WO2019245246A1 - Adhesive composition - Google Patents

Abstract

The present invention provides an adhesive composition capable of exhibiting excellent adhesive strength, causing no bubbling and peeling even after high-temperature processes, and being easily separated through photo-curing in a delaminating step.

Description

 2019/245246 1 »（： 1 ^ 1 {2019/007282

[Name of invention]

 Pressure-sensitive adhesive composition

 Technical Field

 Cross Citation with Related Application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0071077 dated June 20, 2018 and Korean Patent Application No. 10-2019-0070664 dated June 14, 2019. All content disclosed in the literature is included as part of this specification.

 The present invention relates to an adhesive composition.

 Background Art

 Recently, the trend of miniaturization, thinning, and large-capacity of electronic devices has been expanded, and the necessity for higher density and higher integration of semiconductor packages is rapidly increasing. Reflecting this, the size of the semiconductor chip is getting bigger and the thickness of the chip is getting thinner.

 The thin semiconductor chip has a problem of difficulty in handling during the manufacturing process, and thus, a method of temporarily fixing the thin semiconductor chip using an adhesive sheet, and processing, processing, and transferring the temporary semiconductor chip in a temporarily fixed state This is being applied.

 Such an adhesive sheet exhibits excellent adhesion, but in a process of separating a fixed thin semiconductor chip after a series of processes are completed, the adhesive sheet does not damage the semiconductor chip and at the same time peels off the residues on the surface. Should have Moreover, since many processes in the manufacturing process of a semiconductor are performed under high temperature conditions, high heat resistance is calculated | required so that adhesive force may not fall by thermal decomposition during a process. In particular, in the semiconductor process, an ultra high temperature process of 200 or more is performed. When the heat resistance is low, problems of appearance defects due to bubble generation and lifting phenomenon occur between the temporary adhesive sheet and the thin substrate.

On the other hand, as a temporary adhesive material, the ultraviolet curable adhesive which adhesive force falls by ultraviolet irradiation is used recently. By the way, in the case of such an ultraviolet curable adhesive, additives, such as a photoinitiator in an adhesive, are high temperature 2019/245246 1 »（： 1 ^ 1 {2019/007282

Due to pyrolysis in the process or movement of additives, there was an insufficient problem of deterioration of adhesion at the peeling step.

 Accordingly, it is required to develop a pressure-sensitive adhesive material that can be easily detached without foaming and lifting phenomenon in appearance even after a high temperature process as a temporary fixing pressure-sensitive adhesive sheet.

 Detailed Description of the Invention

 [Technical problem]

 The present invention is to provide a pressure-sensitive adhesive composition that exhibits excellent adhesion, does not generate bubbles and floats even after a high temperature process, and can be easily separated by light curing in a peeling step.

 Technical Solution

 According to the invention,

 (&) Silicon based functional group and photoreactive functional group

Binder resin containing (meth) acrylate type resin;

 Photoinitiators; And

 (0) a multifunctional crosslinking agent;

 Having the silicon-based functional group and photoreactive functional group

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

 20 to 95% by weight of the second repeating unit, based on the total weight of the second repeating unit, includes a photoreactive functional group in the side chain. Hereinafter, the pressure-sensitive adhesive composition according to the embodiments of the present invention, the temporary fixing pressure-sensitive adhesive sheet using the same and a manufacturing method thereof will be described in detail.

 Prior to this, the terminology is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention unless expressly stated otherwise.

As used herein, the singular forms “a,” “an” and “the 2019/245246 1 »（： 1 ^ 1 {2019/007282

It includes plural forms as long as they do not represent meaning.

 As used herein, the meaning of "includes" specifies a particular characteristic, region, integer, step, operation, element, and / or component, and other specific characteristics, region, integer, step, operation, element, component, and / or group. It does not exclude the presence or addition of.

 In this specification, terms including ordinal numbers such as 'first' and 'second' are used for the purpose of distinguishing one component from another component 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, the use of a polymer containing a repeating unit having a specific structure as a binder resin in the production of a pressure-sensitive adhesive composition useful for temporary fixing pressure-sensitive adhesive sheets used in the manufacturing process of semiconductors, It can be easily peeled off by implementing the adhesive force, and exhibiting a sufficient adhesive force lowering effect by photo curing in the peeling step after the high temperature process. In addition, due to the improved heat resistance, excellent appearance characteristics can be exhibited without generation of bubbles or lifting in the appearance even during a high temperature process. Accordingly, when the temporary fixing adhesive sheet prepared using the pressure-sensitive adhesive composition is used as a protective film or carrier film in the semiconductor manufacturing process, the efficiency of the semiconductor manufacturing process may be improved, and the quality of the manufactured semiconductor may be improved. Can be.

 I. Adhesive composition

 Specifically, the pressure-sensitive adhesive composition according to an embodiment of the present invention, (3) a binder resin containing a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group, (photoinitiator, and ((:)) multifunctional crosslinking agent Optionally, further comprising (a tertiary amine compound). Hereinafter, each component will be described in detail.

 (3) Binder Resin

In the pressure-sensitive adhesive composition, (3) the binder resin contains a (meth) acrylate resin having a silicone-based functional group and a photoreactive functional group, and 2019/245246 1 »（： 1/10 公 019/007282

The (meth) acrylate resin having a silicone-based functional group and a photoreactive functional group includes (31) a first repeating unit derived from a (meth) acrylate-based monomer containing a silicone-based functional group, and (32) a hydroxy group, a carboxyl group and a nitrogen-containing functional group. A second repeating unit derived from a crosslinkable monomer comprising at least one reactive functional group selected from the group; wherein 20 to 95 wt% of the second repeating unit is contained in the side chain based on the total weight of the second repeating unit of 2). It includes reactive functional groups.

 As such, a first repeating unit derived from a (meth) acrylate 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 part of the second repeating unit is a side chain By including (meth) acrylate resin having a random copolymer structure as a binder resin having a photoreactive functional group in the binder resin, excellent adhesion stability is achieved even in a high temperature process.

5 _{> <} 1,

Can be implemented.

 In the (meth) acrylate resin having the silicone-based functional group and the photoreactive functional group, the first repeating unit of () is a silicone-based

 0-containing a structure derived from a functional group-containing formula (meth) acrylate-based compound

By repeating unit, the silicon-based functional group is a polyalkylsiloxane group bonded with 1 to 200 alkylsiloxanes, a polyarylsiloxane group bonded with 1 to 200 arylsiloxanes, and

In addition, an alkylsiloxane and an arylsiloxane may be mixed to form a polyorganosiloxane group having 2 to 200 bonds, wherein the alkyl is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl or propyl, and the aryl is carbon number such as phenyl It may be an aryl group of 6 to 2. As a specific example, the silicon-based functional group may be any one of functional groups represented by the following Chemical Formulas 18 to 1

Burr

01 ₃ 04

[Formula 113] 2019/245246 1 »(： 1/10 公 019/007282

In the above formulas (1):

The seedlings ₁ to ¾ 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, even more specifically, a hydrogen atom or a methyl group.

