KR20200036605A - Adhesieve sheet for temporary-attachment and methode for producing semiconductor device using the same - Google Patents

Abstract

The present invention provides an adhesive composition method which exhibits excellent adhesion, does not generate bubbles and gaps even after a high temperature process, and can be easily separated by photo-curing in a peeling step. In addition, a temporary fixing adhesive sheet comprises: a base film; and at least one adhesive layer.

Description

Temporary fixing adhesive sheet and manufacturing method of semiconductor device using same {ADHESIEVE SHEET FOR TEMPORARY-ATTACHMENT AND METHODE FOR PRODUCING SEMICONDUCTOR DEVICE USING THE SAME}

The present invention relates to a method for manufacturing a temporary fixing adhesive sheet and a semiconductor device using the same.

Recently, the trend of miniaturization, thinning, and high-capacity of electronic devices has been expanded, and accordingly, the need for high-density and high-density semiconductor packages is rapidly increasing. Reflecting this, the size of the semiconductor chip is getting larger and at the same time, the thickness of the chip is getting thinner.

The thin semiconductor chip has a difficult handling problem during the manufacturing process. Therefore, a method of temporarily fixing a thin semiconductor chip using an adhesive sheet, etc., and processing, processing, and transferring it in a temporarily fixed state Is being applied.

Such a pressure-sensitive adhesive sheet exhibits excellent adhesion, but in a process of separating a fixed thin semiconductor chip after a series of processes is completed, it does not damage the semiconductor chip and at the same time, it has a peeling property that does not leave residues or the like on the surface. Must have. In addition, since many of the processes in the semiconductor manufacturing process are performed under high temperature conditions, high heat resistance is required so that adhesive strength does not decrease due to thermal decomposition or the like during the process. Particularly, in the semiconductor process, an ultra-high temperature process of 200 ° C or higher is performed. When the heat resistance is low, a problem of appearance defects due to air bubbles and floating phenomenon occurs between the temporary adhesive sheet and the thin substrate.

On the other hand, as a temporary adhesive material, an ultraviolet curable pressure-sensitive adhesive whose adhesive strength is lowered by ultraviolet irradiation has been recently used. However, in the case of such an ultraviolet curable pressure-sensitive adhesive, an additive such as a photoinitiator in the pressure-sensitive adhesive is thermally decomposed in a high-temperature process, or due to the migration phenomenon of the additive, there is a problem of insufficient adhesion reduction in a peeling step.

Accordingly, as a temporary fixing adhesive sheet, there is a need for the development of an adhesive material that does not generate bubbles and floats on the exterior even after a high temperature process and is easily removable.

The present invention is to provide an adhesive sheet for temporary fixation that exhibits excellent adhesion and does not generate bubbles and excitation even after a high temperature process, and can be easily separated by light curing in a peeling step.

In addition, the present invention is to provide a semiconductor manufacturing method using the temporary fixing adhesive sheet.

According to an embodiment of the present invention, the base film; And at least one adhesive layer;

The adhesive layer includes a binder resin comprising a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, and contains 10 to 30% by weight of silicone (Si) based on the total weight of the adhesive layer,

The (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group is at least one selected from the group consisting of a first repeating unit derived from a (meth) acrylate-based monomer containing a silicone-based functional group, a hydroxyl group, a carboxyl group, and a nitrogen-containing functional group. A second repeating unit derived from a crosslinkable monomer containing a reactive functional group,

The second repeating unit, based on the total weight of the second repeating unit, provides an adhesive sheet for temporary fixation, wherein the second repeating unit of 20 to 95% by weight includes a photoreactive functional group in the side chain.

According to another embodiment of the present invention, attaching the adhesive layer of the above-mentioned temporary fixing adhesive sheet to a predetermined portion of the semiconductor device; A step of performing a predetermined process with respect to the semiconductor device to which the adhesive sheet is attached; After passing through the predetermined process, irradiating ultraviolet rays to the base film of the temporary fixing adhesive sheet; And detaching the temporary fixing adhesive sheet from the semiconductor device.

Hereinafter, a temporary fixing adhesive sheet according to embodiments of the invention and a method of manufacturing a semiconductor device using the same will be described in detail.

Prior to that, the terminology is only for referring to a specific embodiment, and is not intended to limit the present invention, unless expressly stated in the specification.

Singular forms used herein include plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of 'include' embodies a specific characteristic, region, integer, step, action, element and / or component, and other specific characteristic, region, integer, step, action, element, component and / or group. It does not exclude the existence or addition of.

In addition, in this specification, terms including an ordinal number such as 'first' and 'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, the first component may also be referred to as the second component, and similarly, the second component may be referred to as the first component.

As a result of continuous research by the present inventors, in the manufacture of a temporary fixing adhesive sheet used in a semiconductor manufacturing process, a polymer containing a repeating unit having a specific structure is used as a binder resin for forming an adhesive layer, and at the same time, silicone in the adhesive layer By controlling the content, excellent adhesion is realized during the manufacturing process of the semiconductor, and it can be easily peeled off by exerting a sufficient adhesive strength reduction effect by photocuring in the peeling step after the high temperature process. In addition, by improving heat resistance, it is possible to exhibit excellent appearance characteristics without generating bubbles or floating in the exterior even during a high temperature process. Accordingly, when the temporary fixing adhesive sheet is used as a protective film or a carrier film in a semiconductor manufacturing process, the efficiency of a semiconductor manufacturing process can be improved, and the quality of the manufactured semiconductor can be improved.

I. Temporary fixing adhesive sheet

Specifically, the temporary fixing adhesive sheet according to an embodiment of the invention,

Base film; And

It includes at least one adhesive layer;

The adhesive layer includes a binder resin comprising a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, and contains 10 to 30% by weight of silicone (Si) based on the total weight of the adhesive layer,

The (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group is at least one selected from the group consisting of a first repeating unit derived from a (meth) acrylate-based monomer containing a silicone-based functional group, a hydroxyl group, a carboxyl group, and a nitrogen-containing functional group. Contains a second repeating unit derived from a crosslinkable monomer containing a reactive functional group,

With respect to the total weight of the second repeating unit, 20 to 95% by weight of the second repeating unit includes a photoreactive functional group in the side chain.

In the temporary fixing adhesive sheet, the adhesive layer is located on at least one surface of the base film, and includes the above-mentioned binder resin, but is prepared using an adhesive composition comprising conditions that satisfy the silicone content range included in the adhesive layer. Can be.

Since the silicone present in the adhesive layer exists as a siloxane bond in the acrylate-based binder resin, it has a high binding energy compared to a carbon-carbon bond, and thus can exhibit excellent heat resistance even at high temperatures of 200 ° C. or higher. However, if the content of silicone in the adhesive layer is too high, there is a fear that the adhesive strength of the adhesive layer is lowered, and if it is too low, it may not exhibit sufficient heat resistance at high temperatures, and re-removal after the process may be difficult. Accordingly, in the present invention, the silicone resin is 10% by weight or more, or 12% by weight or more, or 15% by weight or more, 30% by weight or less, and 25% by weight with respect to the total weight of the adhesive layer through controlling the binder resin and the content thereof. % Or less, or 23% by weight or less. When included in the above-mentioned content range, while maintaining excellent adhesion of the adhesive layer, it is possible to prevent heat and air bubbles from rising after improving the heat resistance.

Meanwhile, the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer includes (a) a binder resin containing a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, (b) a photoinitiator, and (c) a multifunctional crosslinking agent. , Optionally (d) further comprising a tertiary amine compound, the content of these constituents may be determined within a range that satisfies the above-described silicone content range in the adhesive layer. Accordingly, the pressure-sensitive adhesive layer prepared using the above-described pressure-sensitive adhesive composition includes the above-mentioned components (a) to (c), and optionally (d), and 10 to 30 weight of silicone based on the total weight of the pressure-sensitive adhesive layer. %. Hereinafter, each component will be described in detail.

(a) Binder resin

In the pressure-sensitive adhesive composition, (a) the binder resin includes a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, and the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, (a1) a first repeating unit derived from a (meth) acrylate-based monomer containing a silicone-based functional group; and (a2) a second repeat derived from a crosslinkable monomer comprising at least one reactive functional group selected from the group consisting of a hydroxy group, a carboxyl group, and a nitrogen-containing functional group. Unit; and the second repeating unit of 20 to 95% by weight based on the total weight of the second repeating unit of (a2) includes a photoreactive functional group in the side chain.

