsequent increase even if it is used in a high-temperature heat treatment step, even if it is used in the high-temperature heat treatment step, and has a composition made of the adhesive composition. The adhesive tape that constitutes the adhesive layer. [Technical means to solve the problem]

The present invention is an adhesive composition, which contains an adhesive component and a silicone-based graft copolymer. The silicone-based graft copolymer has a functional group capable of crosslinking with the adhesive component. The present invention will be described in detail below.

The adhesive composition of one embodiment of the present invention contains an adhesive component. The above-mentioned adhesive component is not particularly limited, and may be a hardening adhesive component or a non-hardening adhesive component, but it is preferably a hardening adhesive component. Among them, the adhesive composition of one embodiment of the present invention is preferably a curable adhesive composition mainly composed of a polymerizable polymer as a curable adhesive component and containing a polymerization initiator. If the adhesive component is a hardening type adhesive component, the adhesive layer composed of the adhesive composition can be well adhered to the adherend before hardening, so it can exhibit a high adhesive force during sticking. Furthermore, by hardening the adhesive component, the elastic modulus of the adhesive layer can be improved. Therefore, by hardening the adhesive component before the heat treatment step or during the heat treatment step, the adhesion increase at high temperature can be suppressed. In addition, by improving the elastic modulus of the adhesive layer, it is also possible to prevent the paste from remaining on the adherend.

Examples of the curable adhesive composition include a photocurable adhesive composition containing the polymerizable polymer and a photopolymerization initiator, or a thermosetting adhesive composition containing the polymerizable polymer and a thermal polymerization initiator.剂组合物。 Agent composition. Among them, in terms of being hardenable by the heat of the heat treatment step and requiring no light hardening equipment or light hardening step, a thermosetting adhesive composition is preferred. When the hardening type adhesive composition is a heat hardening type adhesive composition, it is not necessary to provide an additional hardening step only by passing through the heating step, so the number of steps can also be reduced. In addition, the above-mentioned curable adhesive composition is not particularly limited, but it is preferably an acrylic adhesive composition in terms of excellent heat resistance and weather resistance and being applicable to a wide range of adherends. The structure of the above-mentioned adhesive component is not particularly limited, and it may be a random copolymer, a block copolymer or a graft copolymer.

When the aforementioned adhesive component is a curable adhesive component, the crosslinkable functional group for exhibiting curability is not particularly limited, but it is preferably a radically polymerizable unsaturated bond. That is, it is preferable that the said adhesive component has a radically polymerizable unsaturated bond in a molecule|numerator. When the above-mentioned adhesive component has a radically polymerizable unsaturated bond in the molecule, that is, when the crosslinkable functional group of the curable adhesive component is a radically polymerizable unsaturated bond, it is compared with other Cross-linkable functional groups reduce the polarity of the cross-linking point and increase the cross-link density. Thereby, the elastic modulus of the adhesive layer composed of the adhesive composition is further improved, and the subsequent hyperactivity can be more suppressed. In addition, by increasing the modulus of elasticity, it is also possible to suppress paste residue. Furthermore, the radically polymerizable unsaturated bond system can not only construct a cross-linked structure in the adhesive component, but also a functional group that can be cross-linked with the following polysiloxane-based graft copolymer, and also contributes to Crosslinking of the above-mentioned adhesive components and polysiloxane graft copolymers. When the adhesive component has a functional group capable of crosslinking with the polysiloxane-based graft copolymer other than the aforementioned radically polymerizable unsaturated bond, such functional group is not particularly limited, and examples include carboxyl, Hydroxy, amide, isocyanate group, epoxy group, etc. These functional groups that can be crosslinked with the polysiloxane-based graft copolymer may be used alone or in combination of two or more kinds.

The radically polymerizable unsaturated bond can be introduced by using "a monomer having a radically polymerizable unsaturated bond", for example, when synthesizing the polymerizable polymer. In addition, the radically polymerizable unsaturated bond may also be introduced by obtaining the polymerizable polymer by the following method. That is, the aforementioned polymerizable polymer can be obtained, for example, by pre-synthesizing a (meth)acrylic polymer having a functional group in the molecule (hereinafter referred to as a functional group-containing (meth)acrylic polymer), It is reacted with a compound having a functional group that reacts with the above-mentioned functional group and a radically polymerizable unsaturated bond in the molecule (hereinafter referred to as a functional group-containing unsaturated compound).

The above-mentioned functional group-containing (meth)acrylic polymer is obtained by a conventional method such as free radical polymerization to make alkyl acrylate and/or the carbon number of the alkyl group in the range of 2-18 Or methacrylate, functional group-containing monomers, and other monomers for modification that can be copolymerized with them as needed. This is the same as the case of general (meth)acrylic polymers, which are polymers with adhesiveness at room temperature. The weight average molecular weight of the functional group-containing (meth)acrylic polymer is usually about 200,000 to 2 million.

Examples of the above-mentioned functional group-containing monomers include carboxyl group-containing monomers such as acrylic acid and methacrylic acid; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. Hydroxyl-containing monomers such as 4-hydroxybutyl ester. In addition, as the above-mentioned functional group-containing monomers, for example, epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; isocyanatoethyl acrylate, methyl Monomers containing isocyanate groups such as isocyanatoethyl acrylate; monomers containing amino groups such as aminoethyl acrylate and aminoethyl methacrylate. Furthermore, among the functional groups of the functional group-containing monomers, the unreacted functional groups that are not used in the reaction with the above-mentioned functional group-containing unsaturated compounds become "as a function of being able to cross with the polysiloxane-based graft copolymer Linking functional groups, which contribute to the crosslinking of the above-mentioned adhesive components and the polysiloxane-based graft copolymer." The above-mentioned other monomers for modification that can be copolymerized include, for example, various monomers used in general (meth)acrylic polymers such as vinyl acetate, acrylonitrile, styrene, and maleic anhydride.

