KR101666479B1 - Benzotriazole based (meth)acrylate copolymer and adhesive composition comprising same - Google Patents

Abstract

The present invention relates to an adhesive material for debonding using a laser of a UV wavelength band, particularly a benzotriazole-based (meth) acrylate copolymer useful as a temporary temporary fixing adhesive for semiconductor three-dimensional packaging, (Meth) acrylate copolymer, which comprises (a) a polyvinylidene fluoride oligomer obtained by polymerization of a polyvinylidene fluoride oligomer having an isocyanate group at both ends and a polyfunctional acrylic monomer, and (B) an ethylenically unsaturated monomer containing a carboxyl group, (c) an ethylenically unsaturated monomer containing an epoxy group, and (d) a benzotriazole-based compound containing an ethylenically unsaturated group .

Description

(METH) ACRYLATE COPOLYMER AND ADHESIVE COMPOSITION COMPRISING SAME <br> <br> <br> Patents - stay tuned to the technology BENZOTRIAZOLE BASED (METH) ACRYLATE COPOLYMER AND ADHESIVE COMPOSITION COMPRISING SAME

The present invention relates to an adhesive material for debonding using a laser of a UV wavelength range, particularly a benzotriazole-based (meth) acrylate, which is useful as a temporary temporary fixing adhesive for semiconductor three-dimensional packaging, Lt; / RTI &gt; copolymers and adhesive compositions comprising same.

2. Description of the Related Art In recent years, semiconductor 3D packaging techniques for stacking chips with silicon through electrodes formed in three dimensions have been used for miniaturization and thinning of semiconductor chips.

In order to construct an ultra-thin device wafer having a silicon penetrating electrode, a silicon penetrating electrode is formed on the upper surface of a device wafer on which a circuit is formed, a temporary bump is formed, Use temporary bonding and debonding adhesives to bond. Bonding, debonding, etc. are performed in order to thin the wafer. In order to prevent cracking of the wafer during the high-temperature / high-vacuum passivation process, the adhesive is required to have thermal stability and optical stability in debonding together with heat resistance .

However, in the case of general adhesives, due to the inherent viscoelastic properties of the polymer, the adhesion performance is significantly lowered at a temperature higher than 200 to 250 DEG C, resulting in poor adhesion to the adhesive.

Korean Patent Laid-Open Publication No. 2009-0032681 (published on Apr. 1, 2009)

It is an object of the present invention to provide a bonding material for debonding using a laser of a UV wavelength band, in particular a benzotriazole-based (meth) acrylate, which is useful as a temporary temporary fixing adhesive for semiconductor three- ) Acrylate copolymer.

Another object of the present invention is to provide an adhesive composition comprising the benzotriazole-based (meth) acrylate copolymer and a semiconductor device packaged using the same.

The benzotriazole-based (meth) acrylate copolymer according to the present invention,

(a) a multifunctional acrylic oligomer prepared by polymerization of a carbinol-based silicone-modified urethane oligomer having isocyanate groups at both terminals and a polyfunctional acrylic monomer; (b) an ethylenically unsaturated monomer containing a carboxyl group; (c) an ethylenically unsaturated monomer containing an epoxy group; And (d) a benzotriazole-based compound containing an ethylenically unsaturated group.

The carbinol-based urethane oligomer having an isocyanate group at both terminals used in the preparation of the polyfunctional acrylic oligomer (a) may be one prepared by polymerization of a carbynol-based silicone oligomer and an isocyanate-based monomer.

In the production of a carbino group-modified urethane oligomer having an isocyanate group at both ends, the carbynolic silicone oligomer and isocyanate monomer may be used in a molar ratio of 1: 2.

In addition, the carbyne-based silicone oligomer may be polymethyl silicone including a terminal group of the following formula (1) and a repeating structure of the following formula (2) including a carbinol group:

[Chemical Formula 1]

-ROH

(2)

Wherein R is a linear alkylene group having 1 to 20 carbon atoms, and n may be an integer of 3 to 20.