The first repeating unit derived from a (meth) acrylate-based monomer containing a silicone-based functional group and a second repeating unit derived from a crosslinkable monomer capable of forming a crosslinked structure therewith, and a part of the second repeating unit is a side chain By including a (meth) acrylate-based resin having a random copolymerizable structure having a photoreactive functional group as a binder resin, excellent adhesion stability can be realized even at a high temperature process.

In the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, the first repeating unit of (a1) is a repeating unit comprising a structure derived from a (meth) acrylate-based compound containing a silicone-based functional group, wherein The silicone-based functional group is a polyalkylsiloxane group in which 1 to 200 alkylsiloxanes are bound, a polyarylsiloxane group in which 1 to 200 arylsiloxanes are bound, or a polyorganosiloxane in which 2 to 200 are bonded by mixing alkylsiloxane and arylsiloxane In this case, the alkyl may be an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl or propyl, and the aryl may be an aryl group having 6 to 2 carbon atoms such as phenyl. As a specific example, the silicone-based functional group may be any one of the functional groups represented by the following Chemical Formulas 1a to 1c:

[Formula 1a]

[Formula 1b]

[Formula 1c]

In the formulas 1a to 1c,

R ₁ to R ₄ may each independently be a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more specifically a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more specifically, a hydrogen atom or a methyl group.

In addition, each of the n1 to n3 independently represents an integer of 1 to 200, and more specifically, may be an integer of 5 to 100.

As described above, since the silicone-based functional group included in the first repeating unit has a siloxane bond having a higher binding energy than the carbon-carbon bond, the heat resistance of the binder resin may be increased to increase the thermal decomposition temperature. Accordingly, it is possible to realize excellent adhesion stability even at a high temperature process, and to prevent the occurrence of air bubbles or floating.

More specifically, the first repeating unit of (a1) may include at least one structure derived from a silicon-based functional group-containing (meth) acrylate-based compound represented by Formulas 2a to 2d:

[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

In Chemical Formulas 2a to 2d,

R ₁ to R ₄ may be each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more specifically, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R _a to R _e are each independently hydrogen or a methyl group,

x, y, z, w and v are each independently an integer from 1 to 3,

n1 to n4 each independently represent an integer of 1 to 200, and more specifically, may be an integer of 5 to 100.

In addition, the silicone-based functional group-containing (meth) acrylate-based compound includes a (meth) acrylate group at one end or both ends, and is used for preparing a binder resin such as ethylhexyl acrylate (EHA), hydroxyethyl acrylate (HEA), etc. Random copolymerization with monomers.

The silicone-based functional group-containing (meth) acrylate-based compound may also have a weight average molecular weight (Mw) of 10 to 10,000 g / mol, more specifically 1,000 to 5,000 g / mol. By having a weight average molecular weight in the above range, it can exhibit excellent effects in terms of heat resistance and compatibility.

The silicon-based functional group-containing (meth) acrylate-based compound may be directly prepared by using a known organic chemical reaction, or as Silaplane ™ FM-0721, Silaplane ™ FM-0711, or Silaplane ™ FM-0725 manufactured by JNC. It is commercially available.

The first repeating unit of (a1) may be included in an amount of 10 to 90% by weight based on the total weight of the (meth) acrylate-based resin having the silicone-based functional group and photoreactive functional group. If the content of the first repeating unit is less than 10% by weight, the effect of improving the heat resistance is negligible, and the content of the second repeating unit of (a2) is excessively increased, so that the unreacted functional group that does not participate in the crosslinking reaction is peeled off. Desorption can be difficult. Moreover, when it exceeds 90% by weight, the surface energy of the binder resin is too low, and there is a fear that the adhesive strength of the pressure-sensitive adhesive composition is lowered. More specifically, the first repeating unit of (a1) is 10 to 80% by weight, more specifically 10 to 40% by weight, based on the total weight of the (meth) acrylate-based resin having the silicone-based functional group and photoreactive functional group. It can be included as

In the present invention, the content of each repeating unit in the binder resin can be calculated from the results after nuclear magnetic resonance (NMR) analysis.

On the other hand, the second repeating unit of (a2) in the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, crosslinking comprising at least one functional group selected from the group consisting of a hydroxy group, a carboxyl group, and a nitrogen-containing functional group. As a repeating unit containing a structure derived from a sex monomer, a reactive functional group such as a hydroxy group, a carboxyl group, or a nitrogen-containing functional group in the second repeating unit may react with a polyfunctional crosslinking agent during thermal curing to implement a three-dimensional crosslinking structure. As a result, a high crosslinking density is imparted to the pressure-sensitive adhesive composition, and the cohesive force is increased to exhibit a sufficient fixing force during the semiconductor process.

Specifically, the second repeating unit may be derived from a (meth) acrylate-based monomer containing a hydroxy group, and such monomers include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylic. Rate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, or 2- And hydroxypropylene glycol (meth) acrylate. These may be used alone or in combination of two or more.

In addition, the second repeating unit may be derived from a (meth) acrylic acid or (meth) acrylate-based monomer containing a carboxy group, and such monomers include (meth) acrylic acid and crotonic acid), isocrotonic acid, maleic acid, fumaric acid, itaconic acid, carboxyethyl (meth) acrylate, or carboxypentyl (meth) acrylate. These may be used alone or in combination of two or more. In addition, the second repeating unit may be derived from a (meth) acrylate-based monomer containing a nitrogen-containing functional group such as a nitrile group, a nitrogen-containing vinyl group (N-vinyl group), or an acrylamide group. As (meth) acrylonitrile, N-vinyl pyrrolidone, N-vinyl caprolactam, 3- (n-methylaminopropyl) methacrylamide, etc. are mentioned. These may be used alone or in combination of two or more.

The second repeating unit derived from the crosslinkable monomer may be included in an amount of 10 to 80% by weight based on the total weight of the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group. If the content of the second repeating unit is less than 10% by weight, there is a fear that the durability reliability of the pressure-sensitive adhesive composition is lowered, and when it exceeds 80% by weight, there is a possibility that the adhesive strength and peeling force are lowered. More specifically, the second repeating unit derived from the crosslinkable monomer is 10 to 70% by weight, more specifically 15 to 40% by weight, based on the total weight of the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group. Can be included.

In addition, a part of the second repeating unit may include a photoreactive functional group, specifically, a functional group containing a double bond between carbon and carbon, and may include a vinyl group, an allyl group, or a (meth) acryloyl group, in the side chain.

The photoreactive functional group introduced into the side chain of the second repeating unit reacts with a photoinitiator when irradiated with ultraviolet rays to form a three-dimensional crosslinked structure, and as a result, the adhesive strength of the pressure sensitive adhesive composition is greatly reduced through the action of increasing the modulus of the pressure sensitive adhesive. Order. Accordingly, easy peeling is possible without residual adhesive composition.

The photoreactive functional group is a group consisting of monomers for forming a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, for example, a silicone-containing functional (meth) acrylate-based monomer, a hydroxyl group, a carboxyl group, and a nitrogen-containing functional group. After the copolymerization of the crosslinkable monomer comprising at least one functional group selected from, the second repeating unit by adding or condensing a compound containing a functional group and a photoreactive functional group capable of addition reaction with the functional groups in the crosslinkable monomer Can be introduced into the side chain. Reactive functional groups in the crosslinkable monomer and functional groups capable of addition reaction include isocyanate groups, epoxy groups, or aziridyl groups, and may be appropriately selected according to the type of functional groups included in the second repeating unit.

Specific examples of the compound for introducing the photoreactive functional group, a compound capable of reacting with a hydroxy group in the second repeating unit, (meth) acryloyloxy isocyanate, (meth) acryloyloxy methyl isocyanate, 2- ( Meth) acryloyloxy ethyl isocyanate, 3- (meth) acryloyloxy propyl isocyanate, 4- (meth) acryloyloxy butyl isocyanate, m-propenyl-α, αdimethylbenzyl isocyanate, methacryloyl isocyanate , Or allyl isocyanate; And (meth) acryloyl diisocyanate compounds or polyisocyanate compounds obtained by reacting a diisocyanate compound or a polyisocyanate compound with 2-hydroxyethyl (meth) acrylic acid. Moreover, glycidyl (meth) acrylate or allyl glycidyl ether etc. are mentioned as a compound which can react with the carboxyl group of a 2nd repeating unit.