As the polymerization method of the above-mentioned radical polymerization, a conventionally known method can be used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, and bulk polymerization. The polymerization initiator used in the above radical polymerization is not particularly limited, and examples thereof include organic peroxides and azo compounds. Examples of the above-mentioned organic peroxides include: 1,1-bis(tert-hexly peroxy)-3,3,5-trimethylcyclohexane (1,1-bis(tert-hexly peroxy)-3 ,3,5-trimethylcyclohexane, tert-hexyl peroxy pivalate, tert-butyl peroxy pivalate, 2,5-dimethyl 2,5-bis(2-ethylhexanoyl peroxy)hexane (2,5-dimethyl-2,5-bis(2-ethylhexanoyl peroxy)hexane), peroxy-2-ethylhexanoic acid Tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate -butyl peroxy isobutyrate), tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert- butyl peroxy laurate) and so on. As said azo compound, azobisisobutyronitrile, azobis cyclohexane carbonitrile, etc. are mentioned, for example. These polymerization initiators may be used alone or in combination of two or more kinds.

The functional group-containing (meth)acrylic polymer can also be obtained by living radical polymerization. Living radical polymerization is a polymerization in which the molecular chain grows without being hindered by side reactions such as stop reaction or chain transfer reaction. According to living free radical polymerization, compared with, for example, free radical polymerization, a polymer with a more uniform molecular weight and composition can be obtained, and the generation of low molecular weight components can be suppressed. Therefore, the adhesive composition obtained is adhered at high temperature Hyperplasia is suppressed, and on the other hand, the adhesive composition is not easily peeled off to such an extent that unintentional peeling does not occur.

Living radical polymerization is not particularly limited as long as it is generally used, and examples include the TERP method, the RAFT method, and the NMP method. Organic tellurium compounds are used in the TERP method, RAFT agents are used in the RAFT method, nitroxide compounds are used in the NMP method, and the above-mentioned polymerization initiators such as organic peroxides and azo compounds are combined as necessary. use. In addition, the ATRP method can also be used.

In the above radical polymerization, a dispersion stabilizer can be used. Examples of the dispersion stabilizer include: polyvinylpyrrolidone, polyvinyl alcohol, methylcellulose, ethylcellulose, poly(meth)acrylic acid, poly(meth)acrylate, polyethylene glycol, etc. .

烷、N,N-二甲基甲醯胺等高極性溶劑。該等聚合溶劑可單獨使用，亦可併用2種以上。聚合溫度就聚合速度之觀點而言，較佳為0～110℃。In the case of using a polymerization solvent in the above radical polymerization, the polymerization solvent is not particularly limited. As the aforementioned polymerization solvent, for example, non-polar solvents such as hexane, cyclohexane, octane, toluene, and xylene; or water, methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone, methyl ethyl ketone, etc. can be used. Isobutyl ketone, tetrahydrofuran, two

Highly polar solvents such as alkane and N,N-dimethylformamide. These polymerization solvents may be used alone or in combination of two or more kinds. The polymerization temperature is preferably 0 to 110°C from the viewpoint of the polymerization rate.

As the functional group-containing unsaturated compound that reacts with the above-mentioned functional group-containing (meth)acrylic polymer, depending on the functional group of the above-mentioned functional group-containing (meth)acrylic polymer, the above-mentioned functional group-containing The monomers are the same. For example, when the functional group of the functional group-containing (meth)acrylic polymer is a carboxyl group, an epoxy group-containing monomer or an isocyanate group-containing monomer can be used. In addition, when the functional group is a hydroxyl group, an isocyanate group-containing monomer can be used. Moreover, when the functional group is an epoxy group, a carboxyl group-containing monomer or an amide group-containing monomer such as acrylamide can be used. Furthermore, when the functional group is an amino group, an epoxy group-containing monomer can be used.

The adhesive composition of an embodiment of the present invention may also contain multifunctional oligomers or monomers. The above-mentioned polyfunctional oligomer or monomer preferably has a molecular weight of 10,000 or less, and more preferably has a molecular weight of 5,000 or less and the number of radically polymerizable unsaturated bonds in the molecule is 2 to 20, which can be efficiently To complete the three-dimensional reticulation of the adhesive layer by heating or light irradiation. Such more preferable multifunctional oligomers or monomers include, for example, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, Dineopentaerythritol monohydroxy pentaacrylate, dineopentaerythritol hexaacrylate, or the same methacrylates mentioned above. As the above-mentioned multifunctional oligomer or monomer, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, and commercially available oligoester acrylic acid can also be cited. Esters (oligoester acrylate), the same methacrylates mentioned above, etc. These polyfunctional oligomers or monomers may be used alone or in combination of two or more kinds.

、十二烷基-9-氧硫𠮿

、二甲基-9-氧硫𠮿

、二乙基9-氧硫𠮿

、α-羥基環己基苯基酮、2-羥基甲基苯基丙烷等光自由基聚合起始劑。該等光聚合起始劑可單獨使用，亦可併用2種以上。As described above, the adhesive composition of one embodiment of the present invention is preferably a curable adhesive composition that has a polymerizable polymer as a curable adhesive component as a main component and contains a polymerization initiator. The above-mentioned polymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators and thermal polymerization initiators. The above-mentioned photopolymerization initiator can be activated by irradiating light with a wavelength of 250 to 800 nm, for example. Examples of such photopolymerization initiators include acetophenone derivative compounds such as methoxyacetophenone; benzoin ether-based compounds such as benzoin propyl ether and benzoin isobutyl ether; benzyl dimethyl ketal and acetophenone Light radical polymerization initiators such as ketal derivative compounds such as diethyl ketal. In addition, photo-radical polymerization initiators such as phosphine oxide derivative compounds and bis(η5-cyclopentadienyl) titanocene derivative compounds can also be cited. Further examples may also be: diphenyl ketone, Michele ketone, chloro-9-oxysulfur 𠮿

, Dodecyl-9-oxysulfur 𠮿

, Dimethyl-9-oxysulfur 𠮿

, Diethyl 9-oxysulfur 𠮿

, Α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethyl phenyl propane and other photo radical polymerization initiators. These photopolymerization initiators may be used alone or in combination of two or more kinds.

Examples of the thermal polymerization initiator include those that decompose by heat to generate active radicals that initiate polymerization and hardening. Specifically, for example, dicumyl peroxide (dicumyl peroxide), di-tertiary butyl peroxide, tertiary butyl peroxybenzoate, tertiary butyl hydroperoxide, Benzoyl peroxide, cumene hydroperoxide, dicumyl hydroperoxide, p-menthane hydroperoxide, di-tertiary butyl peroxide, etc.