The polyfunctional acrylic monomer used in the preparation of the (a) multifunctional acrylic oligomer may be at least one selected from the group consisting of hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol pentaacrylate, Acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tripropylene glycol (meth) acrylate, (Meth) acrylate, tricyclodecane dimethanol diacrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (Meth) acrylate, propoxylated neopentylglycol di (meth) acrylate, dicyclopentadienyl di (meth) acrylate, bisphenol A (Meth) may be selected from acrylate, trimethylol propyl tri (meth) acrylate and mixtures thereof.

In the preparation of the polyfunctional acrylic oligomer (a), the carbinol-based silicone oligomer having an isocyanate group at both terminals and the polyfunctional acrylic monomer may be used in a molar ratio of 1: 2 to 2: 3.

The ethylenically unsaturated monomers (b) containing a carboxyl group may be selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and mixtures thereof.

The ethylenically unsaturated monomer containing the carboxyl group (b) may be used in an amount of 1 to 1.5 mol per 1 mol of the (a) polyfunctional acrylic oligomer.

The ethylenically unsaturated monomer containing the epoxy group (c) may be an unsaturated carboxylic acid glycidyl ester compound.

The ethylenically unsaturated monomer containing the epoxy group (c) may be used in an amount of 1 to 1.5 moles per mole of the polyfunctional acrylic oligomer (a).

The benzotriazole compound (d) containing an ethylenic unsaturated group may be a compound absorbing light having a wavelength of 300 to 360 nm.

The benzotriazole-based compound containing the ethylenically unsaturated group (d) may be at least one selected from the group consisting of 2- [3- (2H-benzotriazole-2-yl) -4- hydroxyphenyl] ethyl (meth) 2- (3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propyl (meth) (meth) acrylate, a mixture of these compounds, or a mixture thereof, such as 2- [3- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl &Lt; / RTI &gt;

The benzotriazole-based compound containing the ethylenically unsaturated group (d) may be used in an amount of 0.1 to 0.5% by weight based on the total weight of the components (a) to (d) for the preparation of the benzotriazole-based (meth) acrylate copolymer have.

The polymerization for the production of the benzotriazole-based (meth) acrylate copolymer can be carried out by photo-curing by ultraviolet irradiation.

The adhesive composition according to another aspect of the present invention includes the above benzotriazole-based (meth) acrylate copolymer.

A semiconductor device according to another aspect of the present invention is packaged using the above benzotriazole-based (meth) acrylate copolymer.

Other details of the embodiments of the present invention are included in the following detailed description.

The benzotriazole-based (meth) acrylate copolymer according to the present invention is improved in thermal stability and optical stability by bonding a benzotriazole-based compound, which is an ultraviolet absorber and a stabilizer, through ultraviolet curing, It is possible to debond using a laser of UV wavelength band. Accordingly, the benzotriazole-based (meth) acrylate copolymer is particularly useful as a temporary temporary fixing adhesive for semiconductor three-dimensional packaging requiring high thermal stability and light stability.

FIG. 1 is a result of confirming the presence or absence of chemical bonding in an adhesive material through spectroscopic analysis by FTIR.
2 is a graph showing the results of thermogravimetric analysis of the benzotriazole-based (meth) acrylate copolymer of Example 1 according to the present invention in Test Example 1. FIG.
3 is a graph showing the results of measurement of the shrinkage ratio of the benzotriazole-based (meth) acrylate copolymer of Example 1 according to the present invention in ultraviolet rays.
4 is a graph showing the results of evaluating the degree of curing of the benzotriazole-based (meth) acrylate copolymer of Example 1 according to the present invention in Test Example 3. Fig.
FIG. 5 is a result of confirming the presence or absence of chemical bonding in the adhesive material before and after debonding through spectroscopic analysis by FTIR.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The present invention provides a benzotriazole-based (meth) acrylate copolymer produced by polymerization of the following components (a) to (d):

 (a) a multifunctional acrylic oligomer prepared by polymerization of a carbinol-based silicone-modified urethane oligomer having isocyanate groups at both terminals and a polyfunctional acrylic monomer;

(b) an ethylenically unsaturated monomer containing a carboxyl group;

(c) an ethylenically unsaturated monomer containing an epoxy group; And

(d) a benzotriazole-based compound containing an ethylenic unsaturated group

The present invention also provides an adhesive composition comprising the benzotriazole-based (meth) acrylate copolymer described above.