The above-described photoreactive functional group may be included in the second repeating unit of 20 to 95% by weight based on the total weight of the second repeating unit. When the content of the second repeating unit into which the photoreactive functional group is introduced is less than 20% by weight, the adhesive strength decreases due to ultraviolet irradiation is insufficient, and when it exceeds 95% by weight, the cohesive strength of the pressure-sensitive adhesive composition before ultraviolet irradiation may be lowered. . In consideration of the remarkable effect of improving the peeling force due to the introduction of the photoreactive functional group, the second repeating unit in which the photoreactive functional group is introduced is 60 to 95% by weight, more specifically 70 to 95% of the total weight of the second repeating unit. A photoreactive functional group may be included in the second repeating unit by weight.

In addition, in the present invention, the (meth) acrylate-based resin having the silicone-based functional group and the photoreactive functional group, in addition to the first repeating unit of (a1) and the second repeating unit of (a2), optionally (a3) other ( A third repeating unit derived from a meth) acrylate-based compound may be further included.

The (a3) third repeating unit is a repeating unit derived from a (meth) acrylate-based compound that does not contain a specific functional group described above, specifically, a silicon-based functional group, a hydroxy group, a carboxyl group, and a nitrogen-containing functional group, an aliphatic (meth) acrylate , A cycloaliphatic (meth) acrylate, or a repeating unit including a structure derived from an aromatic (meth) acrylate.

Examples of the aliphatic (meth) acrylate include an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (Meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, pentyl (meth) acrylate, 2- And ethylhexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, or isononyl (meth) acrylate.

Examples of the alicyclic (meth) acrylate include cycloalkyl (meth) acrylate having a cycloalkyl group having 3 to 30 carbon atoms, and specifically, isobornyl acrylate (IBOA) and trimethylcyclohexyl acrylate. , Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl methacrylate, or dicyclopentenyloxymethacrylate.

Examples of the aromatic (meth) acrylate include alkyl (meth) acrylates having an aromatic group having 6 to 30 carbon atoms, and specifically, phenylpropyl (meth) acrylate and o-phenylphenol EO (meth). Acrylate, 3-phenylphenoxypropyl (meth) acrylate, or phenol EO (meth) acrylate.

Among them, the adhesive strength can be easily controlled without lowering the cohesive strength of the adhesive composition, and the wettability, water resistance, and peelability of the adhesive composition on the wafer surface can be further increased. It may further include a repeating unit derived from a (meth) acrylate compound having an alkyl group having 1 to 6 carbon atoms.

The (a3) third repeating unit may be included in an amount of 5 to 80% by weight based on the total weight of the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group. If the content of the third repeating unit is less than 5% by weight, there is a fear that the durability reliability of the pressure-sensitive adhesive composition is lowered, and when it exceeds 80% by weight, there is a possibility that the adhesive strength and peeling force are lowered.

More specifically, when the (a3) third repeating unit is further included, 10 to 80 weight of the first repeating unit of (a1) above with respect to the total weight of the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group. %, 10 to 70% by weight of the second repeating unit of (a2), and 5 to 80% by weight of the third repeating unit of (a3), and more specifically, the first repeating unit of (a1) 10 to 40% by weight, 15 to 40% by weight of the second repeating unit of (a2), and 40 to 75% by weight of the third repeating unit of (a3). When each repeating unit in the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group is included in the above-mentioned content range, it is possible to exhibit better adhesive strength and peel strength after ultraviolet irradiation without fear of deteriorating durability reliability of the adhesive composition. have.

The (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group may be prepared through a polymerization reaction for a mixture of monomers providing each repeating unit, and then introduced through a photoreactive functional group.

Specifically, the polymerization reaction may be a solution polymerization, photo polymerization, bulk polymerization, suspension polymerization or emulsion polymerization, and the like, and the process is easy, and the thermal initiator is used in that the produced polymer can have excellent uniformity. It can be carried out by the solution polymerization method used. In the solution polymerization, after mixing the initiator in a state in which the (meth) acrylate-based compound containing the silicone functional group, the crosslinkable monomer, and optionally the monomer containing the other (meth) acrylate-based compound are uniformly mixed, 50 to It can be carried out at a polymerization temperature of 140 ℃. At this time, the initiator may be an azo-based initiator such as azobis isobutyronitrile or azobiscyclohexane carbonitrile; And peroxide-based initiators such as benzoyl peroxide or acetyl peroxide, and any one or a mixture of two or more of them can be used.

After the completion of the polymerization reaction, in order to introduce a photoreactive functional group to a part of the second repeating unit derived from a crosslinkable monomer in the resulting polymerization reaction product, a functional group capable of addition reaction with a reactive functional group in the crosslinkable monomer, and A (meth) acrylate-based resin having a silicone-based functional group and a photo-reactive functional group can be prepared by adding a compound containing a photoreactive functional group, and condensing or adding a reaction.

In the present invention, the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group may exhibit excellent effects when applied to a pressure-sensitive adhesive composition through control of the type and content of monomer materials and polymerization conditions during its preparation. So that physical properties such as weight average molecular weight and glass transition temperature can be adjusted. Specifically, in the present invention, the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group may have a weight average molecular weight (Mw) of 50,000 g / mol to 2,000,000 g / mol, and more specifically 700,000 g / mol To 1,500,000 g / mol. When having a weight average molecular weight in the above range, it is preferable because it exhibits proper coating properties and cohesive strength, and does not cause a problem such as a residue remaining in the adherend in the peeling step.

In addition, in this specification, a weight average molecular weight means the weight average molecular weight (unit: g / mol) of polystyrene conversion measured by gel permeation chromatography (GPC). In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC, detectors and analytical columns, such as a commonly known analytical device and a differential refractive index detector, can be used, and the temperature conditions are generally applied. , Solvent, flow rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ° C, a chloroform solvent (Chloroform), and a flow rate of 1 mL / min.

In the present invention, the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group has a glass transition temperature (Tg) of -100 ° C to -5 ° C, more specifically -70 ° C to -10 ° C, more More specifically, it may be -50 ° C to -35 ° C. When having a glass transition temperature in the above range, it is preferable because it exhibits proper coating properties and cohesiveness, and has excellent adhesion workability in the initial bonding step, and does not cause problems such as residues remaining on the adherend in the peeling step.

In the present invention, the glass transition temperature (Tg) of the (meth) acrylate-based resin having the silicon-based functional group and the photoreactive functional group was measured by a differential scanning colorimer (DSC).

In addition, the binder resin of (a) may further include a compound used as a binder resin in a conventional pressure-sensitive adhesive composition, in addition to the (meth) acrylate-based resin having the aforementioned silicone-based functional group and photoreactive functional group. In this case, the compound may further include 20% by weight or less, more specifically 1 to 5% by weight, based on the total weight of the binder resin, within a range not inhibiting the effect in the present invention.

The binder resin (a) having the above-described configuration may be included in an amount of 50 to 97% by weight based on the total weight of the pressure-sensitive adhesive composition. When the content of the binder resin is less than 50% by weight, it is difficult to secure coating properties and workability, and when it exceeds 97% by weight, it is difficult to obtain sufficient adhesive strength. More specifically, (a) the binder resin may be included in 70 to 95% by weight based on the total weight of the pressure-sensitive adhesive composition.

(b) Photoinitiator

In addition, in the pressure-sensitive adhesive composition, the photoinitiator (b) is a component having activity at a wavelength of 250 nm or more, and is a component that initiates photopolymerization at a wavelength transmitted from the above-described base film and easily lowers the adhesive strength of the pressure-sensitive adhesive layer. When used in combination with an amine compound to be used, the effect of lowering the adhesion due to photo-curing can be further improved.

The photoinitiator (b) is, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothione Oxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, dodecyl thioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl- 1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester and A mixture of oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and And 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. More specifically, isopropyl thioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide can be used. These may be used alone or in combination of two or more. The above-described photoinitiators have excellent activity by ultraviolet rays transmitted through the base film, and when used in combination with a tertiary amine compound to be described later, synergistic effect can realize a sufficient adhesion reduction in the photo-curing step.