The adhesive composition of one embodiment of the present invention contains a polysiloxane-based graft copolymer. The so-called polysiloxane-based graft copolymer means a copolymer in which the polysiloxane part becomes a graft chain. If the adhesive composition contains a silicone-based graft copolymer, when the adhesive tape using the adhesive composition of one embodiment of the present invention is used in the high-temperature heat treatment step, the silicone-based graft copolymer aggregates It is at the interface between the adhesive layer and the adherend, so it can prevent the subsequent hyperactivity.

In the past, the polysiloxane compound has a structure to the extent that it has a functional group at the end of the polysiloxane compound, and most of the molecule becomes the polysiloxane part. Therefore, there are situations in which when the polysiloxane is used to a degree that can reduce the subsequent acceleration, it becomes the cause of the decrease in the initial adhesion. In the adhesive composition of one embodiment of the present invention, the polysiloxane compound is a polysiloxane-based graft copolymer, so the adhesive composition composed of the adhesive composition can be adhered by parts other than the polysiloxane part The polarity of the surface of the agent layer is in an appropriate range, which can suppress the decrease in initial adhesion. In addition, by making the polysiloxane site a graft chain instead of the main chain, the number of the polysiloxane site can be easily increased, and therefore, a high adhesion enhancement suppression performance can be exerted.

The above-mentioned polysiloxane-based graft copolymer is not particularly limited as long as it has the following functional group capable of crosslinking with the above-mentioned adhesive component and a graft chain containing a polysiloxy group. Among them, from the viewpoint that the initial adhesive force and the adhesive force after the heat treatment step can be advantageously controlled, it is preferable to make a monomer containing a functional group capable of crosslinking with the adhesive component, and a polysiloxane It is formed by copolymerizing the raw material monomer mixture of "macro monomer" and "other monomers as needed".

Examples of the polysiloxane macromonomers include acrylic polysiloxane macromonomers, styrene polysiloxane macromonomers, and the like. Among them, in terms of excellent heat resistance and weather resistance, acrylic polysiloxane macromonomers are preferred, and acrylic polysiloxane macromonomers represented by the following structural formulas (1) and (2) are more preferred. body.

Here, R represents a (meth)acrylic group-containing functional group, such as a (meth)acrylic group, and X and Y each independently represent an integer of 0 or more. Furthermore, the upper limit of X and Y is not particularly limited, and is, for example, 500 or less, especially 200 or less.

The content of the polysiloxane macromonomer in the raw material monomer mixture is preferably 1% by weight or more and 90% by weight or less. By setting the content of the polysiloxane macromonomer within the above-mentioned range, the adhesion increase at high temperature can be suppressed, and the obtained adhesive composition can exhibit higher initial adhesion. From the standpoint of further suppressing the subsequent increase and further improving the initial adhesion, the lower limit of the content of the polysiloxane macromonomer in the raw material monomer mixture is more preferably 5% by weight, and the more preferable lower limit is 10% by weight. A more preferable upper limit is 80% by weight, and a more preferable upper limit is 60% by weight. That is, the content of the structural unit derived from the polysiloxane macromonomer in the polysiloxane-based graft copolymer is preferably 1% by weight or more and 90% by weight or less. The lower limit of the content of the structural unit derived from the polysiloxane macromonomer is more preferably 5% by weight, still more preferably the lower limit is 10% by weight, the more preferable upper limit is 80% by weight, and the more preferable upper limit is 60% by weight.

The polysiloxane-based graft copolymer has a functional group capable of crosslinking with the adhesive component. By making the polysiloxane-based graft copolymer have a functional group capable of crosslinking with the adhesive component, the polysiloxane-based graft copolymer gathered at the interface with the adherend and the adhesive component are cross-linked and fixed, Therefore, the suppression effect of subsequent hyperactivity can be improved. In addition, by fixing the silicone-based graft copolymer to the adhesive component, the contamination of the adherend caused by the silicone-based graft copolymer can be suppressed.

The functional group that can be cross-linked with the adhesive component is appropriately selected according to the functional group possessed by the adhesive component. Examples include carboxyl groups, radically polymerizable unsaturated bonds, hydroxyl groups, amide groups, and isocyanate groups. , Epoxy and so on. Examples of monomers having functional groups capable of being crosslinked with the above-mentioned adhesive components include monomers having carboxyl groups such as (meth)acrylic acid, 2-(meth)acryloxyethyl isocyanate and the like having isocyanate Monomers of acid groups, etc. In addition, as a monomer having a functional group capable of being crosslinked with the above-mentioned adhesive component, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. may also be exemplified Monomers, monomers having amide groups such as (meth)acrylamide, monomers having epoxy groups such as glycidyl (meth)acrylate, etc. Among them, in terms of improving the crosslinking density and the elastic modulus of the adhesive layer composed of the adhesive composition, and further suppressing the increase in adhesion at high temperatures, it is a function capable of crosslinking with the adhesive composition The group is preferably a radically polymerizable unsaturated bond. These functional groups that can be cross-linked with the adhesive component may be used alone or in combination of two or more kinds. The functional group capable of being crosslinked with the adhesive component can be introduced, for example, by using "a monomer having a functional group capable of being crosslinked with the adhesive component" for the raw material monomer mixture. In addition, when the functional group that can be crosslinked with the adhesive component is a radically polymerizable unsaturated bond, the raw material monomer containing the "(meth)acrylic monomer having a functional group" can be used The mixture is radically polymerized, and then a monomer having a radically polymerizable unsaturated bond and a functional group that reacts with the above-mentioned functional group is reacted and introduced.