The present invention also provides a semiconductor device packaged using the above benzotriazole-based (meth) acrylate copolymer.

Hereinafter, a benzotriazole-based (meth) acrylate copolymer, an adhesive composition containing the same, and a semiconductor device packaged using the same will be described in detail.

(A) a multifunctional acrylic oligomer prepared by polymerization of a carbinol-based silicone-modified urethane oligomer having isocyanate groups at both terminals and a polyfunctional acrylic monomer; (b) an ethylenically unsaturated monomer containing a carboxyl group; (c) an ethylenically unsaturated monomer containing an epoxy group; And (d) a benzotriazole-based (meth) acrylate copolymer prepared by polymerization of a benzotriazole-based compound.

Hereinafter, each component used in the preparation of the copolymer according to one embodiment of the present invention will be described in more detail.

(a) a polyfunctional acrylic oligomer

The polyfunctional acrylic oligomer may be prepared by polymerizing a polyfunctional acrylic monomer with a carbino-based urethane oligomer having a isocyanate group at both terminals.

The carbinol-based silicone-modified urethane oligomer having isocyanate groups at both ends may be produced by a polymerization reaction of a carbinol-based silicone oligomer with an isocyanate-based monomer.

According to the present invention, a carbinol-based urethane oligomer is first prepared by reacting a carbinol-based silicone oligomer with an isocyanate-based monomer, and then the acrylic monomer is polymerized.

If stepwise polymerization of the carbinol-based silicone oligomer, isocyanate-based monomer, and acrylic monomer is carried out as described above, it is possible to control the stepwise increase of the adhesion of the polymer and the increase of the heat resistance. .

The carbinol-based silicone oligomer which can be used in the production of a carbinol-based urethane oligomer having an isocyanate group at both ends thereof can be used without any particular limitation as long as it is a silicone oligomer containing at least one carbon-bonded hydroxyl group (COH) as a carbinol group Do.

Specifically, a dimethylsiloxane-based oligomer comprising a terminal group of the following formula (1) and a repeating unit of the following formula (2) including a carbinol group may be preferable because of excellent heat resistance:

[Chemical Formula 1]

-ROH

(2)

R is a linear alkylene group having 1 to 20 carbon atoms (e.g., methylene, ethylene, propylene, or n-butylene), and n may be an integer of 3 to 20.

More specifically, it may be a carbinol-based silicone oligomer of the following formula:

(3)

The above-mentioned carbinol-based silicone oligomer may be commercially available or may be prepared by a conventional method.

In one example, the carbyne-based silicone oligomer can be prepared by reacting a hydride-terminated polysiloxane and an alcohol having at least one vinyl group.

In addition, it is preferable that the carbinol-based silicone oligomer has a weight average molecular weight of 300 to 2,000 g / mol. If the weight average molecular weight of the carbinol-based silicone oligomer is out of the above range, the mechanical properties such as tensile strength of the copolymer may be deteriorated.

The isocyanate-based monomer which can be used for producing a carbino-based urethane oligomer having an isocyanate group at both terminals by polymerization with the above-described carbyne-based silicone oligomer includes two or more isocyanate groups and is selected from the group consisting of a carbinol group and a urethane reaction Can be used without any particular limitation.