 In addition, the 111 to 113 each independently represent an integer of 1 to 200, more specifically, may be an integer of 5 to 100,

 As described above, since the silicon-based functional group included in the first repeating unit has a siloxane bond having a higher binding energy than the carbon lanso bond, the thermal decomposition temperature of the binder resin may be increased by increasing the thermal resistance of the binder resin. Accordingly, it is possible to implement excellent adhesion stability even at high temperature process, and also to prevent the occurrence of bubble outing and the like.

Than the first repeating unit of the specific () is, the following formulas ₂₃ to

2 (1), which may include at least one structure derived from a (meth) acrylate compound containing a silicone-based functional group:

 [Formula 2

[Formula ¾] 2019/245246 1 »（： 1/10 公 019/007282

In Chemical Formulas 23 to 2,

 ¾ to ¾ 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,

 ¾ to ¾ are each independently hydrogen or methyl,

 X,, and V are each independently an integer of 1 to 3,

 111 to 114 each independently represent an integer of 1 to 200, and more specifically, an integer of 5 to 100.

 In addition, the (meth) acrylate compound containing a silicone-based functional group includes a (meth) acrylate group at one or both ends, and for the production of binder resins such as ethyl nucleo acrylate (班), hydroxyethyl acrylate (quasi, etc.). Random copolymerization with monomers.

The (meth) acrylate-based compound containing an additive silicone-based functional group may also have a weight average molecular weight (¾) of 10 to 10,000 g / mol, more specifically 1,000 to 5,000 _§ ^ ₀ 1. By having the weight average molecular weight of the above range can exhibit an excellent effect in terms of heat resistance and compatibility. 2019/245246 1 »（： 1 ^ 1 {2019/007282

The (meth) acrylate compound containing a silicone-based functional group is made of a known company

Commercially available such as FM-0725 and the like.

 The first repeating unit of () may be included in an amount of 10 to 90% by weight based on the total weight of the (meth) acrylate resin having the silicon-based functional group and the photoreactive functional group. When the content of the first repeating unit is less than 10% by weight, the effect of improving heat resistance is insignificant, and the content of the second repeating unit of 2) is excessively increased, so that when peeled off due to the residual of unreacted functional groups that do not participate in the crosslinking reaction Desorption can be difficult. Moreover, when it exceeds 90 weight%, the surface energy of binder resin will become low too much and there exists a possibility that the adhesive force of an adhesive composition may fall. More specifically, the first repeating unit of (31) is 20 to 80% by weight, more specifically 20 to 40% by weight based on the total weight of the (meth) acrylate resin having the silicon-based functional group and the photoreactive functional group. It may be included as.

 In the present invention, the content of each repeating unit in the binder resin can be calculated through analysis.

 On the other hand, the second repeating unit of (32) in the (meth) acrylate resin having a silicone-based functional group and a photoreactive functional group is a 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 including a structure derived from an acidic monomer, a reactive functional group such as a hydroxyl group, a carboxyl group, or a nitrogen-containing functional group in the second repeating unit may react with a multifunctional crosslinking agent during thermal curing to implement a three-dimensional crosslinked structure. As a result, a high crosslinking density can be imparted to the pressure-sensitive adhesive composition, and cohesion force can be increased to exhibit 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, such monomers are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acryl Latex, 4-hydroxybutyl (meth) acrylate, 6-hydroxynuclear (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-hydroxyethylene glycol

(Meth) acrylate or 2-hydroxypropylene glycol (meth) acrylate, etc. are mentioned. These may be used alone or in combination of two or more. The second repeating unit may be derived from a (meth) acrylic acid or a (meth) acrylate monomer containing a carboxyl group, and such monomers include (meth) acrylic acid ((meth) acryl ic acid) and crotonic acid ( crotoni c acid), isocrotonic acid, malei c acid, fumar ic acid, itaconic acid, carboxyethyl (meth) acrylate, or carboxypentyl (meth) acrylate. These may be used alone or in combination of two or more thereof. In addition, the second repeating unit may be derived from a (meth) acrylate monomer containing a nitrogen-containing functional group such as a nitrile group, a nitrogen-containing vinyl group (N-vinyl group), or an acrylamide group. (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 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, the durability and reliability of the pressure-sensitive adhesive composition may be lowered. If the content of the second repeating unit is more than 80% by weight, the adhesion and peeling force may be lowered. More specifically, the second repeating unit derived from the crosslinkable monomer is 10 to 70% by weight, and more specifically 20 to 40% by weight, based on the total weight of the (meth) acrylate resin having a silicone-based functional group and a photoreactive functional group. May be included.

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

The photoreactive functional group introduced into the side chain of the second repeating unit reacts with the photoinitiator upon ultraviolet irradiation to form a three-dimensional crosslinked structure, and as a result, the adhesive force of the pressure-sensitive adhesive composition is greatly reduced through the action of increasing the modulus of the pressure-sensitive adhesive. Let's do it. Accordingly, easy peeling is possible without remaining of the pressure-sensitive adhesive composition. 2019/245246 1 »（： 1 ^ 1 {2019/007282

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

 Specific examples of the compound for introducing the photoreactive functional group include a compound capable of reacting with a hydroxyl 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, di-propenyl-da, 01-dimethylbenzyl isocyanate, methacryloyl Isocyanates, or allyl isocyanates; Diisocyanate compounds or polyisocyanate compounds

(Meth) acryloyl diisocyanate compound, polyisocyanate compound, etc. which are obtained by making it react with (meth) acrylic-acid 2-hydroxyethyl are mentioned. Moreover, glycidyl (meth) acrylate, allyl glycidyl ether, etc. are mentioned as a compound which can react with the carboxyl group of a 2nd repeating unit. The photoreactive functional group may be included by substituting 20 to 95% by weight of the second repeating unit with respect to 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 decrease in adhesion by ultraviolet irradiation is not sufficient, and when the content of the second repeating unit exceeds 95% by weight, the cohesion of the pressure-sensitive adhesive composition may be lowered before UV irradiation. . Considering the remarkable effect of the peeling force improvement effect due to the introduction of the photoreactive functional group, the second repeating unit into which the photoreactive functional group is introduced is 60 to 95% by weight based on the total weight of the second repeating unit, and more specifically 70 to 95 To the second repeating unit by weight 2019/245246 1 »（： 1 ^ 1 {2019/007282

Photoreactive functional groups may be included.

In the present invention, the (meth) acrylate resin having the silicone-based functional group and the photoreactive functional group may optionally contain ( ₃ 3) other (other than the first repeating unit of () and the second repeating unit of (32)). It may further include a third repeating unit derived from a meth) acrylate compound.

 The (33) third repeating unit is an aliphatic (meth) acrylate as a repeating unit derived from a (meth) acrylate-based compound that does not contain the specific functional group described above, specifically, a silicone-based functional group, a hydroxyl group, a carboxyl group and a nitrogen-containing functional group. It may be a repeating unit containing a structure derived from alicyclic (meth) acrylate, aromatic (meth) acrylate, and the like.

 As said aliphatic (meth) acrylate, the alkyl (meth) acrylate which has a C1-C20 alkyl group is mentioned, Specifically, methyl

(Meth) acrylate, ethyl (meth) acrylate, 11-propyl (meth)) acrylate, isopropyl (meth) acrylate, 11-butyl (meth) acrylate, 1; -butyl (Meth) acrylate,

(Meth) acrylate, pentyl (meth) acrylate, 2-ethylnuclear chamber (meth) acrylate, 2-ethylbutyl (meth) acrylate, 11-octyl (meth) acrylate isooctyl (meth) acrylate, Or isononyl (meth) acrylate.