The content of the "monomer having a functional group capable of crosslinking with the adhesive component" in the raw material monomer mixture is preferably 0.1% by weight or more and 10% by weight or less. By setting the blending amount of the "monomer having a functional group capable of crosslinking with the above-mentioned adhesive component" within the above range, even if the adhesive component and the silicone-based graft copolymer are sufficiently crosslinked, the adhesive component A sufficient cross-linking structure can also be constructed inside, so the adhesion acceleration at high temperature can be more suppressed. From the standpoint of further suppressing the adhesion enhancement at high temperature, the blending amount of the "monomer having a functional group capable of crosslinking with the adhesive component" is more preferably 0.5% by weight or more, and more preferably 2% by weight Above, it is more preferably 8% by weight or less, and still more preferably 5% by weight or less. That is, the content of the structural unit derived from the "monomer having a functional group capable of crosslinking with the adhesive component" in the polysiloxane-based graft copolymer is preferably 0.1% by weight or more and 10% by weight or less. The content of the structural unit derived from the "monomer having a functional group capable of crosslinking with the above-mentioned adhesive component" is more preferably 0.5% by weight or more, more preferably 2% by weight or more, more preferably 8% by weight or less, and further Preferably it is 5 weight% or less. In addition, when the functional group that can be crosslinked with the above-mentioned adhesive component is a radically polymerizable unsaturated bond, relative to 100% by weight of the raw material monomer mixture, the reaction "with the above-mentioned radically polymerizable unsaturated bond The blending amount of "monomer" is preferably 0.5% by weight or more, more preferably 1% by weight or more, and still more preferably 2% by weight or more. The blending amount of the "monomer having the aforementioned radically polymerizable unsaturated bond" is preferably 10% by weight or less, more preferably 8% by weight or less, and still more preferably 5% by weight or less.

The functional group capable of crosslinking with the adhesive component is preferably a functional group that reacts with the adhesive component by heating. Since the functional groups that can be crosslinked with the above-mentioned adhesive components react by heating, the heat of the high-temperature treatment step can be used to carry out the crosslinking reaction. Therefore, the crosslinking steps such as photohardening steps can be reduced, and the productivity can be improved. . As the "functional group capable of crosslinking with the adhesive component" that reacts with the adhesive component by heating, for example, a radically polymerizable unsaturated bond, a transesterified hydroxyl group, and the like can be cited.

The above-mentioned polysiloxane-based graft copolymer preferably has a polar functional group. In addition, the term “polar functional group” here includes both of the following: a polar functional group that is a functional group capable of being crosslinked with the adhesive component, and a polar functional group that is not crosslinked with the adhesive component. The polysiloxane-based graft copolymer has a polar functional group, which can improve the initial adhesion of the obtained adhesive composition. As said polar functional group, a hydroxyl group, a carboxyl group, etc. are mentioned, for example. The polar functional group can be introduced by using a monomer having the polar functional group for the raw material monomer mixture. Examples of the monomer having the above-mentioned hydroxyl group include 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and the like. Examples of monomers having the above-mentioned carboxyl group include (meth)acrylic acid, 2-(meth)acryloxyethyl succinic acid, 2-(meth)acryloxyethyl-phthalic acid, 2 -(Meth)acryloyloxyethylhexahydrophthalic acid, β-carboxyethyl (meth)acrylate, etc.

The content of the monomer having the polar functional group in the raw material monomer mixture is preferably 0.1% by weight or more and 50% by weight or less. By making the content of the monomer having the polar functional group in the above range, the initial adhesive force of the obtained adhesive composition can be improved, and the polysiloxane-based graft copolymer can be easily aggregated in and The interface of the adhesive. From the viewpoint of further improving the high initial adhesion and making the polysiloxane-based graft copolymer more likely to aggregate at the interface with the adherend, the content of the monomer having the above-mentioned polar functional group is more preferably 0.5% by weight or more, It is more preferably 1% by weight or more, and still more preferably 2% by weight or more. The content of the monomer having the above-mentioned polar functional group is more preferably 40% by weight or less, still more preferably 30% by weight or less, still more preferably 10% by weight or less, still more preferably 8% by weight or less, most preferably 5 Weight% or less. That is, the content of the structural unit derived from the monomer having the polar functional group in the polysiloxane-based graft copolymer is preferably 0.1% by weight or more and 50% by weight or less. The content of the structural unit derived from the monomer having the aforementioned polar functional group is more preferably 0.5% by weight or more, still more preferably 1% by weight or more, and still more preferably 2% by weight or more. The content of the structural unit derived from the monomer having the above-mentioned polar functional group is more preferably 40% by weight or less, still more preferably 30% by weight or less, still more preferably 10% by weight or less, and still more preferably 8% by weight or less , Particularly preferably 5% by weight or less.

Examples of the above-mentioned other monomers include alkyl (meth)acrylates. Examples of the alkyl (meth)acrylates include 2-ethylhexyl acrylate, butyl acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, and propyl (meth)acrylate. , N-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, Isononyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and the like. In addition, as the above-mentioned other monomers, for example, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-butoxyethyl (meth)acrylate Ester, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. Among them, in terms of imparting a moderate adhesive force, 2-ethylhexyl acrylate is preferred.

The above-mentioned polysiloxy graft copolymer preferably has a structure represented by the following structural formula (3). The polysiloxane-based graft copolymer having a structure as shown in the following structural formula (3), because the polysiloxane part is a graft chain, the number of the polysiloxane part can be easily adjusted, and it can be compared with the previous polysiloxane compound More restrained and then hyperactive. In addition, the polysiloxane graft copolymer having a structure as the following structural formula (3) has a radically polymerizable unsaturated bond as a functional group that can be crosslinked with the adhesive component, so the crosslink density with the adhesive component Improved, can more inhibit the subsequent hyperactivity, and can reduce the pollution of the adherend. Furthermore, the polysiloxane-based graft copolymer having a structure such as the following structural formula (3) has a polar functional group, so the initial adhesion is improved, and even when the polysiloxane site is increased, the initial adhesion can be suppressed The reduction of power.

Here, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a methyl group or a hydrogen atom, and R ₅ , R ₆ , and R ₇ each independently represent 1 to 18 having a linear or branched carbon chain A saturated hydrocarbon group with three carbon atoms, R ₈ represents a functional group containing a (meth)acrylic acid group, and R ₉ represents a polar functional group containing group. L, M, N, O, and P each independently represent an integer of 0 or more.

From the viewpoint of optimizing the polarity of the adherend interface, the above-mentioned saturated hydrocarbon group having a linear or branched carbon chain of 1 to 18 carbon atoms in the above structural formula (3) preferably has a carbon number It is 3 or more, more preferably 6 or more, and preferably 15 or less, and more preferably 12 or less.

As the functional group containing the (meth)acrylic acid group in the above structural formula (3), for example, it has 1 to 18 carbon atoms (preferably 2 to 15 carbon atoms, more preferably 3 to 12) (Carbon atoms) containing (meth)acrylic functional groups.