Specific examples include toluene diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-1,4-diisocyanate, 4,4'-diphenylmethane-diisocyanate, xylene diisocyanate, 2,2- , 4'-diisocyanate, p-phenylenediisocyanate, m-phenylene diisocyanate, diphenyl-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, 1-chlorobenzene- Diisocyanate, 4,4 ', 4 "-triisocyanatotriphenylmethane, 1,3,5-triisocyanatobenzene, 4,4'-dicyclohexylmethane diisocyanate, cyclohexane-1, Diisocyanate, cyclohexane-1,2-diisocyanate, hydrogenated xylene diisocyanate, m- or p-tetramethylxylene diisocyanate, hexane-1,6-diisocyanate, 2,2,4-trimethylhexane- , 6-diisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, butane- Diisocyanate, 1,12-dodecane diisocyanate, isophorone diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, and the like. One of isocyanate-based monomers may be used alone or a mixture of two or more thereof may be used.

The polymerization reaction of the above-described carbinol-modified silicone oligomer with an isocyanate-based monomer can be carried out by a usual urethane reaction, and the reaction conditions during the urethane reaction are not particularly limited.

However, it is preferable that the carbinol-based silicone oligomer and isocyanate-based monomer are used in a molar ratio of 1: 2. If the content of the isocyanate-based monomer is excessively larger than that of the carbinol-based silicone oligomer, the chemical reaction between the unreacted isocyanate-based monomer and water or another reactive monomer may proceed, which is not preferable.

The carbinol-based urethane oligomer having an isocyanate group at both terminals prepared by the above polymerization reaction has a structure in which the dimethylsiloxane repeating unit is bonded to an isocyanate group-containing functional group by a urethane bond, and more specifically, Structure: &lt; RTI ID = 0.0 &gt;

[Chemical Formula 4]

Wherein n is the same as defined above.

Wherein X and Y are each independently a functional group derived from an isocyanate compound.

Examples of the polyfunctional acrylic monomer capable of producing a polyfunctional acrylic oligomer by polymerization reaction with a carbinol-based silicone-modified urethane oligomer having an isocyanate group at both terminals produced by the polymerization reaction include: An acrylic compound containing at least one functional group capable of reacting with an isocyanate group located at both ends may be used.

Specific examples include hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tri (meth) acrylate, (Meth) acrylate, tricyclodecane dimethanol diacrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane di (Meth) acrylate, dicyclopentadienyl di (meth) acrylate, bisphenol A di (meth) acrylate, Agent) acrylate, and the like, but trimethyl-propyl tri (meth) acrylate, and the like. Among the above-mentioned polyfunctional acrylic monomers, one type may be used alone, or a mixture of two or more types may be used. As used herein, the term &quot; (meth) acrylic &quot; means that it includes acryl and methacrylic. For example, (meth) acrylate includes acrylic ester and methacrylic ester.

The polymerization reaction of the carbinol-based urethane oligomer having an isocyanate group at both ends with the polyfunctional acrylic monomer can also be carried out by a urethane reaction.

At this time, it is preferable that the carbinol-based silicone oligomer having an isocyanate group at both ends and the polyfunctional acrylic monomer are used in a molar ratio of 1: 2 to 2: 3. If the content of the polyfunctional acrylic monomer is excessively larger than that of the carbinol-based silicone modified oligomer having isocyanate groups at both terminals, there is a fear that viscosity increase due to progress of plasticization of the adhesive is inhibited. On the other hand, the content of the polyfunctional acrylic monomer , There is a fear that the curing reaction may not proceed during the UV irradiation due to the decrease of the acrylic monomer for UV curing.

The polymerization may be carried out at a temperature ranging from room temperature to 70 ° C under catalytic conditions.

The polyfunctional acrylic oligomer prepared by the polymerization reaction as described above comprises a structural unit derived from a carbinol-based oligomer, an isocyanate-based monomer-derived structural unit and a polyfunctional acrylic monomer-derived structural unit, wherein the structural units are linear Respectively. Specifically, the structural unit derived from the polyfunctional acrylic monomer may be a repeating unit represented by the following formula (2).