 Examples of the alicyclic (meth) acrylates include cycloalkyl (meth) acrylates having a cycloalkyl group having 3 to 30 carbon atoms, and specifically, isobornyl acrylate (1%, trimethylcyclonuclear acryl). And a cyclopentyl (meth) acrylate, a cyclonuclear chamber (meth) acrylate, a dicyclopentanyl methacrylate, or a dicyclopentenyl oxy methacrylate.

As said aromatic (meth) acrylate, the alkyl (meth) acrylate etc. which have a C6-C30 aromatic group are mentioned, Specifically, a phenylpropyl (meth) acrylate and the ₀ -phenylphenol 明 (meth) Acrylate, 3-phenylphenoxypropyl (meth) acrylate, or phenol ¾) (meth) acrylate 2019/245246 1 »（： 1 ^ 1 {2019/007282

And the like.

 Among them, an alkyl group having 1 to 12 carbon atoms, more preferably, in that adhesive strength can be easily controlled without lowering the cohesive force of the adhesive composition, and the wettability, water resistance and peelability to the wafer surface of the adhesive composition can be further increased. It may be preferable to further include a (meth) acrylate compound-derived repeating unit having an alkyl group having 1 to 6 carbon atoms.

The ( _¾ 3) third repeating unit may be included in an amount of 5 to 70% by weight based on the total weight of the (meth) acrylate resin having a silicon-based functional group and a photoreactive functional group. When the content of the third repeating unit is less than 5% by weight, the durability of the pressure-sensitive adhesive composition may be lowered. When the content of the third repeating unit is higher than 70% by weight, the adhesion and peeling force may be lowered.

More specifically, when the ( ₃ 3) third repeating unit is further included, 20 to 80 weight of the first repeating unit of 1) based on the total weight of the (meth) acrylate resin having a silicon-based functional group and a photoreactive functional group %, 10 to 70% by weight of the second repeating unit of 2), and 5 to 70% by weight of the third repeating unit of 3), and more specifically 20 to 40 of the first repeating unit of (). % By weight, 20 to 40% by weight of the second repeating unit of (x2), and 40 to 60% by weight of the third repeating unit of the above (33). 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-described content range, it is possible to exhibit more excellent adhesive strength and peeling force after irradiation with ultraviolet light without fear of lowering the durability of the pressure-sensitive adhesive composition. have.

 In the present invention, the (meth) acrylate-based resin having the silicon-based functional group and the photoreactive functional group may be prepared through the introduction of a photoreactive functional group after the polymerization reaction with respect to a mixture of monomers providing each repeating unit.

Specifically, the polymerization reaction may be solution polymerization, photopolymerization, bulk polymerization, suspension polymerization, or emulsion polymerization, and the like, and among these, the process may be easy, and the polymer to be produced may have excellent uniformity in that it has excellent uniformity. It can be carried out by the solution polymerization method used. The solution polymerization is crosslinkable with a (meth) acrylate compound containing a silicone-based functional group After mixing the initiator in a state in which monomers, and optionally monomers including other (meth) acrylate-based compounds are uniformly mixed, may be carried out at a polymerization temperature of 50 to 140 ° C. At this time, the initiator may be azo initiator such as azobis isobutyronitrile or azobiscyclonucleic acid carbonitrile; Peroxide-based initiators, such as benzoyl peroxide or acetyl peroxide, etc. are mentioned, Any one or a mixture of two or more of these may be used.

 In order to introduce the photoreactive functional group into a part of the second repeating unit derived from the crosslinkable monomer in the completion of the polymerization reaction and the resulting polymerization reactant, as described above, the functional group capable of addition reaction with the reactive functional group in the crosslinkable monomer and By adding a compound containing a photoreactive functional group, and by adding or reacting the addition, a (meth) acrylate-based resin having a silicon-based functional group and a photoreactive functional group can be prepared.

 In the present invention, the (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group can exhibit an excellent effect when applied to the pressure-sensitive adhesive composition through the control of the type and content of the monomer material and polymerization conditions, etc. 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 the silicon-based functional group and the photoreactive functional group may have a weight average molecular weight «of 50, 000 g / mol to 2,000,000 g / mol, preferably 700,000 g / mol to l It may be 500,000g / mol, or l, 000,000g / mol to l, 200, 000g / mol. In the case where the weight average molecular weight is in the above range, proper coating properties and cohesive strength are exhibited, and thus problems such as residues remaining in the adherend in the peeling step are preferable.

In addition, in this specification, a weight average molecular weight means the weight average molecular weight (unit: g / mol) of polystyrene conversion measured by the gel permeat ion chromatography (GPC) method. In the process of measuring the weight average molecular weight of polystyrene conversion measured by the GPC method, a detector and an analytical column such as a conventionally known analytical device and a differential refractive index detector (Refractive Index Detector) can be used, Temperature conditions, solvents, f low rate can be applied. Specific examples of the measurement conditions include a temperature of 30 ^° C, chloroform solvent (Chloroform) and f low rate of 1 mL / min. In the present invention, the (meth) acrylate resin having a silicone-based functional group and a photoreactive functional group has a glass transition temperature (Tg) of -100 ^° C to -5 ^° C, preferably -70 ^° C to -10 ^° C, or -45 to -30 ^° C. When the glass transition temperature is in the above range, it exhibits an appropriate coating property and cohesive force, and is excellent in adhesion workability in the initial adhesion 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 DSC (Diferental Al Scanning Color imer).

In addition, in the present invention, 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 a silicone-based functional group and a photoreactive functional group. In this case, the compound may be included in the range that does not inhibit the effect in the present invention, specifically 20% by weight or less, more specifically 10 to 5% by weight relative to the total weight of the binder resin.

 (A) binder resin having the above configuration may be included in 50 to 97% by weight relative to the total weight of the pressure-sensitive adhesive composition. If the content of the binder resin is less than 50% by weight, it is difficult to secure the coating property and workability, and if it exceeds 97% by weight, it is difficult to obtain sufficient adhesive force. More specifically, (a) the binder resin may be included in 70 to 90% by weight based on the weight of the pressure-sensitive adhesive composition.

(b) photoinitiators

 On the other hand, in the present invention, (b) the photoinitiator is a component having an activity at a wavelength of 250nm or more, and is a component to easily start the photopolymerization at the wavelength transmitted from the base film to reduce the adhesive force of the adhesive layer, the amine compound described later When used in combination with, the effect of lowering the adhesion by photocuring can be further improved.