In the above structural formula (3), the polar functional group-containing group includes, for example, a polar functional group-containing saturated hydrocarbon group and an unsaturated hydrocarbon group. From the viewpoint of controlling adhesion, a polar functional group-containing saturated hydrocarbon group is preferred. More preferably, it is a saturated hydrocarbon group having 1 to 18 carbon atoms (more preferably 3 to 15 carbon atoms) having a polar functional group. Examples of the polar functional group contained in the polar functional group-containing group include a carboxyl group and a hydroxyl group. From the viewpoint of suppressing subsequent increase, the polar functional group is preferably a hydroxyl group.

The above-mentioned L, M, N, O and P in the above-mentioned structural formula (3) are each independently 0 or more, so that it is easier to gather at the interface with the adherend, and from the viewpoint of effectively suppressing the subsequent increase, it is preferably 10 Above, it is more preferably 50 or more, still more preferably 100 or more, and preferably 500 or less, more preferably 300 or less, and still more preferably an integer of 200 or less.

The above-mentioned polysiloxane-based graft copolymer preferably has a weight average molecular weight of 400,000 or less. If the molecular weight of the polysiloxane-based graft copolymer is in the above range, the polysiloxane-based graft copolymer becomes easy to move in the adhesive layer, and can be more concentrated at the interface with the adherend, so it can be more Inhibition followed by hyperactivity. From the viewpoint of further suppressing the subsequent increase, the weight average molecular weight is preferably 200,000 or less, and more preferably 100,000 or less. The upper limit of the weight average molecular weight is not particularly limited, but from the viewpoint of suppressing contamination of the adherend, it is preferably 5000 or more. In addition, the said weight average molecular weight can be calculated|required by a polystyrene standard by a GPC method, for example. Specifically, for example, the "2690 Separations Module" manufactured by Water Co., Ltd. can be used as the measuring device, the "GPC KF-806L" manufactured by Showa Denko Co., Ltd. can be used as the column, and ethyl acetate can be used as the solvent. The sample flow rate is 1 mL/min. , Measure the column temperature at 40℃.

The production method of the above-mentioned polysiloxane-based graft copolymer is not particularly limited, and it can be obtained by radically polymerizing the above-mentioned raw material monomer mixture in a solvent. As the polymerization method of the above-mentioned radical polymerization, the same method as the above-mentioned adhesive component can be used.

The content of the polysiloxane-based graft copolymer in the adhesive composition of one embodiment of the present invention is preferably 0.1% by weight or more and 20% by weight or less. By making the content of the above-mentioned polysiloxane-based graft copolymer in the adhesive composition at least 0.1% by weight, it is possible to further suppress the increase in adhesion at high temperatures. By making the content of the above-mentioned polysiloxane-based graft copolymer 20% by weight or less, the initial adhesive force of the adhesive composition can be improved, and the white turbidity of the adhesive composition can be suppressed, and the adhesive composition can be separated Perform the steps of using light such as alignment. In addition, since the polysiloxane-based graft copolymer tends to accumulate at the interface of the adherend, it can suppress the adhesion increase in a smaller amount than the conventional polysiloxane compound. From the viewpoint of further suppressing the adhesion enhancement and white turbidity at high temperature, the content of the polysiloxane-based graft copolymer in the adhesive composition is more preferably 1.5% by weight or more, and more preferably 3% by weight or more. The content of the above-mentioned polysiloxane-based graft copolymer is more preferably 15% by weight or less, still more preferably 10% by weight or less, still more preferably 8% by weight or less, and particularly preferably 5% by weight or less.

The adhesive composition of one embodiment of the present invention preferably contains a crosslinking agent. The crosslinking agent can sufficiently crosslink the adhesive component and the polysiloxane-based graft copolymer. In addition, by containing the crosslinking agent, the cohesive force of the adhesive composition is improved, and therefore the initial adhesive force can be improved. The said crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent, etc. are mentioned. Among them, an epoxy-based crosslinking agent is preferred in terms of more improvement in the cohesive force of the adhesive component.

The content of the crosslinking agent in the adhesive composition of one embodiment of the present invention is preferably 0.01-20% by weight. By containing the crosslinking agent in the above range, the adhesive component and the polysiloxane-based graft copolymer can be sufficiently crosslinked, and the cohesive force of the adhesive component can be increased to further improve the initial adhesive force. From the viewpoint of further improving the initial adhesion, the lower limit of the content of the crosslinking agent is more preferably 0.05% by weight, furthermore preferably the lower limit is 0.1% by weight, the more preferable upper limit is 10% by weight, and the more preferable upper limit is 5 weight%.

The adhesive composition of one embodiment of the present invention may also optionally contain a gas generator that generates gas by stimulation, or an inorganic filler, heat stabilizer, antioxidant, antistatic agent, plasticizer, resin, Well-known additives such as surfactants and waxes.

The manufacturing method of the adhesive composition of one embodiment of the present invention is not particularly limited. For example, it can be obtained by: adding the above-mentioned polymer manufactured by the above-mentioned method to the solution of the adhesive component manufactured by the above-mentioned method. Silicon-oxygen graft copolymer and other additives as needed and mixed.

The use of the adhesive composition of one embodiment of the present invention is not particularly limited, and can be suitably used as an adhesive composition for forming the adhesive layer of the adhesive tape. In addition, one aspect of the present invention is also an adhesive tape having a substrate and an adhesive layer laminated on at least one side of the substrate, and the adhesive layer is composed of an adhesive composition according to an embodiment of the present invention.

The adhesive tape of one embodiment of the present invention has a base material. The material constituting the aforementioned substrate is preferably a material having heat resistance. Examples of the above-mentioned materials with heat resistance include: polyethylene terephthalate, polyethylene naphthalate, polyacetal, polyamide, polycarbonate, polyphenylene ether, and polybutylene terephthalate. Ester, ultra-high molecular weight polyethylene, syndiotactic polystyrene, polyarylate, polyether, polyether sulfide, polyphenylene sulfide, polyether ether ketone, polyimide, poly Etherimines, fluororesins, liquid crystal polymers, etc. Among them, in terms of excellent heat resistance, polyimide is preferred.

The thickness of the aforementioned substrate is not particularly limited, and the preferred lower limit is 25 μm, the more preferred lower limit is 50 μm, the preferred upper limit is 250 μm, and the more preferred upper limit is 125 μm. By setting the above-mentioned base material in this range, an adhesive tape excellent in handleability can be obtained.