The (b) photoinitiator, (a) with respect to 100 parts by weight of the binder resin, 0.1 to 40 parts by weight, more specifically 1 to 20 parts by weight may be included, when included in the content range, effective curing reaction Induction, it is possible to prevent the deterioration of physical properties due to residual components after curing. When the content of the photoinitiator is less than 0.1 part by weight, it may be difficult to sufficiently induce a curing reaction, and when it exceeds 40 parts by weight, there is a fear that the coating property is deteriorated because it does not have a sufficient viscosity.

(c) multifunctional crosslinking agent

In addition, in the pressure-sensitive adhesive composition, (c) the multifunctional crosslinking agent reacts with a functional group contained in the (meth) acrylate-based resin having a silicone-based functional group and a photo-reactive functional group in the (a) binder resin component, thereby cohesive strength of the pressure-sensitive adhesive composition. It acts to improve.

Specifically, one or more compounds selected from the group consisting of isocyanate compounds, aziridine compounds, epoxy compounds and metal chelate compounds may be used, and the isocyanate compounds, aziridine compounds, epoxy compounds and metal chelate compounds Silver may be used without particular limitation as long as it is a compound commonly used in the art.

Examples of the isocyanate-based compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoboron diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate, and any one of the polyols (ex And one or more selected from the group consisting of reactants with trimethylol propane). In addition, examples of the aziridine-based compound are N, N'-toluene-2,4-bis (1-aziridinecarboxamide), N, N'-diphenylmethane-4,4'-bis (1-aziridinecar Copyamide), triethylene melamine, bisisopropaloyl-1- (2-methylaziridine) and tri-1-aziridinylphosphine oxide. Examples of the epoxy compound include ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, N, N, N, N-tetraglycidyl ethylenediamine and glycerin diglycidyl ether. One or more selected from the group consisting of, in addition, examples of the metal chelate-based compound, aluminum, iron, zinc, tin, titanium, antimony, magnesium and / or vanadium polyvalent metal is acetyl acetone or ethyl acetoacetate Compounds coordinated to the back may be used, but are not limited thereto.

The (c) multifunctional crosslinking agent may be included in 0.01 to 30 parts by weight based on 100 parts by weight of the (a) binder resin, and more specifically, 0.1 to 10 parts by weight. When the content of the multifunctional crosslinking agent is less than 0.01 part by weight, the cohesive force of the adhesive layer is lowered, and there is a possibility that cohesive failure occurs during a high temperature process, and when it exceeds 30 parts by weight, the adhesive layer does not sufficiently secure the adhesive force before photocuring. There is a risk of peeling or lifting.

(d) tertiary amine compounds

In addition, the pressure-sensitive adhesive composition may optionally further include (d) a tertiary amine compound together with the components (a) to (c) described above.

When the (d) tertiary amine compound is used in combination with the above-described (b) photoinitiator, it is possible to realize a curing reaction increase even after a high temperature process through a synergistic effect. Specifically, in the case of the (d) tertiary amine compound, it acts as a hydrogen donor, thereby synergizing with a photoinitiator through radical generation.

The (d) tertiary amine compound is, for example, ethyl-p-dimethyl amino benzoate, methyl-p-dimethyl amino benzoate, 2-ethylhexyl-p-dimethyl amino benzoate, octyl-p-dimethyl amino And benzoate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, and N, N-dihydroxyethyl-p-toruidiene. More specifically, ethyl-p-dimethyl amino benzoate, Or 2-ethylhexyl-p-dimethyl amino benzoate can be used. These may be used alone or in combination of two or more.

The tertiary amine compound may be included in an amount of 100 to 2000 parts by weight based on 100 parts by weight of the photoinitiator, and more specifically, in an amount of 200 to 1500 parts by weight. When included in the above-described content range, it is possible to maximize the synergy effect according to the combination. When the content of the tertiary amine compound is less than 100 parts by weight, it is insufficient to give sufficient reactivity to the photoinitiator, and when it exceeds 2000 parts by weight, the pressure-sensitive adhesive composition may not have a sufficient viscosity, and thus there is a fear that coating property is deteriorated.

In addition to the above-mentioned components, the pressure-sensitive adhesive composition is within a range that does not affect the effect of the invention, tackifying resin, initiator, low molecular weight, epoxy resin, curing agent, UV stabilizer, antioxidant, colorant, reinforcing agent, antifoaming agent, surfactant , One or more additives selected from the group consisting of blowing agents, organic salts, thickeners and flame retardants may be further included.

The method of forming the adhesive layer on at least one surface of the base film using the adhesive composition containing the above components is not particularly limited, for example, by applying and drying the adhesive composition directly on the base film to form an adhesive layer A method or a method in which a pressure-sensitive adhesive composition is applied and dried once on a peelable substrate to form an adhesive layer, and a method of laminating the formed adhesive layer on a base film through transfer or the like can be used.

At this time, the method of applying and drying the pressure-sensitive adhesive composition is not particularly limited, and for example, a composition containing each of the above components is directly or diluted with a suitable organic solvent, such as a comma coater, gravure coater, die coater or reverse coater. After coating by means of, a method of drying the solvent for 10 seconds to 30 minutes at a temperature of 60 ° C to 200 ° C may be used. In addition, in the above process, an aging process for advancing a sufficient crosslinking reaction of the adhesive may be additionally performed.

The thickness of the adhesive layer is not particularly limited, but may be specifically, 5 to 100 μm. When formed in the thickness range, it is possible to support in a high temperature process of the semiconductor, and peeling is possible without damage in the peeling step of the adhesive sheet.

In the pressure-sensitive adhesive sheet for temporary fixation according to an embodiment of the present invention, the pressure-sensitive adhesive layer is manufactured by the above-described pressure-sensitive adhesive composition, thereby realizing sufficient adhesion during the semiconductor manufacturing process even under high temperature conditions, and adhesion by light curing in the peeling step. It is easy to fall. In particular, by using a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group as a binder resin, even if the wavelength is transmitted from the base film at a relatively low transmittance, excellent light-initiating efficiency and excellent adhesive strength deterioration effect even after high temperature processing Can be implemented. In addition, when the amine-based compound is further included, a synergistic effect with the photoinitiator may increase the curing reaction even after a high temperature process.

Specifically, the adhesive sheet for temporary fixation has an adhesive strength change rate of the adhesive layer defined according to Equation 1 below 30% or less.

[Equation 1]

Rate of change in adhesive strength of the adhesive layer (%) = A2 * 100 / A1

In Equation 1, A1 is the adhesive strength of the adhesive layer after heat treatment at 240 to 260 ° C. for 1 to 20 minutes,

A2 is the adhesive strength of the adhesive layer measured after irradiating the heat-treated adhesive layer with ultraviolet light having a composite wavelength in the range of 200 nm to 500 nm in an amount of 100 mJ / cm ² to 2000 mJ / cm ² .

The rate of change in the adhesive strength of the adhesive layer of Equation 1 is an index that realizes excellent adhesive strength even through high temperature conditions during the semiconductor manufacturing process, and is an index showing a sufficient adhesive strength lowering effect in the peeling step by photocuring. The adhesive sheet for fixing is applied to the manufacturing process of semiconductors by satisfying the value of the adhesive force change rate of Equation 1 below 30%, thereby significantly improving process efficiency and manufacturing high-quality semiconductors.

The adhesive sheet for temporary fixation according to an embodiment of the present invention may include one or more adhesive layers as described above, and accordingly, the adhesive layer may be formed on one side or both sides of the base film.

On the other hand, in the temporary fixing adhesive sheet according to an embodiment of the present invention, the base film may be a polymer base film, specifically, a glass transition temperature (Tg) may be a polymer base film having a temperature of 60 ° C or higher. When the glass transition temperature of the base film satisfies 60 ° C. or higher, it exhibits sufficient heat resistance, so that problems such as wrinkles and deformations do not occur during a high temperature process, so that the semiconductor process can be easily performed.

When the glass transition temperature of the base film is less than 60 ° C, it may affect the process due to problems such as deterioration and deformation under high temperature conditions occurring during the manufacturing process of the semiconductor. Accordingly, defects in the semiconductor process may occur. More specifically, the glass transition temperature of the base film may be 70 ° C or higher or 90 ° C or higher. In this case, the above-described effect can be further improved.