The polyfunctional acrylic oligomer preferably has a weight average molecular weight of 1000 to 50,000 g / mol. When the weight average molecular weight of the polyfunctional acrylic oligomer is less than 100 g / mol, the coating is not uniform on the substrate due to low viscosity due to low viscosity. When the weight average molecular weight is more than 50,000 g / mol, coating on the substrate becomes difficult due to high viscosity Which is undesirable.

The following Reaction Scheme 1 shows the preparation reaction of the polyfunctional acrylic oligomer according to the present invention. The following Reaction Scheme 1 is only one example for illustrating the present invention, but the present invention is not limited thereto

[Reaction Scheme 1]

When the carbinol-based silicone oligomer (i) is subjected to a polymerization reaction with isophorone diisocyanate (ii) as an isocyanate-based compound, the carbinol group and the isocyanate group of the carbinol-based silicone oligomer are bonded to each other through a urethane bond A carbino-based silicone-modified urethane oligomer (iii) containing an isocyanate group is formed. As a result, when a carbino-based urethane oligomer having an isocyanate group and containing isocyanate groups is reacted with hydroxyethyl methacrylate as a polyfunctional acrylic monomer, a urethane bond between the isocyanate group and the hydroxy group is reacted with the A multi-functional acrylic oligomer (1a) is prepared.

As another example, the functional group of the polyfunctional acrylic oligomer produced by the above-described production method varies depending on the kind of the polyfunctional acrylic monomer reacted with the carbino-based silicone modified urethane oligomer having an isocyanate group at both terminals .

(1) is a case where pentaerythritol triacrylate (v) is used as the polyfunctional acrylic monomer, and (2) is a case where the polyfunctional acrylic monomer And dipentaerythritol pentaacrylate (vi) is used. The following reaction formula (2) is an example for illustrating the present invention, but the present invention is not limited thereto.

[Reaction Scheme 2]

(b) an ethylenically unsaturated monomer containing a carboxyl group

The ethylenically unsaturated monomer containing the carboxyl group serves to enhance the adhesive strength in the production of the benzotriazole-based (meth) acrylate copolymer.

Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, and one kind or a mixture of two or more of them may be used .

The ethylenically unsaturated monomer containing a carboxyl group may be contained in an amount of 1 to 1.5 mol per 1 mol of the above-mentioned component a). When the content of the monomer having a carboxyl group is less than 1 mol, there is a fear of lowering of the adhesive strength, while when it exceeds 1.5 mol, there is a fear of breakage of the substrate upon UV laser irradiation due to a strong adhesive force.

(c) an ethylenically unsaturated monomer containing an epoxy group

The ethylenically unsaturated monomer containing an epoxy group plays a role of a compound capable of thermosetting with an ethylenically unsaturated monomer containing a carboxyl group. Specific examples thereof include glycidyl (meth) acrylate, methylglycidyl Unsaturated carboxylic acid glycidyl ester-based compounds containing an epoxy group in the molecule such as acrylate can be used.

The ethylenically unsaturated monomer containing the epoxy group may be contained in an amount of 1 to 1.5 moles per 1 mole of the above-mentioned component a). If the content of the ethylenically unsaturated monomer containing an epoxy group is less than 1 mol, the thermosetting reaction proceeds less and the adhesion may be lowered. If the content of the ethylenically unsaturated monomer is more than 1.5 mol, the ethylenically unsaturated monomer containing an epoxy group may be plasticized There is a concern.

(d) a benzotriazole-based compound containing an ethylenic unsaturated group

The benzotriazole-based compound may be a benzotriazole-based compound having an ethylenic unsaturated group capable of undergoing polymerization reaction with the above-mentioned component (a) without particular limitation, and in consideration of the light absorptivity of the finally- A benzotriazole-based compound containing an ethylenic unsaturated group capable of absorbing light having a wavelength of from 360 nm to 360 nm may be preferable.