The adhesive tape of one embodiment of the present invention has an adhesive layer laminated on at least one side of the substrate. The adhesive layer is composed of the adhesive composition of one embodiment of the present invention.

The gel fraction of the adhesive layer is not particularly limited, but is preferably less than 90% by weight. By making the above-mentioned gel fraction less than 90% by weight, a higher adhesive force can be exerted during application. From the viewpoint of further improving the initial adhesive force, the gel fraction of the adhesive layer is more preferably 80% by weight or less, and more preferably 70% by weight or less. The lower limit of the gel fraction of the adhesive layer is not particularly limited, but from the viewpoint of handleability, it is preferably 20% by weight or more. The gel fraction of the adhesive layer can be adjusted according to the type of the adhesive component, the type and amount of the crosslinking agent, and the like. Furthermore, when the adhesive layer is a hardening type adhesive layer, the gel fraction of the adhesive layer means the gel fraction before curing by light such as ultraviolet rays or heating (initial Gel fraction).

In addition, the gel fraction of the adhesive layer can be specifically measured by the following method. First, scrape 0.1 g of the adhesive from the adhesive layer, immerse it in 50 mL of toluene, and shake it for 24 hours at a temperature of 23° C. and 200 rpm with a shaker. After shaking, use a metal screen (mesh#200 mesh) to separate the toluene from the adhesive that absorbs toluene and swells. Dry the separated adhesive at 110°C for 1 hour. Measure the weight of the adhesive including the metal mesh after drying, and calculate the gel fraction using the following formula (1). Gel fraction (weight %) = 100×(W _1- W ₂ )/W ₀ (1) (W ₀ : initial adhesive weight, W ₁ : dried adhesive weight including metal mesh, W ₂ : The initial weight of the metal screen)

The thickness of the adhesive layer is not particularly limited, but preferably the lower limit is 3 μm and the upper limit is 100 μm. If the thickness of the adhesive layer is in the above range, it can be bonded to the support with sufficient adhesive force. From the same viewpoint, the lower limit of the thickness of the adhesive layer is more preferably 5 μm, and the upper limit is more preferably 50 μm.

The manufacturing method of the adhesive tape of one embodiment of the present invention is not particularly limited, and conventionally known methods can be used. For example, it can be manufactured by applying a solution of the adhesive composition of one embodiment of the present invention on a film that has undergone a mold release treatment, and drying it to form an adhesive layer and bonding it to the substrate .

The use of the adhesive tape of one embodiment of the present invention is not particularly limited. As far as it is difficult to increase the adhesion even at high temperatures, it can be used in the manufacture of semiconductor devices, such as those with heat treatment steps exceeding 200°C. Suitable for use as an adhesive tape for protective components. [Effects of Invention]

According to the present invention, it is possible to provide an adhesive composition capable of suppressing subsequent proliferation even when applied to a high-temperature heat treatment step, and an adhesive layer composed of the adhesive composition. The adhesive tape.

The following examples are given to illustrate the aspects of the present invention in further detail, but the present invention is not limited to these examples.

(Example 1) (Preparation of adhesive component A) Prepare a reactor equipped with a thermometer, agitator, and cooling tube. Add 79 parts by weight of 2-ethylhexyl acrylate (2EHA), 1 part by weight of acrylic acid (AAc), and 20 parts by weight of 4-hydroxybutyl acrylate (4HBA) into the reactor. After parts by weight, 0.01 parts by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate, the reactor was heated to start reflux. Then, 0.01 parts by weight of 1,1-bis(tertiary hexyl peroxide)-3,3,5-trimethylcyclohexane was added as a polymerization initiator in the above-mentioned reactor, and the polymerization was started under reflux. Next, after 1 hour and 2 hours after the initiation of the polymerization, 0.01 parts by weight of 1,1-bis(tertiary hexyl peroxide)-3,3,5-trimethylcyclohexane were added, and then at the start of the polymerization After 4 hours, 0.05 parts by weight of third hexyl peroxide trimethyl acetate was added to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution of a functional group-containing acrylic polymer was obtained. Then, with respect to 100 parts by weight of the resin solid content of the ethyl acetate solution of the functional group-containing acrylic polymer obtained, 8 parts by weight of 2-methacryloxyethyl isocyanate (MOI in the table) was added The reaction proceeds to obtain a solution containing the adhesive component A.

Then, the obtained solution containing the adhesive component A was diluted to 50 times with tetrahydrofuran (THF), and the obtained diluted solution was filtered with a filter made of polytetrafluoroethylene with a pore size of 0.2 μm. After that, the obtained filtrate was supplied to a gel permeation chromatograph to perform GPC measurement. The polystyrene conversion molecular weight of the adhesive component is measured, and the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) are obtained. As a result, Mw: 570,000, and Mw/Mn: 6.4. In addition, the measuring equipment and measuring conditions are as follows. Gel permeation chromatography: e2695 Separations Module (manufactured by Waters) Detector: Differential refractometer (2414, manufactured by Waters) String: GPC KF-806L (manufactured by Showa Denko Corporation) Standard sample: STANDRAD SM-105, manufactured by Showa Denko Corporation Sample flow rate: 1 mL/min Column temperature: 40℃

(Preparation of adhesive component B) Except that 2-methacryloxyethyl isocyanate was not used, a solution containing adhesive component B was obtained in the same manner as adhesive component A, and Mw and Mw/Mn were measured.