As the polymer base film, for example, polyimide, polyamideimide, polyetheretherketone, polyethyleneterephthalate and polyethylenenaphthalate. It may include one or more polymer compounds selected from the group consisting of polyphenylene sulfide and polyamide. More specifically, it may include polyimide, polyamide or polyamideimide.

When the base film includes a mixture of two or more types of polymers, the films each containing the above-described polymers may be a film having a structure in which two or more layers are stacked, or a film having a single-layer structure in which two or more of the above-described polymers are included. It might be.

In addition, the base film includes the above-mentioned heat-resistant polymer component, and at the same time, the transmittance at a wavelength of 300 nm or more satisfies 50% or more, so that the photoinitiator in the adhesive layer described later can easily initiate a photopolymerization reaction.

When the substrate film has a transmittance of less than 50% at a wavelength of 300 nm or more, the light absorption of the photoinitiator of the adhesive layer may not be sufficient, so that the adhesive strength may not be sufficiently reduced in the step of separating the adhesive sheet.

The thickness of the base film is not particularly limited, and may generally be formed to a thickness of 5 to 500 μm, and more specifically, to a thickness of 10 to 300 μm or a thickness of 25 to 100 μm. In this case, it is possible to support in a high temperature process of the semiconductor, and peeling is possible without damage in the peeling step of the adhesive sheet.

The base film may be subjected to additional treatment to improve performance within a range not affecting the desired effect of the present invention. For example, conventional physical or chemical treatments such as mat treatment, corona discharge treatment, primer treatment or crosslinking treatment may be applied to the surface of the base film.

In addition, the temporary fixing adhesive sheet according to an embodiment of the present invention may further include a release film formed on the adhesive layer.

Examples of the release film that can be used are polyethylene terephthalate films, polytetrafluoroethylene films, polyethylene films, polypropylene films, polybutene films, polybutadiene films, vinyl chloride copolymer films, or polyimide films. And plastic films.

The surface of the release film as described above may be molded with one or more types of alkyd, silicone, fluorine, unsaturated ester, polyolefin or wax. Among them, it may be a release agent such as an alkyd-based, silicone-based or fluorine-based material having heat resistance.

The release film may be formed to a thickness of about 10 μm to 500 μm, more specifically, about 20 μm to 200 μm, but is not limited thereto.

The manufacturing method of the temporary fixing adhesive sheet having the above-described structure is not particularly limited except for forming the adhesive layer using the above-described adhesive composition. For example, a method of sequentially forming an adhesive layer and a release film (if necessary) on a base film, or separately preparing a release film having an adhesive layer, and laminating it on a base film may be used. have.

As described above, the method of forming the adhesive layer on the base film is to form an adhesive layer by directly applying and drying the adhesive composition on the base film, or by applying and drying the adhesive composition on the peelable substrate once and then drying the adhesive layer. And a method of laminating the formed adhesive layer on the base film through transfer or the like can be used. At this time, the method of applying and drying the pressure-sensitive adhesive composition to form the pressure-sensitive adhesive layer is as described above.

In addition, the lamination method in the above is not particularly limited, a hot roll laminate or a lamination press method may be used, and may be a hot roll laminate method in terms of double continuous process possibility and efficiency. The hot roll laminate method may be performed at a temperature of 10 ° C to 100 ° C at a pressure of 0.1 Kgf / cm 2 to 10 Kgf / cm 2, but is not limited thereto.

1 and 2 show a cross-sectional view of the adhesive sheet 10 for temporary fixing according to an embodiment of the present invention.

Referring to Figure 1 (a), the temporary fixing adhesive sheet 10 according to an embodiment of the present invention may have a structure in which the base film 100 and the adhesive layer 200 are laminated.

When the adhesive sheet 10 is applied to a semiconductor manufacturing process, the surface 200 (a) on which the base film 100 of the adhesive layer 200 is not formed may be attached to a predetermined portion of the semiconductor device. have.

Referring to Figure 1 (b), temporary fixing adhesive sheet 10 according to an embodiment of the present invention is a structure in which the base film 100, the adhesive layer 200 and the release film 300 are sequentially stacked You can.

When the adhesive sheet 10 is applied to the manufacturing process of a semiconductor, after peeling the release film 300 from the adhesive layer 200, one side of the adhesive layer 200 from which the release film 300 is peeled is a semiconductor It can be attached to any part of the device.

Referring to Figure 2 (a), the temporary fixing adhesive sheet 10 according to an embodiment of the present invention may be a structure in which two adhesive layers 210 and 220 are formed on both sides of the base film 100, respectively. .

In this case, the first adhesive layer 210, the base film 100, and the second adhesive layer 220 may be sequentially stacked.

When the adhesive sheet 10 is applied to a semiconductor manufacturing process, a surface on which any one base film 100 of the adhesive layer is not formed may be attached to a predetermined portion of the semiconductor device. For example, the surface 220 (a) on which the base film 100 of the second adhesive layer 220 is not formed may be attached to a predetermined portion of the semiconductor device.

Referring to Figure 2 (b), temporary fixing adhesive sheet 10 according to an embodiment of the present invention is a first release film 310, the first adhesive layer 210, the base film 100, the second The adhesive layer 220 and the second release film 320 may be sequentially stacked.

When the pressure-sensitive adhesive sheet 10 is applied to a semiconductor manufacturing process, the release films 310 and 320 are peeled from the second pressure-sensitive adhesive layers 210 and 220, and then the release films 310 and 320 are peeled off. One surface of the layers 210 and 220 may be attached to a predetermined portion of the semiconductor device.

Thereafter, in the peeling step of the adhesive sheet 10, the second adhesive layer 220 may be photocured by irradiating ultraviolet light toward the first adhesive layer 210 and passing through the lower substrate film 100. Accordingly, the adhesive strength of the adhesive layer 200 is lowered, and the adhesive sheet 10 for temporary fixing can be easily peeled from the semiconductor device.

Typically, during the manufacture of a semiconductor device, a process performed under high temperature conditions is included. In this case, there is a problem that the base film or the adhesive layer is thermally decomposed, or additives contained in the adhesive layer are detached. In this case, during the manufacturing process of the semiconductor, sufficient adhesive strength was not realized, or sufficient adhesive strength reduction was not realized in the peeling step by light curing of the adhesive sheet.

The adhesive sheet for temporary fixation according to the present invention forms a base film with a heat-resistant polymer having UV transmittance, and forms an adhesive layer with a specific component capable of improving photopolymerization initiation and reactivity in the wavelength range of the base film, All of the above-described problems can be improved, and accordingly, the manufacturing process efficiency of the semiconductor can be improved and the quality of the manufactured semiconductor can be improved.

Accordingly, the temporary fixing adhesive sheet according to one embodiment of the present invention may be used as a carrier film and protection of a semiconductor process.

II. Method for manufacturing semiconductor device

According to another embodiment of the present invention, a method of manufacturing a semiconductor device using the above-described temporary fixing adhesive sheet is provided.

Typically, during the manufacture of a semiconductor device, a process performed under high temperature conditions is included. In this case, there is a problem that the base film or the adhesive layer is thermally decomposed, or additives contained in the adhesive layer are detached. In this case, sufficient adhesive strength was not realized during the manufacturing process of the semiconductor, or sufficient adhesive strength was not reduced in the peeling step due to photocuring of the adhesive sheet.

The adhesive sheet for temporary fixation according to the present invention forms a base film with a heat-resistant polymer having UV transmittance, and forms an adhesive layer with a specific component capable of improving photopolymerization initiation and reactivity in the wavelength range of the base film, All of the above-mentioned problems were improved. Accordingly, it was confirmed that the manufacturing process efficiency of the semiconductor was improved and the quality of the manufactured semiconductor was very excellent.

A method of manufacturing a semiconductor device according to an embodiment of the present invention comprises the steps of attaching the adhesive layer of the above-mentioned temporary fixing adhesive sheet to a predetermined portion of the semiconductor device; A step of performing a predetermined process with respect to the semiconductor device to which the adhesive sheet is attached; After passing through the predetermined process, irradiating ultraviolet rays to the base film of the temporary fixing adhesive sheet; And detaching the temporary fixing adhesive sheet from the semiconductor device.

In the present invention, the above-mentioned temporary fixing adhesive sheet includes all of the above-mentioned contents, and the manufacturing method of the semiconductor device is different from other commonly known manufacturing methods except for detailed process conditions described later. Can be applied without.