The photoinitiator (b), for example, thioxanthone, 2-chlorothioxanthone, 2- 2019/245246 1 »（： 1 ^ 1 {2019/007282

Methyl thioxanthone, 2, 4- dimethyl thioxanthone, isopropyl thioxanthone, 2, 4-dichlorothioxanthone 2 4-diethyl thioxanthone 2 4-diisopropyl thioxanthone, dodecyl thioxanthone , Bis (2,4,6-trimethylbenzoyl) -phenylphosphineoxide, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one, oxy-phenyl-acetic Acid 2- [2-Oxo-2-phenyl-acetoxy-ethoxy] -ethylester and oxy-phenyl-acetic acid

Mixture of 2- [2-hydroxy-ethoxy] -ethylester, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2,4,6-trimethyl Benzoyl-diphenal-phosphine oxide and the like. Preferably, isopropyl thioxanthone and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide can be used. These may be used alone or in combination of two or more thereof. The photoinitiators are excellent in activity by ultraviolet rays transmitted through the base film, and when used in combination with the tertiary amine compound described below, synergistic effect can realize a sufficient decrease in adhesion in the photocuring step.

 In the present invention, the 0>) photoinitiator, may be included in 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the (3) binder resin, when included in the content range Induces an effective curing reaction and prevents a decrease in physical properties due to remaining 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 the content of the photoinitiator exceeds 40 parts by weight, the coating property may be lowered due to not having a moderate viscosity.

(X) polyfunctional crosslinking agent

 In the present invention, the (0) polyfunctional crosslinking agent reacts with a functional group contained in the (meth) acrylate resin having a silicone-based functional group and a photoreactive functional group in the binder resin component (3) to improve the cohesive force of the pressure-sensitive adhesive composition. To act.

Specifically, at least one compound selected from the group consisting of an isocyanate compound, an aziridine compound, an epoxy compound, and a metal chelate compound may be used. The isocyanate compound, an aziridine compound, an epoxy compound, and a metal chelate compound may be used. Compound sugar 2019/245246 1 »（： 1 ^ 1 {2019/007282

Any compound commonly used in the art may be used without particular limitation.

Examples of the isocyanate-based compound include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, nuxamethylene diisocyanate, isoborone diisocyanate, tetramethylxylene diisocyanate, naphthalene diisocyanate and any one of the above polyols (near . And at least one selected from the group consisting of reactants with trimethylol propane). Further examples of the aziridine compound include n toluene-2,4-bis (1-aziridine-carboxamide), N ¹ - diphenylmethane-4, ^41-bis (1-aziridine-carboxamide), And one or more selected from the group consisting of triethylene melamine, bisisoprotaloyl-1- (2-methylaziridine) and tri-1-aziridinylphosphine oxide. Examples of the epoxy-based compound include at least one selected from the group consisting of ethylene glycol diglycidyl ether, triglycidyl ether, trimethylolpropane triglycidyl ether, comparative tetraglycidyl ethylenediamine and glycerin diglycidyl ether Examples of the metal chelate compound include compounds in which polyvalent metals such as aluminum, iron, zinc, tin, titanium, antimony, magnesium, and / or vanadium are coordinated with acetyl acetone, ethyl acetoacetate, or the like. May be used, but is not limited thereto.

 In this invention, the said ((:) polyfunctional crosslinking agent is said (3) binder resin.

It may be included in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 10 parts by weight. When the content of the multifunctional crosslinking agent is less than 0. (1) parts by weight, the cohesive force of the adhesive layer may be lowered to cause cohesive failure during the high temperature process. There is a possibility that peeling or lifting may occur due to insufficient securing.

(Tertiary amine compound

On the other hand, in the present invention, the pressure-sensitive adhesive composition may optionally further include a ((3) tertiary amine compound together with the components of the above ( ₃ ) to (). 2019/245246 1 »（： 1 ^ 1 {2019/007282

The ((1) tertiary amine compound may realize a curing reaction increase even after a high temperature process through the synergy effect when used in combination with the photoinitiator described above. Specifically, in the case of the (tertiary amine compound, it acts as a radical donor Generating synergies with photoinitiators can be achieved.

The ((1) tertiary amine compound is, for example, ethyl-1) -dimethyl amino benzoate, methyl-dimethyl amino benzoate, 2-ethylnucleyl-1 ₎ -dimethyl amino benzoate, octyl-! ₎ -Dimethyl amino benzoate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, non-dihydroxyethyl- torudiene, and the like, preferably, ethyl-1) -dimethyl amino benzoate Or 2-ethylnuclear chamber-! ₎ -Dimethyl amino benzoate can be used. These may be used alone or in combination of two or more thereof.

 In the present invention, the tertiary amine compound may be included in an amount of 100 to 2000 parts by weight, and more preferably 200 to 1500 parts by weight, based on 100 parts by weight of the photoinitiator. When included in the above content range, it is possible to maximize the synergistic effect of the combination. If the content of the tertiary amine compound is less than 100 parts by weight, it is insufficient to give moderate reactivity to the photoinitiator, and if it exceeds 2000 parts by weight, the pressure-sensitive adhesive composition may not have a sufficient viscosity, there is a fear that the coating properties.

 In the present invention, the pressure-sensitive adhesive composition is a tackifying resin, initiator, low molecular weight, epoxy resin, curing agent, UV stabilizer, antioxidant, colorant, reinforcing agent, antifoaming agent, surfactant, foaming agent within a range that does not affect the effect of the invention It may optionally further comprise one or more additives selected from the group consisting of organic salts, thickeners and flame retardants. II. Temporary Fixing Adhesive Sheet

 According to another embodiment of the present invention, a base film and an adhesive layer are provided, and the adhesive layer is provided with a temporary fixing adhesive sheet including the adhesive composition.

The pressure-sensitive adhesive layer is manufactured by the pressure-sensitive adhesive composition, thereby realizing sufficient adhesive force during the manufacturing process of the semiconductor even under high temperature conditions, and peeling 2019/245246 1 »（： 1 ^ 1 {2019/007282

It is easy to reduce the adhesive force by the light curing in the step. In particular, by using a (meth) acrylate-based resin having a silicone-based functional group and a photoreactive functional group as the binder resin, even if the wavelength is transmitted at a relatively low transmittance from the base film, excellent photo-initiation efficiency and excellent adhesive force lowering effect even after high temperature process 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, in the present invention, the temporary fixing pressure-sensitive adhesive sheet is 30% or less of the adhesive force change rate of the pressure-sensitive adhesive layer defined in accordance with Equation 1 below.

 [Equation 1]

 Change rate of adhesive force of adhesive layer (%) = Show 2 X 100 / yarn

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

Show 2 is the adhesive force of the pressure-sensitive adhesive layer measured after irradiating the heat-treated pressure-sensitive adhesive layer with ultraviolet light of a composite wavelength in the region of 200 ^ to 500ä at 1001/011 ² to 20001 八: mi ² light.

 The adhesive force change rate of the pressure-sensitive adhesive layer of Equation (1) is an index that exhibits excellent adhesive force even when subjected to high temperature conditions in the semiconductor manufacturing process, and exhibits sufficient adhesive force lowering effect in the peeling step by photocuring. The adhesive sheet for fixing is applied to the semiconductor manufacturing process by satisfying the adhesive force change rate value of Equation 1 below 30%, thereby significantly improving the process efficiency and manufacturing a high quality semiconductor. Base Film

In the temporary fixing adhesive sheet of the present invention, the base film may be a polymer base film, preferably the glass transition temperature 0¾）

It may be a polymer base film or more. The glass transition temperature of the base film

By satisfying the above, it exhibits sufficient heat resistance, and thus, a problem such as wrinkles and deformation does not occur during the high temperature process so that the semiconductor process can be easily performed. 2019/245246 1 »（： 1 ^ 1 {2019/007282

In the present invention, when the glass transition temperature of the base film is less than 60, it may affect the process due to problems such as deterioration and deformation under high temperature conditions generated during the manufacturing process of the semiconductor. As a result, defects in the semiconductor process may occur. The glass transition temperature of the base film is preferably

It may be abnormal. In this case, the above effects can be further improved.