(Preparation of polysiloxy graft copolymer A) Prepare a reactor equipped with a thermometer, agitator, and cooling tube. Add 89 parts by weight of 2-ethylhexyl acrylate (2EHA), 10 parts by weight of polysiloxane macromonomer, and 1 part by weight of acrylic acid (AAc) into the reactor. After 0.01 part by weight of lauryl mercaptan and 80 parts by weight of ethyl acetate, the reactor was heated to start reflux. Then, 0.01 parts by weight of 1,1-bis(tertiary hexyl peroxide)-3,3,5-trimethylcyclohexane was added as a polymerization initiator in the above-mentioned reactor, and the polymerization was started under reflux. Next, after 1 hour and 2 hours after the initiation of the polymerization, 0.01 parts by weight of 1,1-bis(tertiary hexyl peroxide)-3,3,5-trimethylcyclohexane were added, and then at the start of the polymerization After 4 hours, 0.05 parts by weight of third hexyl peroxide trimethyl acetate was added to continue the polymerization reaction. Then, 8 hours after the start of the polymerization, an ethyl acetate solution of the polysiloxane-based graft copolymer A was obtained. For the obtained polysiloxane-based graft copolymer A, Mw and Mw/Mn were measured by the same method as the preparation of the adhesive component A. Furthermore, the polysiloxane giant single system uses the following ones. Polysiloxane giant monomer: KF-2012, single-terminal methacrylic acid modified PDMS, manufactured by Shin-Etsu Chemical

(Preparation of polysiloxy graft copolymer B) Prepare a reactor equipped with a thermometer, agitator, and cooling tube. Add 39 parts by weight of 2-ethylhexyl acrylate (2EHA), 60 parts by weight of polysiloxane macromonomer, and 4-hydroxybutyl acrylate (4HBA) into the reactor. ) After 1 part by weight, 0.01 part by weight of lauryl mercaptan, and 80 parts by weight of ethyl acetate, the reactor is heated to start reflux. Then, 0.01 parts by weight of 1,1-bis(tertiary hexyl peroxide)-3,3,5-trimethylcyclohexane was added as a polymerization initiator in the above-mentioned reactor, and the polymerization was started under reflux. Next, after 1 hour and 2 hours after the initiation of the polymerization, 0.01 parts by weight of 1,1-bis(tertiary hexyl peroxide)-3,3,5-trimethylcyclohexane were added, and then at the start of the polymerization After 4 hours, 0.05 parts by weight of third hexyl peroxide trimethyl acetate was added to continue the polymerization reaction. Then, 8 hours after the start of polymerization, an ethyl acetate solution of a functional group-containing acrylic polymer was obtained. Then, with respect to 100 parts by weight of the resin solid content of the ethyl acetate solution of the obtained functional group-containing acrylic polymer, 0.5 parts by weight of 2-methacryloxyethyl isocyanate (MOI in the table) was added The reaction proceeds to obtain a solution containing the polysiloxy graft copolymer B. With respect to the obtained polysiloxane-based graft copolymer B, Mw and Mw/Mn were measured by the same method as the preparation of the adhesive component A.

(Preparation of polysiloxy graft copolymer C～E) The monomer composition was set as shown in Table 1. Except for this, the polysiloxane-based graft copolymer C to E was obtained in the same manner as the preparation of the polysiloxane-based graft copolymer B, and the Mw and Mw/ Mn.

(Preparation of polysiloxy graft copolymer F) The monomer composition was set as shown in Table 1. Except for this, the polysiloxane-based graft copolymer F was obtained in the same manner as the preparation of the polysiloxane-based graft copolymer A, and Mw and Mw/Mn were measured.

[Table 1] Adhesive component A Adhesive component B composition 2EHA 79 79 AAc 1 1 4HBA 20 20 MOI 8 - Molecular weight Mw (ten thousand) 57 57 The molecular weight distribution Mw/Mn 6.4 6.4 Polysiloxy graft copolymer A Polysiloxane graft copolymer B Polysiloxy graft copolymer C Polysiloxane graft copolymer D Polysiloxy graft copolymer E Polysiloxane graft copolymer F composition 2EHA 89 39 37 35 30 40 Polysiloxane giant monomer 10 60 60 60 60 60 AAc 1 - - - - - 4HBA - 1 3 5 10 - MOI - 0.5 1.5 2.5 5 - Molecular weight Mw (ten thousand) 7.1 4.9 5.3 5.2 5.6 5.6 The molecular weight distribution Mw/Mn 2.8 1.7 1.7 1.8 1.8 1.8

(Example 1) With respect to 100 parts by weight of the solid content of the obtained solution containing adhesive component A, 5.0 parts by weight of polysiloxane-based graft copolymer A as a peeling aid, 1.0 part by weight of thermal polymerization initiator, and epoxy-based 0.1 parts by weight of the crosslinking agent was used to obtain an adhesive composition solution. Next, apply the adhesive composition solution to the mold release treatment surface of the polyethylene terephthalate film that has been subjected to mold release treatment with a doctor blade so that the thickness of the dried film becomes 40 μm, and perform it at 110°C Heat and dry for 5 minutes to obtain an adhesive layer. The obtained adhesive layer was bonded to the corona-treated surface of a transparent polyethylene naphthalate film with a thickness of 50 μm, which was corona-treated on one side, to obtain an adhesive tape. In addition, as the thermal polymerization initiator and the crosslinking agent, the following were used. Thermal polymerization initiator: PERBUTYL O, manufactured by NOF Corporation Epoxy crosslinking agent: Tetrad C, manufactured by Mitsubishi Gas Chemical Company

(Examples 2 to 16, Comparative Examples 1 to 5) The types and blending amounts of the used adhesive components, peeling aids, polymerization initiators, and crosslinking agents were set as shown in Tables 2 and 3, except that the adhesive tape was obtained in the same manner as in Example 1 . In addition, as the peeling aid, polymerization initiator, and crosslinking agent, the following were used. Polysiloxane diacrylate: EBECRYL350, manufactured by DAICEL-ALLNEX Silicone oil: KF-96-10cs, manufactured by Shin-Etsu Chemical Co., Ltd. Photopolymerization initiator: Esacure One, manufactured by Nihon SiberHegner Isocyanate-based crosslinker: Coronaate L45, manufactured by Tosoh Corporation

[Evaluation] The adhesive tapes obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Tables 2 and 3.