More specifically, the present invention relates to a process for producing 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl (meth) 2-yl) -4-hydroxyphenyl] ethyl (meth) acrylate, 2- [3- (2H-benzotriazol- 2-yl) -4-hydroxyphenyl] propyl (meth) acrylate), 2- [3- (2H-benzotriazol- Benzotriazol-2-yl) -4-hydroxy-5-tert-buthylphenyl] ethyl (meth) acrylate, 2- [3- (5-chloro- 2-yl) -4-hydroxy-5-tert-butylphenyl] ethyl meth (meth) acrylate ) acrylate. Of these, a single type or a mixture of two or more types may be used.

The benzotriazole-based compound may be contained in an amount of 0.1 to 0.5% by weight based on the total weight of the components for producing the copolymer. When the content of the benzotriazole-based compound is less than 0.1% by weight, the effect of UV absorption is insignificant. When the content of the benzotriazole-based compound exceeds 0.5% by weight, the adhesion of the copolymer may be deteriorated.

(E) (meth) acrylate-based monomers may also be used together with the above-mentioned components in the production of the benzotriazole-based (meth) acrylate copolymer according to the present invention.

Specific examples of the (e) (meth) acrylate monomer include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, Acrylate, dicyclopentanyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl acrylate, n-butyl acrylate, n-butyl acrylate, Acrylate, methoxyethylene glycol acrylate, methoxyethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol acrylate, isobornyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, Glycol acrylate, stearyl acrylate, 2-hydroxyethyl acrylate Monoacrylate selected from the root, 2-hydroxypropyl acrylate and the amino group consisting of ethyl acrylate; And acrylate partially or wholly substituted with methacrylate in the monoacrylate molecule may be used.

The (meth) acrylate monomer may be used in an appropriate amount to further improve the heat resistance, light stability and thermal stability of the copolymer.

The benzotriazole-based (meth) acrylate copolymer according to the present invention can be prepared by mixing the above components (a) to (d) and optionally (e) and irradiating ultraviolet light to photo-cure.

The photocuring may be carried out without a solvent, or may be carried out in a solvent in which the components are dissolved. When the reaction is carried out in a solvent, a polar solvent may be used as the solvent, and tetrahydrofuran, dioxane, dimethylformamide or the like may be used from the viewpoint of control of the reaction and ease of handling.

In addition, photoinitiators may be further included in the mixture of the above-mentioned components as a usual additive in the photocuring.

Examples of the photoinitiator include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, hydroxyacetonephenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, Acetophenone-based compounds such as 2,2'-dichloro-4-phenoxyacetophenone; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, (4-dimethylamino) benzophenone, 4-dichlorobenzophenone, 3,3'- Benzophenone-based compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; A thioxanthone system such as thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone or 2-chlorothioxanthone, compound; Benzoin compounds such as benzoin, benzoin ether, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether; Triazine, 2- (4 '-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (Methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) (Trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl s-triazine, 2- (naphtho-1-yl) -4,6- Triazine compounds such as bis (trichloromethyl) -s-triazine or 2- (4-methoxynaphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine; Carbazole-based compounds; Diketone-based compounds; Diazo compounds; Or a nonimidazole-based compound. These may be used singly or in a mixture of two or more.

The photoinitiator may be included in an amount of 0.1 to 10% by weight based on the total weight of the mixture.

In addition, it is preferable that the photocuring is carried out at room temperature.

The benzotriazole-based (meth) acrylate copolymer prepared by photo-curing the above-mentioned components is semi-cured and contains repeating units derived from the constituents of (a) to (d).

The benzotriazole-based (meth) acrylate copolymer as described above is improved in heat stability and light stability by bonding a benzotriazole-based compound used as a stabilizer and a UV absorber through ultraviolet curing. Thus, Is particularly useful as an adhesive material for debonding using an ultraviolet absorbing semi-hardening adhesive for temporary three-dimensional packaging of semiconductors.

Accordingly, according to another embodiment of the present invention, there is provided an adhesive composition comprising the above copolymer.

The adhesive composition specifically includes a copolymer and a solvent as described above, and the copolymer may be included in an amount of 20 to 90% by weight based on the total weight of the adhesive composition.