In the present invention, as the polymer base film, for example,

Polyetheretherketone (1) 01 no 01 01),

Polyethylene terephthalate (1) 01 61; 1171611 6 1) 111: 1131 6) and polyethylenenaphthalate (5) 01 61 ± 7161½1 1) 111: 1131 6).

Polyphenylene sulfide (01 1) 11611716116 3111 ^ (16) and polyamide () ¾ may include at least one polymer compound selected from the group consisting of (¾), preferably polyimide, polyamide Or polyamideimide.

 In the present invention, when the base film contains a mixture of two or more kinds of polymers, a film having a structure in which two or more layers of films including each of the aforementioned polymers are laminated or a single layer containing two or more of the aforementioned polymers includes both films. It is.

 In addition, the base film includes the heat-resistant polymer component described above, and satisfies a transmittance of 50% or more at a wavelength of 300 to 1 or more, thereby allowing the photoinitiator in the adhesive layer described later to easily start the photopolymerization reaction.

 When the base film has a transmittance of less than 50% at a wavelength of 300 ä or more, light absorption of the photoinitiator of the pressure-sensitive adhesive layer may not be sufficient, and a drop in adhesive force may not be sufficient in the step of separating the pressure-sensitive adhesive sheet.

The thickness of the base film is not particularly limited, and may be generally formed in a thickness of 5 to 500_, preferably in a thickness of 10 to 300_ or a thickness of 25 to 100_. In this case, it can be supported in the high temperature process of the semiconductor, peeling without damage in the peeling step of the adhesive sheet 2019/245246 1 »（： 1 ^ 1 {2019/007282

It is possible.

 The base film may be subjected to additional treatment to improve the performance within the range that does not affect the desired effect of the present invention. For example, conventional physical or chemical treatments such as matt treatment, corona discharge treatment, primer treatment or crosslinking treatment can be applied to the surface of the base film. Adhesive layer

 In the temporary fixing adhesive sheet of the present invention, the adhesive layer may be formed on one surface of the base film, and includes the above-described pressure-sensitive adhesive composition.

 The method for forming the pressure-sensitive adhesive layer containing the above components on the base film is not particularly limited, and for example, a method for forming the pressure-sensitive adhesive layer by coating the pressure-sensitive adhesive layer forming composition of the present invention directly on the base film, or A method of applying a composition for forming an adhesive layer on a peelable substrate to prepare an adhesive layer, and a method of transferring the adhesive layer onto a base film using the peelable substrate may be used.

At this time, the method of coating and drying the adhesive layer-forming composition is not particularly limited. For example, a comma coater, a gravure coater, a die coater or a reverse coater may be diluted as it is, or diluted with a suitable organic solvent. After apply | coating by well-known means, etc., the method of drying a solvent for 10 second-30 minutes at the temperature of 60 degrees-2001: can be used. In addition, in the above process, to proceed with sufficient crosslinking reaction of the pressure-sensitive adhesive

Additional processes can be performed.

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

In addition, in the present invention, the temporary fixing adhesive sheet may further include a release film formed on the adhesive layer. Examples of release films that can be used include polyethylene terephthalate film, polytetrafluoroethylene film, polyethylene film, polypropylene film, polybutene film, polybutadiene film, 2019/245246 1 »（： 1 ^ 1 {2019/007282

And one or more plastic films such as a vinyl chloride copolymer film or a polyimide film.

 The surface of the release film as described above may be released by one or more kinds of alkyd-based, silicon-based, fluorine-based, unsaturated ester-based, polyolefin-based, or wax-based or the like. Particularly, release agents such as alkyd-based, silicon-based or fluorine-based compounds having heat resistance are preferable.

 The release film is usually 10 / pad to 500！, preferably may be formed to a thickness of about 20 ~ 200 / year, but is not limited thereto.

 Temporary fixing adhesive sheet according to the present invention can be used as a protective film and a carrier film of the semiconductor process.

 In addition, the temporary fixing adhesive sheet according to the present invention may include one or more adhesive layers, and thus may be formed on one side or both sides of the base film.

 In addition, the method of manufacturing the temporary fixing adhesive sheet is not particularly limited, and for example, a method of sequentially forming an adhesive layer and a release film (if necessary) on the base film, or the adhesive layer on the base film After separately forming the formed release film, a method of laminating it may be used.

 In the above, the lamination method is not particularly limited, and hot roll lamination or lamination press method may be used, and the hot lamination method is preferable in view of the possibility of double continuous process and efficiency. The hot roll lamination method may be performed at a pressure of 0.1 hour / to 10 group / at a temperature of 10 to 1001 :, but is not limited thereto.

 Figures 3 to 3, and 23 to 3/4 show a cross-sectional view of the temporary fixing adhesive sheet 10 according to an embodiment of the present invention, respectively.

 Referring to FIG. 1, the temporary fixing adhesive sheet 10 according to the embodiment of the present invention may have a structure in which the base film 100 and the adhesive layer 200 are stacked. When the adhesive sheet 10 is applied to a semiconductor manufacturing process, the surface 200 (3) 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, for temporarily fixing according to an embodiment of the present invention 2019/245246 1 »（： 1 ^ 1 {2019/007282

The adhesive sheet 10 may have a structure in which the base film 100, the adhesive layer 200, and the release film 300 are sequentially stacked.

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

When reference to Fig. _23, one adhesive sheet 10 for temporary fixing in accordance with an embodiment of the present invention may be a structure formed of each of the two adhesive layers 210 and 220 on both surfaces of the base film 100.

 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 one of the adhesive films 100 is not formed may be attached to a predetermined portion of the semiconductor device. For example, the surface 220 () 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 ¾, the temporary fixing adhesive sheet 10 according to an embodiment of the present invention is the first release film 310, the first adhesive layer 210, the base film 100, the second 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 off 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, 220 may be attached to a portion of the semiconductor device.

 Subsequently, in the peeling step of the adhesive sheet 10, ultraviolet rays are irradiated to the first adhesive layer 210 to pass through the lower base film 100, and the second adhesive layer 220 may be photocured. As a result, the adhesive force of the adhesive layer 200 may be lowered, and thus the temporary fixing adhesive sheet 10 may be easily peeled from the semiconductor device.

Typically, the manufacturing of the semiconductor device includes a process performed under high temperature conditions, in which case, there is a problem that the base film or the adhesive layer is thermally decomposed, or the additive contained in the adhesive layer is detached. In this case, sufficient adhesive force may not be realized during the manufacturing process of the semiconductor, or 2019/245246 1 »（： 1 ^ 1 {2019/007282

In the peeling step by photocuring, sufficient adhesive force was not realized. By temporarily fixing the adhesive sheet according to the present invention by forming a base film with a heat-resistant polymer having ultraviolet rays, by forming a pressure-sensitive adhesive layer with a specific component that can improve the photopolymerization initiation and reactivity in the transmission wavelength region of the base film, The above-described problems can all be improved, and thus, the manufacturing process efficiency of the semiconductor can be improved and the quality of the manufactured semiconductor can be improved.