(Initial gel fraction) Scrape 0.1 g of the adhesive from the adhesive layer of the adhesive tape, immerse it in 50 mL of toluene, and use a shaker to shake for 24 hours at a temperature of 23°C and 200 rpm. After shaking, use a metal screen (mesh#200 mesh) to separate the toluene from the adhesive that absorbs toluene and swells. Dry the separated adhesive at 110°C for 1 hour. Measure the weight of the adhesive including the metal mesh after drying, and use the following formula (1) to calculate the gel fraction. Gel fraction (weight %) = 100×(W _1- W ₂ )/W ₀ (1) (W ₀ : initial adhesive weight, W ₁ : dried adhesive weight including metal mesh, W ₂ : The initial weight of the metal screen)

(Evaluation of initial adhesion and adhesion after heating) The adhesive tape was cut into a width of 25 mm to obtain a test piece. Place the adhesive layer of the obtained test piece on a glass plate (manufactured by Songlang Glass Industry Co., Ltd., large glass slide with white edging No. 2). Secondly, a rubber roller of 2 kg was reciprocated on the test piece at a speed of 300 mm/min to bond the test piece and the glass plate. Then, it left still at 23 degreeC for 1 hour, and produced the test sample. For the test sample after standing, perform a 180° tensile test at a peeling speed of 300 mm/min in accordance with JIS Z0237 to determine the initial adhesion. Then, the measurement sample prepared by the same method as the above was heat-treated at 220°C for 2 hours. After leaving it to cool, perform a 180° tensile test by the same method as above to measure the adhesive force after heating. In addition, the adhesive strength after heating of Comparative Examples 2 to 4 could not be measured because the paste remained on the entire surface of the glass plate.

(Evaluation of pollution) The glass plate after the measurement of the adhesive force after heating was visually observed, and the residue was evaluated based on the following criteria. ◎: No residue ○: There is residue in a part (less than 10% of the attached area) △: There is residue in a part (a wider range than 10% of the attached area and less than 30%) ×: There are residues on the whole surface (a wider range than 30% of the attached area)

[Table 2] Example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Adhesive component A 100 - 100 100 100 100 100 100 100 100 - 100 100 100 100 100 Adhesive component B - 100 - - - - - - - - 100 - - - - - Stripping aid Polysiloxy graft copolymer A 5.0 5.0 - - - - - - - - - - - - - - Polysiloxane graft copolymer B - - 5.0 - - - - - - - - - - - - - Polysiloxy graft copolymer C - - - 5.0 - - - - - - - - - - - - Polysiloxane graft copolymer D - - - - 5.0 - - - - - - - - - - - Polysiloxy graft copolymer E - - - - - 0.5 1.0 5.0 10.0 5.0 5.0 5.0 20.0 30.0 5.0 5.0 Polysiloxane diacrylate - - - - - - - - - - - - - - - - Silicone oil - - - - - - - - - - - - - - - - Polymerization initiator Thermal polymerization initiator 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 - 1.0 1.0 1.0 1.0 1.0 1.0 Photopolymerization initiator - - - - - - - - - 1.0 - - - - - - Crosslinking agent Epoxy crosslinking agent 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 - 0.1 0.1 0.5 1.0 Isocyanate-based crosslinking agent - - - - - - - - - - - 0.1 - - - - Evaluation Initial gel fraction (weight%) 49 51 48 55 50 51 45 50 55 52 49 53 57 60 82 90 Initial adhesion (N/25 mm) 2.5 2.5 2.8 3.0 3.0 2.5 1.9 1.8 1.5 1.8 2.0 2.0 1.3 1.1 0.9 0.7 Adhesion after heating (N/25 mm) 0.3 2.3 0.3 0.3 0.3 0.5 0.3 0.2 0.2 0.2 1.8 0.2 0.2 0.2 0.2 0.2 Pollution evaluation 〇 〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 〇 ◎ 〇 △ 〇 〇

[table 3] Comparative example 1 2 3 4 5 Adhesive component A 100 100 - 100 100 Adhesive component B - - 100 - - Stripping aid Polysiloxy graft copolymer A - - - - - Polysiloxane graft copolymer B - - - - - Polysiloxy graft copolymer C - - - - - Polysiloxane graft copolymer D - - - - - Polysiloxy graft copolymer E - - - - - Polysiloxane graft copolymer F - - - - 5.0 Polysiloxane diacrylate 5.0 - - - - Silicone oil - - - 5 - Polymerization initiator Thermal polymerization initiator 1.0 1.0 1.0 - - Photopolymerization initiator - - - - - Crosslinking agent Epoxy crosslinking agent 0.1 0.1 0.1 0.1 0.1 Isocyanate-based crosslinking agent - - - - - Evaluation Initial gel fraction (weight%) 46 44 49 47 48 Initial adhesion (N/25 mm) 0.2 3.5 2.5 2.0 2.5 Adhesion after heating (N/25 mm) 0.2 - - - - Pollution evaluation 〇 X X X X [Industrial availability]

According to the present invention, it is possible to provide an adhesive composition capable of suppressing subsequent acceleration even when applied to a high-temperature heat treatment step, and an adhesive composed of the adhesive composition. Layer of adhesive tape.

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Claims (10)

An adhesive composition contains an adhesive component and a polysiloxane-based graft copolymer. The polysiloxane-based graft copolymer has a functional group capable of crosslinking with the adhesive component. The adhesive composition according to claim 1, wherein the adhesive composition is a hardened adhesive composition containing a polymerization initiator. The adhesive composition of claim 1 or 2, wherein the adhesive component has a radically polymerizable unsaturated bond in the molecule. The adhesive composition of 2 or 3, wherein the functional group in the polysiloxane-based graft copolymer that can be crosslinked with the adhesive component is a radically polymerizable unsaturated bond. The adhesive composition of 2, 3 or 4, wherein the functional group capable of crosslinking with the adhesive component in the polysiloxane-based graft copolymer is a functional group that reacts with the adhesive component by heating. The adhesive composition of 2, 3, 4, or 5, wherein the above-mentioned polysiloxane-based graft copolymer has a polar functional group. The adhesive composition of 2, 3, 4, 5 or 6, wherein the above-mentioned polysiloxy graft copolymer has a structure shown in the following structural formula:

, Here, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a methyl group or a hydrogen atom, and R ₅ , R ₆ , and R ₇ each independently represent 1 to 1 having a linear or branched carbon chain A saturated hydrocarbon group with 18 carbon atoms, R ₈ represents a functional group containing (meth)acrylic acid group, R ₉ represents a group containing polar functional group, L, M, N, O and P each independently represent an integer of 0 or more . The adhesive composition of 2, 3, 4, 5, 6, or 7, wherein the content of the polysiloxane-based graft copolymer in the adhesive composition is 0.1-20% by weight. An adhesive tape having a substrate and an adhesive layer laminated on at least one side of the substrate, and the adhesive layer is composed of the adhesive composition of claim 1, 2, 3, 4, 5, 6, 7 or 8. Constituted. Such as the adhesive tape of claim 9, wherein the gel fraction of the adhesive layer is less than 90% by weight.