The solvent is not particularly limited as long as it is usually used in an adhesive composition. Specific examples thereof include diacetone alcohol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, iso Butyl alcohol, isopropyl alcohol, n-butyl alcohol, n-propyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, ethyl acetate, butyl acetate, xylene or toluene.

The solvent may be contained in an appropriate amount in consideration of the processability of the adhesive composition. Specifically, the solvent is included in an amount such that the adhesive composition has a viscosity of 5 to 30 cps. Considering the application, handleability, and drying time of the adhesive composition desirable.

The adhesive composition may further include usual additives for enhancing the effect of the adhesive composition, such as leveling agents, curing accelerators, and the like.

According to another embodiment of the present invention, there is provided a semiconductor device packaged using the above adhesive composition.

Specifically, the semiconductor device comprises a wiring board, an adhesive layer which is located on the chip mounting surface of the wiring board and which contains a cured product of the adhesive composition comprising the benzotriazole-based (meth) acrylate copolymer, And a semiconductor chip.

Since the semiconductor device can be manufactured according to a conventional semiconductor device manufacturing method except that an adhesive composition comprising a benzotriazole-based (meth) acrylate copolymer according to the present invention is used for forming an adhesive layer, A detailed description of the manufacturing method will be omitted.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Example  One

Synthesis of a carbinol-based modified silicone oligomer (Shin-Etsu Silicone, X-22-160AS, Mw: 940) (3) having the following structure and isofrone diisocyanate (Bayer MaterialScience, Desmodur I, Mw: 228) To synthesize a carbinol-based silicone-modified urethane oligomer having isocyanate groups at both ends, and then a urethane reaction was induced at a molar ratio of 1: 2 with hydroxyethyl methacrylate (Mw: 130) as a polyfunctional acrylic monomer to obtain a polyfunctional acrylic oligomer .

1 mol of acrylic acid (Mw: 72) and glycidyl methacrylate (Mw: 142) were added to 1 mole of the above-prepared polyfunctional acrylic oligomer, and 2- [3- (2H- 2-yl) -4-hydroxyphenyl] ethyl methacrylate (Mw: 323) (4) was added in an amount of 0.1% by weight based on the total weight of the adhesive composition. The resultant mixture was irradiated with ultraviolet rays to induce copolymerization by curing to produce benzotriazole-based (meth) acrylate. The irradiation conditions were preferably a light dose of 1000 dose and a normal temperature condition.

(3)

(3)

(4)

(4)

FIG. 1 is a result of confirming the presence or absence of chemical bonding in an adhesive material through spectroscopic analysis by FTIR. Referring to FIG. 1, 1725 1000 or more when irradiated dose amount of light at ambient temperature conditions ^- 1750 cm - the photo-reaction via reduction of the acrylate peak ¹ was confirmed proceeds.

Comparative Example

Except that only methyl 2- [3- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl methacrylate (Mw: 323) was not added. .

Test Example  1: Evaluation of thermal stability

Thermogravimetric analysis was performed to evaluate the thermal stability and heat resistance of the benzotriazole-based (meth) acrylate copolymer according to the present invention.

Specifically, the benzotriazole-based (meth) acrylate copolymer prepared in Example 1 was heated at a rate of 3 ° C / min to observe the weight reduction rate up to 500 ° C. The results are shown in Fig.

As shown in FIG. 2, it was confirmed that the initial thermal decomposition temperature was increased and the thermal stability was improved according to the amount of ultraviolet light.

Test Example  2. Ultraviolet Contraction ratio  evaluation

The photoconduction ratio of the benzotriazole-based (meth) acrylate copolymer according to the present invention was measured for evaluating the light stability by ultraviolet rays.

Specifically, the benzotriazole-based (meth) acrylate copolymer prepared in Example 1 was irradiated with ultraviolet rays for 300 seconds at an output of 10 mW, and the light shrinkage ratio was observed. The results are shown in Fig.