In a method for manufacturing a semiconductor device according to an embodiment of the present invention, a predetermined process for the semiconductor device may be performed under a temperature condition of 60 to 300 ° C, and even through such a high temperature process, a semiconductor manufacturing process Among them, sufficient adhesive strength is realized, and sufficient adhesive strength reduction can be realized in the peeling step by photocuring of the adhesive sheet.

In the method of manufacturing a semiconductor device according to an embodiment of the present invention, the ultraviolet irradiation step is a step of initiating photo-curing of the adhesive layer, and thus, the adhesive sheet can be easily peeled from the semiconductor device due to a decrease in the adhesive strength of the adhesive layer. Have it.

In the method of manufacturing a semiconductor device according to an embodiment of the present invention, when the temporary fixing adhesive sheet further includes a release film, before attaching the adhesive layer of the adhesive sheet to a predetermined portion of the semiconductor device, from the adhesive layer It may further include the step of peeling the release film.

According to the above-described method, it was confirmed that the manufacturing process efficiency of the semiconductor device was improved and the quality of the manufactured semiconductor was excellent.

The pressure-sensitive adhesive composition according to the present invention exhibits adequate adhesion during the semiconductor manufacturing process, and the adhesive strength is sufficiently lowered during photo-curing, so that peeling is easy. Bubbles and lifting do not occur even after the high temperature process. Accordingly, the pressure-sensitive adhesive composition according to the present invention is useful for the production of temporary fixing pressure-sensitive adhesive sheets.

1 and 2 schematically show a cross-sectional structure of an adhesive sheet 10 for temporary fixing according to an embodiment of the present invention.
3 is a photograph of the appearance after observing the heat treatment process for the temporary fixing adhesive sheet according to Example 1.
4 is a photograph of the appearance after observing the heat treatment process for the temporary fixing adhesive sheet according to Comparative Example 1.

Hereinafter, preferred embodiments are presented to help understanding of the invention. However, the following examples are only for illustrating the invention, and the invention is not limited thereto.

<Preparation of adhesive composition>

Preparation Example 1

Nitrogen gas is refluxed, and the reactor is installed with a cooling device for easy temperature control. Ethylhexyl acrylate (EHA) 72.5g, silicone (meth) acrylate (Silaplane ™ FM-0721 manufactured by JNC, Mw = 5000g / mol) 10g And a mixture of monomers consisting of 17.5 g of hydroxyethyl acrylate (HEA). Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 20g (85.5 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were mixed with the primary reactant in 0.08 g, and reacted at 40 ° C. for 24 hours. An ultraviolet curing machine was introduced into the polymer side chain in the primary reactant to prepare a binder resin (a-1).

100 g of the binder resin (a-1), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Preparation Example 2

Nitrogen gas was refluxed, and the reactor was installed with a cooling device to facilitate temperature control. Ethylhexyl acrylate (EHA) 62.5g, silicone (meth) acrylate (Jila's Silaplane ™ FM-0721) 20g and hydroxyethyl acrylate (HEA) A mixture of monomers consisting of 17.5 g was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 20g (85.5 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were mixed with the primary reactant in 0.08 g, and reacted at 40 ° C. for 24 hours. An ultraviolet curing machine was introduced into the polymer side chain in the primary reactant to prepare a binder resin (a-2).

100 g of the binder resin (a-2), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Preparation Example 3

52.5 g of ethylhexyl acrylate (EHA), 30 g of silicone (meth) acrylate (Silaplane ™ FM-0721, manufactured by JNC) and hydroxyethyl acrylate in a reactor equipped with a cooling device so that nitrogen gas is refluxed and temperature control is easy. (HEA) A mixture of monomers consisting of 17.5 g was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 20g (85.5 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were mixed with the primary reactant in 0.08 g, and reacted at 40 ° C. for 24 hours. An ultraviolet curing machine was introduced into the polymer side chain in the primary reactant to prepare a binder resin (a-3).

100 g of the binder resin (a-3), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Preparation Example 4

42.5 g of ethylhexyl acrylate (EHA), 40 g of silicone (meth) acrylate (Silaplane ™ FM-0721, manufactured by JNC) and hydroxyethyl acrylate in a reactor equipped with a cooling device so that nitrogen gas is refluxed and temperature control is easy. (HEA) A mixture of monomers consisting of 17.5 g was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 20g (85.5 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were mixed with the primary reactant in 0.08 g, and reacted at 40 ° C. for 24 hours. An ultraviolet curing machine was introduced into the polymer side chain in the primary reactant to prepare a binder resin (a-4).

100 g of the binder resin (a-4), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Comparative Production Example 1

A mixture of monomers consisting of 82.5 g of ethylhexyl acrylate (EHA) and 17.5 g of hydroxyethyl acrylate (HEA) was added to a reactor in which nitrogen gas was refluxed and a cooling device was installed to facilitate temperature control. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 20g (85.5 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were mixed with the primary reactant in 0.08 g, and reacted at 40 ° C. for 24 hours. An ultraviolet curing machine was introduced into the polymer side chain in the primary reactant to prepare a binder resin (b-1).

100 g of the binder resin (b-1), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Comparative Production Example 2

77.5 g of ethylhexyl acrylate (EHA), 5 g of silicone (meth) acrylate (Silaplane ™ FM-0721, manufactured by JNC) and hydroxyethyl acrylate in a reactor equipped with a cooling device so that nitrogen gas is refluxed and temperature control is easy. (HEA) A mixture of monomers consisting of 17.5 g was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 20g (85.5 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were mixed with the primary reactant in 0.08 g, and reacted at 40 ° C. for 24 hours. An ultraviolet curing machine was introduced into the polymer side chain in the primary reactant to prepare a binder resin (b-2).

100 g of the binder resin (b-2), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Comparative Production Example 3

22.5 g of ethylhexyl acrylate (EHA), 60 g of silicone (meth) acrylate (Silaplane ™ FM-0721, manufactured by JNC) and hydroxyethyl acrylate in a reactor equipped with a cooling device so that nitrogen gas is refluxed and temperature control is easy. (HEA) A mixture of monomers consisting of 17.5 g was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 20g (85.5 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were mixed with the primary reactant in 0.08 g, and reacted at 40 ° C. for 24 hours. An ultraviolet curing machine was introduced into the polymer side chain in the primary reactant to prepare a binder resin (b-3).

100 g of the binder resin (b-3), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Comparative Production Example 4

Nitrogen gas was refluxed and a reactor was installed with a cooling system to facilitate temperature control. Ethylhexyl acrylate (EHA) 62.5g, silicone (meth) acrylate (Silaplane ™ FM-0721, manufactured by JNC) 20g and hydroxyethyl acrylate (HEA) A mixture of monomers consisting of 17.5 g was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 10g (42.7 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were added to the primary reactant in 0.045 g, and reacted at 40 ° C. for 24 hours. An ultraviolet curing machine was introduced into the polymer side chain in the primary reactant to prepare a binder resin (b-4).

100 g of the binder resin (b-4), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Comparative Production Example 5

Nitrogen gas was refluxed and a reactor was installed with a cooling system to facilitate temperature control. Ethylhexyl acrylate (EHA) 62.5g, silicone (meth) acrylate (Silaplane ™ FM-0721, manufactured by JNC) 20g and hydroxyethyl acrylate (HEA) A mixture of monomers consisting of 17.5 g was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and sufficiently mixed at 30 ° C. for 60 minutes or more while nitrogen was injected to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ° C, and 0.1 g of a reaction initiator V60 ™ (manufactured by Daejung Chemical Co., Ltd., Azobisisobutylonitrile) was added in portions to initiate the reaction, followed by polymerization for 6 hours to prepare a primary reactant.

Methacryloyl isocyanate (MOI) 22.9g (97 mol% relative to HEA in the primary reactant) and catalyst (DBTDL: dibutyl tin dilaurate) were added to the primary reactant, 0.091g, and reacted at 40 ° C for 24 hours. To prepare a binder resin (b-5) by introducing an ultraviolet curing machine into the polymer side chain in the primary reactant.

100 g of the binder resin (b-5), 2.0 g of toluene diisocyanate (TDI) as a multifunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl amino as an amine compound An adhesive composition was prepared by mixing 6.0 g of benzoate.