 【Effects of the Invention】

 The pressure-sensitive adhesive composition according to the present invention exhibits an appropriate adhesive force during the semiconductor manufacturing process, and at the time of photocuring, the adhesive force sufficiently decreases and peeling is easy. Bubbles and lifting are not generated even after the high temperature process. Accordingly, the pressure-sensitive adhesive composition according to the present invention is useful for the preparation of the temporary fixing pressure-sensitive adhesive sheet.

【Brief Description of Drawings】

Degree

11 to 11), and FIGS. 23 to 3/4 schematically show the cross-sectional structure of the temporary fixing adhesive sheet 10 according to one embodiment of the present invention.

 Figure 3 is a photograph observing the appearance after the heat treatment process for the temporary fixing adhesive sheet according to Example 1.

 Figure 4 is a photograph observing the appearance after the heat treatment process for the temporary fixing adhesive sheet according to Comparative Example 1.

 <Explanation of Codes ñ

 10 ： Temporary Fixing Adhesive Sheet

 100 ： base film

 200 ： adhesion layer

 300 ： release film

 [Best form for implementation of the invention]

 Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only to illustrate the invention, not limited to the invention only.

<Production of Adhesive Composition> Preparation Example 1

 62.5 g of ethyl nuclear acrylate (EHA) in a reactor equipped with a refrigeration system for reflux of nitrogen gas and easy temperature control

A mixture of monomers consisting of 20 g of (meth) acrylate (Si lap laneä FM-0721 manufactured by JNC) and 17.5 g of hydroxyethyl acrylate (HEA) was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and thoroughly mixed at 30 ^° C. for 60 minutes while injecting nitrogen to remove oxygen into the reactor. After that, the temperature was kept at 65 ^° C., and the reaction initiator Azobi si sobutyloni trle (V-60ä manufactured by Wako Pure Chemi cal Industries) O. lg was added in portions, and the reaction was initiated. The reaction was prepared.

20 g of methacryloyl isocyanate (MOI) (85.5 mol% based on HEA in the first reactant) and 0.08 g of a catalyst (dibutyl t in di laurate, DBTDL) were combined with the primary reactant at 40 ^° C. for 24 hours. And a UV curable group was introduced into the polymer side chain in the primary reactant to prepare a binder resin (a-1).

 To 100 g of the binder resin (a-1), 2.0 g of toluene diisocyanate (TDI) as a polyfunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethyl as an amine compound A pressure-sensitive adhesive composition was prepared by mixing 6.0 g of amino benzoate. Preparation Example 2

 52.5 g of ethyl nuclear acrylate (EHA) in a reactor equipped with a refrigeration system to allow nitrogen gas to reflux and for easy temperature control

A mixture of monomers composed of 30 g of (meth) acrylate (Si lap laneä FM-0721 manufactured by JNC) and 17.5 g of hydroxyethyl acrylate (HEA) was added thereto. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and thoroughly mixed at 30 ^° C. for 60 minutes while injecting nitrogen to remove oxygen into the reactor. The temperature was then raised to 65 ^° C. and the reaction initiator Azobi si sobutyloni tr i le (V-60ä manufactured by Wako Pure Chemi cal Industr ies) O. split lg into the reaction After the start was polymerized for 6 hours to prepare a primary reaction.

20 g of methacryloyl isocyanate (MOI) (85.5 mol% based on HEA in the first reactant) and 0.08 g of a catalyst (dibutylt in di laurate, DBTDL) were added to the first reactant at 40 ^° C. for 24 hours. By reacting, an ultraviolet curing group was introduced into the polymer side chain in the primary reactant to prepare a binder resin (a-2).

To 100 g of the binder resin (a-2), 2.0 g of toluene diisocyanate (TDI) as a polyfunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethylamino benzo as a tertiary amine compound 6.0 g of eights were mixed to prepare an adhesive composition.

 Preparation Example 3

Nitrogen chamber acrylate (EHA) 37g, butyl acrylate (BA) 25.5g, silicone (meth) acrylate (Si lap laneä FM-manufactured by JNC) in a reactor equipped with a refrigeration system for reflux of nitrogen gas and easy temperature control 0721) A mixture of monomers consisting of 20 g and 17.5 g of hydroxyethyl acrylate (HEA) was added. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and thoroughly mixed at 30 ^° C. for 60 minutes while injecting nitrogen to remove oxygen into the reactor. After the temperature is maintained elevated to 65 ^° C, and the reaction initiator Azobi sisobutyloni tr i le (Wako Pure Chemical Industr. Ies of V-60 manufactured by ^TM) O. After the lg was added in portions and the reaction was initiated, the first reaction product was prepared by polymerization for 6 hours.

The one work as methacrylic the primary reaction product an isocyanate (MOI) 20g and a catalyst (dibutyl di t in l aurate, DBTDL) (l car 85.5 mol% based on HEA in the reactants) blended 0.08g, and at 40 ^° C 24 After reacting for a time, an ultraviolet curing group was introduced into the polymer side chain in the primary reactant to prepare a binder resin (a-3).

To 100 g of the binder resin (a-3), 2.0 g of toluene diisocyanate (TDI) as a polyfunctional crosslinking agent, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator, and ethyl-p-dimethylamino benzo as a tertiary amine compound 6.0 g of eights were mixed to prepare an adhesive composition. Comparative Production Example 1

A mixture of monomers consisting of 82.5 g of ethyl nuclear chamber acrylate and 17.5 g of hydroxyethyl acrylate (HEA) was added to a reactor equipped with a cooling device to allow nitrogen gas to reflux and 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 thoroughly mixed at 30 ^° C. for 60 minutes while injecting nitrogen to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ^° C., and the reaction initiator, V-60 (Azobisisobutylonitrile) O.lg, was added in portions, and the reaction was initiated.

20 g of methacryloyl isocyanate (MOI) (85.5 mol% based on HEA in the first reactant) and 0.08 g of a catalyst (DBTDL: dibutyl tin dilaurate) were added to the first reactant, and reacted at 40 ^° C. for 24 hours. A (meth) acrylate binder resin (b-1) was prepared by introducing an ultraviolet curing group into the polymer side chain in the primary reactant.

 2.0 g of a T () I isocyanate curing agent to the (meth) acrylate binder resin (bi) ioog, 1.2 g of isopropyl thioxanthone (ITX) as a photoinitiator and ethyl-p- as a tertiary amine compound. 6.0 g of dimethyl amino benzoate was mixed to prepare a pressure-sensitive adhesive layer-forming composition. Comparative Production Example 2

Ethyl nuclear chamber acrylate in a reactor equipped with a refrigeration system to allow reflux of nitrogen gas and easy temperature control _. A mixture of 62.5 g, 20 g of silicone (meth) acrylate (Si laplane ™ FM-0721 manufactured by JNC) and 17.5 g of hydroxyethyl acrylate (HEA) was added thereto. Subsequently, 200 g of ethyl acetate (EAc) was added as a solvent based on 100 g of the monomer mixture, and thoroughly mixed at 30 ^° C. for 60 minutes while injecting nitrogen to remove oxygen into the reactor. Thereafter, the temperature was maintained at 65 ^° C., and the reaction initiator, V-60 (Azobisisobutylonitrile) O.lg, was added in portions and the reaction was initiated at the start of polymerization for 6 hours to prepare a primary reactant.