Test Example 1: Binder resin analysis

The content and physical properties (Mw and Tg) of each repeating unit in the binder resins prepared in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 5 were analyzed and measured, and the results are shown in Table 1 below.

(1) Content of each repeating unit in the binder resin: After nuclear magnetic resonance (NMR) analysis, it was calculated from the results.

<Conditions for nuclear magnetic resonance analysis>

Specifically, chloroform D (CDCl ₃ ) containing tetramethylsilane (TMS) as an internal standard material was measured using 1H-NMR (nuclear magnetic resonance) of Bruker Advance 400 as a solvent.

(2) Weight average molecular weight (Mw): It is the weight average molecular weight of polystyrene conversion measured using gel permeation chromatography (GPC).

In detail, it was measured by GPC using the PS standard using the Agilent 1200 series. Specifically, it was measured using an Agilent 1200 series instrument using a Polymer Laboratories PLgel MIX-B 300 mm length column, wherein the measurement temperature was 30 ° C, the solvent used was chloroform, and the flow rate was 1 mL / min. Samples were prepared at a concentration of 10 mg / 10 mL, then supplied in an amount of 200 μL, and the Mw value was derived using an assay curve formed using a polystyrene standard. As for the molecular weight (g / mol) of the polystyrene standard, 9 species of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000 were used.

(3) Glass transition temperature (Tg): Measured using a differential scanning calorimeter (DSC).

Specifically, it was measured using a DSC (TA instrument, Q-20) at a heating rate of 10 ° C./min in a nitrogen atmosphere. Samples were prepared by placing 5 g of the binder resin in which the residual solvent was dried in an aluminum pan. Tg was analyzed by using the second heating curve of the sample measured under temperature conditions ranging from -70 to 100 ° C.

Binder resin type Content of repeating unit in binder resin Mw (g / mol) Tg (℃) First repeating unit derived from silicone (meth) acrylate
(Based on the total weight of binder resin, weight%) HEA-derived second repeat unit
(Based on the total weight of binder resin, weight%) 3rd repeat unit derived from EHA
(Based on the total weight of binder resin, weight%) Introduction of photoreactive functional groups 2nd repeat unit
(Based on the total weight of the second repeating unit derived from HEA,% by weight) Preparation Example 1 a-1 10 17.5 72.5 95 1,070,000 -45.6 Preparation Example 2 a-2 20 17.5 62.5 95 1,100,000 -43.6 Preparation Example 3 a-3 30 17.5 52.5 95 1,070,000 -38.5 Preparation Example 4 a-4 40 17.5 42.5 95 1,100,000 -35.7 Comparative Production Example 1 b-1 0 17.5 82.5 95 1,200,000 -48.4 Comparative Production Example 2 b-2 5 17.5 77.5 95 1,180,000 -46.8 Comparative Preparation Example 3 b-3 60 17.5 22.5 95 1,120,000 -31.0 Comparative Preparation Example 4 b-4 20 17.5 62.5 15 1,100,000 -49.9 Comparative Preparation Example 5 b-5 20 17.5 62.5 99.9 1,100,000 -41.6

<Preparation of temporary adhesive sheet>

Example 1

The pressure-sensitive adhesive composition of Preparation Example 1 was coated on a release-treated polyethylene terephthalate film (38 μm thick, glass transition temperature (Tg): 120 ° C.), and then dried at 110 ° C. for 3 minutes to form an adhesive layer of about 30 μm thickness. Formed. The formed pressure-sensitive adhesive layer was laminated on a 50 μm-thick base film polyimide (Tg: 350 ° C.) and then aged to obtain a temporary fixing pressure-sensitive adhesive sheet.

Examples 2 to 4, and Comparative Examples 1 to 5

An adhesive sheet for temporary fixation was prepared in the same manner as in Example 1, except that the base film and the adhesive composition described in Table 2 below were applied.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Base film Polyimide Polyimide Polyimide Polyimide Polyimide Polyimide Polyimide Polyimide Polyimide Adhesive composition for forming an adhesive layer Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Comparative Production Example 1 Comparative Production Example 2 Comparative Production Example 3 Comparative Production Example 4 Comparative Production Example 5

Experimental Example 2: Analysis of adhesive layer

Elemental analysis was performed using SEM-EDX on the adhesive layer in the temporary fixing adhesive sheet prepared according to Examples and Comparative Examples, and the results are shown in Table 3 below.

<Element analysis method>

Measurement equipment: Jeol JSM-7610F field emission scanning electron microscope

The sample was coated with Pt 6 nm to prevent the adhesive layer from being charged, and then SEM-EDX analysis was performed on a vacuum. The acceleration voltage was 15 Kv, the working distance was 8 mm, and the applied current was set to the irradiation current value 10 set in the software. For the EDX analysis, OXFORD INSTRUMENTS 'Aztec® software was used to analyze the content ratio of each element.

Silicone acrylate content relative to the total weight of the binder resin (% by weight) EDS analysis results The content of each element in the adhesive layer
(weight%) C O Si Other elements Example 1 10 82.99 3.08 12.33 Balance Example 2 20 69.98 8.64 16.19 Balance Example 3 30 63.22 11.19 19.06 Balance Example 4 40 57.26 14.61 22.65 Balance Comparative Example 1 0 92.41 1.13 0 Balance Comparative Example 2 5 85.76 2.83 8.65 Balance Comparative Example 3 60 39.08 22.80 31.98 Balance Comparative Example 4 20 68.18 8.49 15.88 Balance Comparative Example 5 20 68.66 7.91 16.56 Balance

* The total sum of the elements in the adhesive layer is 100% by weight, and further includes other elements in the balance other than C, Si, and O.

Experimental Example 3: Evaluation of adhesive strength and peel strength

For the temporary fixing adhesive sheet prepared according to Examples and Comparative Examples, the adhesive strength and the peeling strength due to light curing were evaluated in the following manner, and the results are shown in Table 4.

In detail, after cutting the adhesive sheet for temporary fixation prepared in Examples and Comparative Examples to have a width of 25 mm, Sample A (before heat treatment) attached to a silicon wafer using a 2 kg roller was prepared. Next, a temporary fixing adhesive sheet attached to a silicon wafer was left in an oven at 250 ° C. for 10 minutes to prepare Sample B (after heat treatment), which was heat treated. It irradiated with ultraviolet rays (with a mercury lamp having a combined wavelength of 200nm to 500nm region) of each of the light amount 1000mJ / cm ² Conditions for Sample B underwent the sample A and the heat treatment is not a heat treatment prepared in the above on the substrate film side, and Stable The adhesive force (gf / 25mm) was measured at a speed of 300 mm / min and an angle of 180 degrees using a texture analyzer of Micro Systems.

Moreover, the change rate of the adhesive force of the adhesive layer was calculated according to the following equation (1) from the measured adhesive force.

[Equation 1]

Rate of change in adhesive strength of the adhesive layer (%) = A2 * 100 / A1

(In Equation 1, A1 is the adhesive strength of the adhesive layer after heat treatment at 240 to 260 ° C for 1 to 20 minutes, and A2 is 100 mJ / cm of ultraviolet rays having a complex wavelength of 200 nm to 500 nm in the heat-treated adhesive layer. ^It is the adhesive strength of the adhesive layer measured after irradiation with a light amount of ² to 2000 mJ / cm ² )

In addition, bubble generation and excitation in the heat-treated Sample B were visually observed. The results are shown in Figs. 3 and 4, respectively. 3 and 4 are photographs showing the appearance after the heat treatment process for the temporary fixing adhesive sheets of Example 1 and Comparative Example 1, respectively.

Sample A without heat treatment
Evaluation of adhesive force (gf / 25mm) Sample B after heat treatment
Evaluation of adhesive force (gf / 25mm) Adhesion change rate (%) Sample B after heat treatment
Evaluation of appearance characteristics
(Bubble and excitement) Before UV irradiation After UV irradiation Before UV irradiation After UV irradiation Example 1 38 6 135 33 24.4 Not occurring Example 2 31 5 98 25 25.5 Not occurring Example 3 27 5 77 21 27.3 Not occurring Example 4 25 4 69 19 27.5 Not occurring Comparative Example 1 43 11 347 193 55.6 Occur Comparative Example 2 41 8 313 166 53.0 Occur Comparative Example 3 Warrior Warrior Warrior Warrior - Not occurring Comparative Example 4 67 43 512 381 74.4 Occur Comparative Example 5 Warrior 15 Warrior Warrior - Occur

As can be seen from the experimental results for Sample B after the heat treatment of Table 4, the adhesive sheets for temporary fixation of Examples 1 to 4 prepared according to the present invention have a large decrease in adhesive strength after a high temperature thermal process, and when peeled from a silicon wafer It was confirmed that removal is possible without adhesive residue. In addition, the adhesive sheet for temporary fixation of Examples 1 to 4 had no deterioration in appearance characteristics, such as bubble generation or floating, even after the heat treatment process at a high temperature of 250 ° C. On the other hand, the adhesive sheet for temporary fixation of Comparative Example 1 prepared using (meth) acrylate-based resin containing only a photoreactive functional group without a silicone-based functional group as a binder resin, shows a high adhesive strength even after a heat treatment process, and is a silicon wafer. When peeling from the adhesive residue was generated, and after the heat treatment process, bubbles and floats were generated on the surface.

In addition, as a binder resin, a (meth) acrylate-based resin containing a silicone-based functional group is used, but the adhesive for temporary fixation of Comparative Example 2, wherein the content of silicone in the adhesive layer is less than 10% by weight based on the total weight of the adhesive layer The sheet exhibited a high adhesive strength even after the heat treatment process, resulting in an adhesive residue when peeling from the silicon wafer, and as in Comparative Example 1, air bubbles and floatation occurred on the surface after the heat treatment process.

In addition, as a binder resin, a (meth) acrylate-based resin containing a silicone-based functional group is used, but the adhesive for temporary fixation of Comparative Example 3, wherein the content of silicone in the adhesive layer is more than 30% by weight relative to the total weight of the adhesive layer The sheet was transferred before and after the heat treatment process.

Further, as the binder resin, a (meth) acrylate-based resin containing a photoreactive functional group is used together with a silicone-based functional group, but the content of the second repeating unit in which the photoreactive functional group is introduced is in the (meth) acrylate-based resin. The adhesive sheet for temporary fixation of Comparative Example 4, which contains less than 20% by weight based on the total weight of the second repeating unit, shows a high adhesive strength even after the heat treatment process, resulting in adhesive residue when peeling from the silicon wafer, Comparative Example 1 Likewise, bubbles and excitation occurred on the surface after the heat treatment process.

In addition, for the temporary fixation of Comparative Example 5, the content of the second repeating unit in which the photoreactive functional group was introduced exceeds 95 wt% with respect to the total weight of the second repeating unit in the (meth) acrylate resin. In the case of the pressure-sensitive adhesive sheet, transfer occurred after the heat treatment process, and as in Comparative Examples 1 and 2, bubbles and excitation occurred on the surface after the heat treatment process.

10: Temporary fixing adhesive sheet
100: base film
200: adhesive layer
300: release film

Claims (19)

Base film; And
It includes at least one adhesive layer;
The adhesive layer includes a binder resin comprising a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, and contains 10 to 30% by weight of silicone (Si) based on the total weight of the adhesive layer,
The (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group is at least one selected from the group consisting of a first repeating unit derived from a (meth) acrylate-based monomer containing a silicone-based functional group, a hydroxyl group, a carboxyl group, and a nitrogen-containing functional group. Contains a second repeating unit derived from a crosslinkable monomer containing a reactive functional group,
20 to 95% by weight relative to the total weight of the second repeating unit, the second repeating unit includes a photoreactive functional group in the side chain, a temporary fixing adhesive sheet.
According to claim 1,
The photoreactive functional group is a vinyl group, an allyl group or a (meth) acryloyl group, a temporary fixing adhesive sheet.
According to claim 1,
The silicone-based functional group-containing (meth) acrylate-based monomer includes at least one of silicone (meth) acrylates represented by the following Chemical Formulas 2a to 2d, and a temporary fixing adhesive sheet.
[Formula 2a]

[Formula 2b]

[Formula 2c]

[Formula 2d]

In Chemical Formulas 2a to 2d,
R ₁ to R ₄ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R _a to R _e are each independently hydrogen or a methyl group,
x, y, z, w and v are each independently an integer from 1 to 3,
n1 to n4 are each independently an integer of 1 to 200.
According to claim 1,
The hydroxy group, the carboxyl group and the crosslinkable monomer comprising at least one functional group selected from the group consisting of nitrogen-containing functional groups, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxy Hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth ) Acrylate, (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, (meth) acrylonitrile, N-vinyl A temporary fixing adhesive sheet comprising one or two or more selected from the group consisting of pyrrolidone, N-vinyl caprolactam and 3- (n-methylaminopropyl) methacrylamide.
According to claim 1,
The first repeating unit, the adhesive sheet for temporary fixation, contained in 10 to 90% by weight relative to the total weight of the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group.
According to claim 1,
The (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group further comprises a third repeating unit derived from a (meth) acrylate-based compound having an alkyl group having 1 to 12 carbon atoms, a temporary fixing adhesive sheet.
According to claim 1,
The (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group has a weight average molecular weight of 50,000 g / mol to 2,000,000 g / mol and a glass transition temperature of -100 ° C to -5 ° C, temporary fixation adhesive Sheet.
According to claim 1,
The adhesive layer further comprises a photoinitiator and a multifunctional crosslinking agent, or further comprising a photoinitiator, a multifunctional crosslinking agent and a tertiary amine compound, temporary fixing adhesive sheet.
The method of claim 8,
The photoinitiator, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4- Diethyl thioxanthone, 2,4-diisopropyl thioxanthone, dodecylthioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1 [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl ester, oxy-phenyl-acetic acid 2- [2-hydroxy-ethoxy] -ethyl ester, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2,4,6-trimethylbenzoyl- At least one kind selected from the group consisting of diphenyl-phosphine oxide, an adhesive sheet for temporary fixation.
The method of claim 8,
The multifunctional crosslinking agent comprises an isocyanate-based compound, an aziridine-based compound, an epoxy-based compound and at least one compound selected from the group consisting of a metal chelate-based adhesive sheet for temporary fixation.
According to claim 1,
The adhesive layer has a change in adhesive strength of 30% or less according to Equation 1 below, temporary fixing adhesive sheet:
[Equation 1]
Rate of change in adhesive strength of the adhesive layer (%) = A2 * 100 / A1
In Equation 1, A1 is the adhesive strength of the adhesive layer after heat treatment at 240 to 260 ° C. for 1 to 20 minutes,
A2 is the adhesive strength of the adhesive layer measured after irradiating the heat-treated adhesive layer with ultraviolet light having a complex wavelength in the range of 200 nm to 500 nm in an amount of 100 mJ / cm ² to 1000 mJ / cm ² .
According to claim 1,
remind The base film is an adhesive sheet for temporary fixing, which is a polymer base film having a glass transition temperature (Tg) of 60 ° C or higher.
According to claim 1,
The base film includes at least one polymer compound selected from the group consisting of polyimide, polyamideimide, polyether ether ketone, polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide and polyamide, and temporary fixing adhesive Sheet.
According to claim 1,
A temporary release adhesive sheet further comprising a release film on one surface of the adhesive layer on which the base film is not formed.
According to claim 1,
An adhesive layer is formed on one surface of the base film,
Further comprising a release film on the surface of the adhesive layer is not formed, the temporary adhesive sheet for fixing.
According to claim 1,
The adhesive layer is formed of two layers,
Adhesive layers are formed on both sides of the base film,
The adhesive sheet for temporary fixation, further comprising a release film on the surface of the adhesive layer is not formed.
According to claim 1,
An adhesive sheet for temporary fixing used as a protective film or a carrier film in a semiconductor process.
Attaching the adhesive layer of the temporary fixing adhesive sheet according to claim 1 to a predetermined portion of a semiconductor device;
A step of performing a predetermined process with respect to the semiconductor device to which the adhesive sheet is attached;
After passing through the predetermined process, irradiating ultraviolet rays to the base film of the temporary fixing adhesive sheet; And
And detaching the temporary fixing adhesive sheet from the semiconductor device.
The method of claim 18,
A predetermined process for the semiconductor device is performed under a temperature condition of 60 ° C to 300 ° C, a method of manufacturing the semiconductor device.

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