10 g (first order reactant) methacryloyl isocyanate (MOI) to the primary reactant 2019/245246 1 »（： 1 ^ 1 {2019/007282

42.7 mol%

11 1 ₃ 6) was mixed with 0.045 yo and reacted at 40 ^° (:) for 24 hours to introduce an ultraviolet curing machine into the polymer side chain in the primary reactant to prepare a binder resin (2). A multifunctional crosslinking agent in the binder resin (13-2) 10½ toluene diisocyanate (11) 1) 2.0 _§, photoinitiators with isopropyl thioxanthone () 0 1.2 _§, and ethyl tertiary amine compounds -) - Dimethyl amino benzoate 6.0 _§ was mixed to prepare a pressure-sensitive adhesive composition. Comparative Production Example 3

Nitrogen gas reflux and acetate in a reactor equipped with a cooling system for easy regulation of temperature haeksil acrylate 62.5 _¾ (silicone (meth) acrylate 20 Dragon and hydroxyethyl acrylate 0世the time of preparation of the mixture of monomers composed of 17.5 _§ It was. Subsequently, 20¾ of ethyl acetate 犯) was added as a solvent based on the monomer mixture 10¾, and the mixture was sufficiently mixed at 30 ^° C. for at least 60 minutes while injecting nitrogen to remove oxygen into the reactor. After that, the temperature was maintained at 65 ° C., and the reaction initiator, ¥ _60 (show 20 3 013111 101111; 1 ^ 1 g), was added in 0. 1 _§ , and the reaction was initiated, followed by polymerization for 6 hours to prepare a primary reactant. .

For the methacryloyl isocyanate 22.9 for the primary reactant (97 mol% based on the four phases in the primary reactant)

A binder resin (13-3) was prepared by mixing 0.09¾ and reacting at 401: for 24 hours to introduce an ultraviolet curing machine into the polymer side chain in the primary reactant. (A multifunctional crosslinking agent to ¾ toluene diisocyanate奸a) of the binder resin (13-3) 10 2.0 _§, isopropyl thioxanthone () as photoinitiator, 0 _§ 1.2, and a tertiary amine compound with ethyl-dimethylaminobenzoate Eight 6. was mixed to prepare a pressure-sensitive adhesive composition, Comparative Preparation Example 4

In the preparation of the pressure-sensitive adhesive composition, a binder resin (1 广 1) in Comparative Preparation Example 1 is used as the binder resin, and further silicone (meth) acrylate is added. A pressure-sensitive adhesive composition was prepared in the same manner as in Preparation Example 1, except that. Specifically, to 80 g of the binder resin (b-1) prepared in Comparative Production Example 1, 20 g of silicone (meth) acrylate, 2.0 g of toluene diisocyanate (TDI) as a polyfunctional crosslinking agent, and isopropyl thioxanthone as a photoinitiator 1.2 g of (Isopropyl thioxanthone, ITX) and 6.0 g of ethyl-p-dimethylamino benzoate were mixed with an amine compound to prepare an adhesive composition.

The content and physical properties (¾ and dragon) of each repeating unit in the binder resins prepared in Preparation Examples 1 to 3 and Comparative Preparation Examples 1 to 3 were analyzed and measured, and the results are shown in Table 1 below.

In Table 1 below, the content of each repeating unit in the binder resin was calculated through analysis. In addition,

It is the weight average molecular weight of polystyrene conversion measured using 灰 ：, and the solvent is the glass transition temperature measured by (：.

 [Table 1]

2019/245246 1 »(： 1 ^ 1 {2019/007282

<Production of Temporary Fixation Adhesive Sheet>

 Example 1

The pressure-sensitive adhesive composition of Preparation Example 1 was applied on a release-treated polyethylene terephthalate film (thickness 38, glass transition temperature: 120 ^° 0) and dried for 3 minutes at 1101: to form an adhesive layer having a thickness of about 30 / sea. . The formed pressure-sensitive adhesive layer was laminated on a base film polyamideimide having a thickness of 5 / / and then aged to obtain a temporary fixing adhesive sheet. Examples 2 to 3 and Comparative Examples 1 to 4

 A temporary fixing adhesive sheet was prepared in the same manner as in Example 1 except for applying the ingredients and the amounts of Table 2 below.

 Table 2

Experimental Example: Evaluation of Adhesion and Peeling Force

 For the temporary fixing adhesive sheet prepared according to the Examples and Comparative Examples, the adhesive force and the peel force according to the light curing was evaluated by the following method, the results are shown in Table 3.

After cutting the temporary fixing adhesive sheets prepared in Examples and Comparative Examples to a width of 25 ä, a sample urine (before heat treatment) attached to a silicon wafer using a 21¾ roller was prepared. Next, Sample B (after heat treatment) was prepared by heat-treating the temporary fixing adhesive sheet attached to the silicon wafer in 250 oven for 10 minutes. On the base film side, irradiated with ultraviolet light (using a mercury lamp having a complex wavelength in the range of 200 nm to 500 nm) under a light quantity of 1000 mJ / cm ² for the sample A without heat treatment and sample B subjected to heat treatment, respectively, Was measured.

 Adhesive force was measured by using a texture analyzer manufactured by Stable Micro Systems, Inc. at 300 mm / min, 180 degree angle, and the results are shown in Table 2 below.

 Moreover, the adhesive force change rate of the adhesion layer was computed from the measured adhesive force according to following formula (1).

 [Equation 1]

 Rate of change of cohesive force of coccyx) A2 x 100 / A1

(In the above Equation 1, after the heat treatment for 10 minutes at 250 ^° C. is the adhesive force of the adhesive layer,

A2 is the adhesive force of the pressure-sensitive adhesive layer measured after irradiating the heat-treated pressure-sensitive adhesive layer with ultraviolet light having a complex wavelength in the range of 200 nm to 500 nm at a light quantity of 100 mJ / cm ² to 2000 mJ / cm ² ).

 In addition, bubble generation and floating in Sample B after heat treatment were visually observed. The results are shown in FIGS. 3 and 4, respectively. 3 and 4 are photographs of the appearance after the heat treatment process for the temporary fixing pressure-sensitive adhesive sheet of Example 1 and Comparative Example 1, respectively.

 Table 3

2019/245246 1 »（： 1 ^ 1 {2019/007282

 In Table 3, means that it is not measured. As can be seen from the experimental results for the sample 8 after the heat treatment of Table 3, the temporary fixing adhesive sheet of Examples 1 to 3 prepared according to the present invention has a large drop in adhesive strength after a high temperature thermal process, and when peeled from the silicon wafer. It was confirmed that it can be removed without adhesive residue. Moreover, the adhesive sheets for temporary fixation of Examples 1-3 did not have the external appearance characteristic deterioration | bubble, such as bubble generation and floating, even after the heat processing process at high temperature of 2501 :. In contrast, the temporary fixing adhesive sheet of Comparative Example 1 prepared using (meth) acrylate-based resins containing only photoreactive functional groups without silicon-based functional groups as binder resins exhibited high adhesive strength even after the heat treatment step, thereby providing a silicon wafer. The adhesive residue occurred at the time of peeling from the surface, and air bubbles and lifting occurred on the surface after the heat treatment process.

 In addition, although the (meth) acrylate type resin containing a photoreactive functional group is used together with a silicone type functional group as binder resin, the content of the 2nd repeating unit into which the said photoreactive functional group was introduce | transduced was in (meth) acrylate type resin. The temporary fixing pressure sensitive adhesive sheet of Comparative Example 2, which contained less than 20% by weight based on the total weight of the low 12 repetition units, exhibited high adhesive strength even after the heat treatment process, and thus adhesive residues were generated when peeling from the silicon wafer. Similarly, bubbles and lifting occurred on the surface after the heat treatment process.

In addition, the photoreactivity _. In the case of the temporary fixing pressure sensitive adhesive sheet of Comparative Example 3, in which the content of the second repeating unit into which the functional group is introduced is included in excess of 95% by weight based on the total weight of the second repeating units in the (meth) acrylate resin, Transfer occurred after the heat treatment process, and bubbles and floating were generated on the surface after the heat treatment process similarly to Comparative Examples 1 and 2.

On the other hand, the pressure-sensitive adhesive of Comparative Example 4 prepared by simply mixing a (meth) acrylate-based binder resin containing only a photoreactive functional group without a silicone-based functional group with a silicone (meth) acrylate, is a (meth) acrylate-based compound during the stirring step. 2019/245246 1 »（： 1/10 公 019/007282

Due to the low compatibility between the binder resin and the silicone (meth) acrylate, phase separation and gelation proceeded, making it impossible to prepare an adhesive sheet.

Claims

2019/245246 1 »(： 1 ^ 1 {2019/007282 【claims】

 [Claim 1]

 (3) having silicon-based functional groups and photoreactive functional groups

Binder resin containing (meth) acrylate type resin;

 Photoinitiators; And

 (0) a multifunctional crosslinking agent;

 Having the silicon-based functional group and photoreactive functional group

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

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

[Claim 2]

 According to claim II,

 Said photoreactive functional group is a vinyl group, an allyl group, or a (meth) acryloyl group, The adhesive composition.

[Claim 3]

 The method of claim 1,

 The silicone-based functional group-containing (meth) acrylate-based monomer, at least one of the silicone (meth) acrylate represented by the following formula 23 to 2 (1), pressure-sensitive adhesive composition.

 [Formula 2

[Formula ¾] 2019/245246 1 »（： 1/10 公 019/007282

In Chemical Formulas 28 to 2 （1,

 ¾ to ¾ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

 ¾ to ¾ are each independently hydrogen or a methyl group,

 X, V, and are each independently an integer of 1 to 3,

 111 to each independently represent an integer of 1 to 200.

[Claim 4]

 The method of claim 1,

 The crosslinkable monomer containing at least one reactive functional group selected from the group consisting of the hydroxy group, the carboxyl group and the nitrogen-containing functional group is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, 6-hydroxynuclear (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, 2019/245246 1 »（： 1 ^ 1 {2019/007282

Carboxyethyl (meth) acrylate Carboxypentyl (meth) acrylate

(Meth) acrylonitrile, I vinyl pyrrolidone,

A pressure-sensitive adhesive composition comprising any one or two or more selected from the group consisting of caprolactam and 3- (11-methylaminopropyl) methacrylamide.

[Claim 5]

 The method of claim 1,

 The first repeating unit is contained in 10 to 90% by weight relative to the total weight of the (meth) acrylate-based resin having a silicon-based functional group and a photoreactive functional group, the pressure-sensitive adhesive composition.

[Claim 6]

 The method of claim 1,

 The (meth) acrylate type resin which has the said silicone type functional group and photoreactive functional group further contains the 3rd repeating unit derived from the (meth) acrylate type compound which has a C1-C12 alkyl group.

[Claim 7]

 The method of claim 1,

 Having the silicon-based functional group and photoreactive functional group

(Meth) acrylate resin is based on the resin weight

 20 to 40% by weight of the first repeating unit derived from a (meth) acrylate monomer containing a silicone-based functional group,

 20 to 40% by weight of a second repeating unit derived from a crosslinkable monomer comprising at least one reactive functional group selected from the group consisting of a hydroxyl group, a carboxyl group and a nitrogen-containing functional group, and

 40 to 60 wt% of a third repeating unit derived from a (meth) acrylate compound having an alkyl group having 1 to 12 carbon atoms,

70 to 95% by weight of the second, based on the total weight of the second repeating unit 2019/245246 1 »（： 1 ^ 1 {2019/007282

The pressure-sensitive adhesive composition, wherein the repeating unit comprises a photoreactive functional group in the side chain.

[Claim 8]

 The method of claim 1,

 Having the silicon-based functional group and photoreactive functional group

The (meth) acrylate-based resin has a weight average molecular weight of 50,000 _/ ½ ₀ to 2,000,00 / mi and a glass transition temperature of -1001 to -51 :.

[Claim 9]

 The method of claim 1,

 Photoinitiator, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropyl thioxanthone, 2,4-dichlorothioxanthone, 2, 4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, dodecyl thioxanthone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1 [4- （ Methylthio) phenyl]-2-morpholinopropane- 1-one, oxy- phenyl- acetic acid 2-[2- oxo- 2- phenyl_ acetoxy- ethoxy]-ethyl ester, oxy- phenyl- acet Ticacid 2- [2-hydroxy-ethoxy] -ethylester, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane_ 1-one and 2,4,6-trimethyl At least one selected from the group consisting of benzoyl-diphenyl-phosphine oxide, pressure-sensitive adhesive composition.

[Claim 10]

 The method of claim 1,

 (The multifunctional crosslinking agent comprises an at least one compound selected from the group consisting of an isocyanate compound, an aziridine compound, an epoxy compound and a metal chelate compound.

[Claim 11]

 The method of claim 1,

The above (photoinitiator 0.1) with respect to 100 weight part of binder resins 2019/245246 1 »（： 1 ^ 1 {2019/007282

To 40 parts by weight, and 0.01 to 30 parts by weight of the ((:) polyfunctional crosslinking agent, pressure-sensitive adhesive composition.

[Claim 12]

 The method of claim 1,

 Furthermore, the adhesive composition containing a tertiary amine compound.

[Claim 13]

 The method of claim 12,

The tertiary amine compound is ethyl-!)-Dimethylamino benzoate, methyl-1 ₎ -dimethylamino benzoate, 2-ethylnucleyl-1 ₎ -dimethylamino benzoate, octyl-dimethylamino benzoate, diethylamino Ethyl methacrylate ， dimethylaminoethyl methacrylate ， non-dihydroxyethyl-! ₎ -Toludiene and mixtures thereof,

 The pressure-sensitive adhesive composition is contained in an amount of 100 to 200 ◦ parts by weight based on 100 parts by weight of the photoinitiator.

[Claim 14]

 A base film, and an adhesive layer,

 The adhesive layer is a temporary fixing adhesive sheet comprising the pressure-sensitive adhesive composition according to claim 1.