As shown in FIG. 3, the benzotriazole-based (meth) acrylate copolymer of Example 1 started to shrink about 50 to 60 seconds later than the comparative example. In addition, the final shrinkage ratio after the ultraviolet irradiation showed that the benzotriazole-based (meth) acrylate copolymer of Example 1 had a shrinkage ratio of 4 to 5%, while the comparative example showed a shrinkage ratio of 6 to 7%. Considering that the difference in shrinkage ratio of 1% due to the nature of the adhesive material for semiconductor processing usually results in cracking of a thin semiconductor wafer with a thickness of several tens of micrometers in the final packaging step and may cause a great problem leading to a decrease in final yield, (Meth) acrylate copolymers according to the present invention exhibit significantly improved light stability properties. In addition, even when using a benzotriazole-based methacrylate having a trace amount of 0.1 to 0.5%, a reduction in the shrinkage ratio of 1% or more is a remarkably improved effect in terms of the light shrinkage effect.

Test Example  3: Evaluation of hardenability

In order to evaluate the degree of curing of the copolymer according to the present invention, the ultraviolet irradiation condition and the curing rate depending on the presence or absence of the benzotriazole-based methacrylate were measured.

Specifically, the gel content before and after the curing was measured and the degree of curing was evaluated at a relative ratio thereof. The results are shown in Fig.

As shown in FIG. 4, the curing rate of Comparative Example 1 in which the benzotriazole-based methacrylate was not included in the copolymer increased in each of the ultraviolet irradiation conditions as compared with Example 1. This means that it is possible to make a semi-hardening state of about 50% in addition to the hardening delay phenomenon due to the radical generation inhibition mechanism due to ultraviolet absorption during curing. Further, it has been confirmed that the present invention can be applied to a semiconductor process by increasing the hardening rate by debonding using a laser of UV wavelength band.

FIG. 5 is a result of confirming the presence or absence of chemical bonding in the adhesive material before and after debonding through spectroscopic analysis by FTIR. Referring to Figure 5, the acid carboxyl group with the glycidyl meth through 150 ℃ or more thermosetting reaction of the methacrylate debonding before and after 800, 1250 cm ^{- 1} peak of the reduction reaction of the epoxy and 1150 cm ^-1 of the alcohol peak of the car 2 Increase.

While the present invention has been particularly shown and described with reference to specific embodiments thereof, those skilled in the art will appreciate that such specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. It is therefore intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (15)

A benzotriazole-based (meth) acrylate copolymer produced by polymerization of the following components (a) to (d):
(a) a multifunctional acrylic oligomer prepared by polymerization of a carbinol-based silicone-modified urethane oligomer having an isocyanate group at both terminals and a multifunctional acrylic monomer produced by the polymerization reaction of a carbinol-based silicone oligomer of the following formula (3) with an isocyanate- ;
(3)

(b) an ethylenically unsaturated monomer containing a carboxyl group;
(c) an ethylenically unsaturated monomer containing an epoxy group; And
(d) a benzotriazole-based compound containing an ethylenically unsaturated group. delete The method according to claim 1,
Wherein the carbynol-based silicone oligomer of Formula 3 and isocyanate-based monomer are used in a molar ratio of 1: 2. The method according to claim 1,
Wherein the polyfunctional acrylic monomer is at least one selected from the group consisting of hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol pentaacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tripropylene glycol diacrylate, trimethylolpropane trioxyethyl (meth) acrylate (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, propoxylated neopentylglycidyl (meth) acrylate, tricyclodecanedimethanol di (Meth) acrylate, dicyclopentadienyl di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylpropyl tri (meth) (Meth) acrylate and mixtures thereof. &Lt; Desc / Clms Page number 24 &gt; The method according to claim 1,
Based silicone-modified urethane oligomer having an isocyanate group at both terminals and a polyfunctional acrylic monomer at a molar ratio of 1: 2 to 1: 1.5 are prepared by polymerization of a carbinol-based silicone oligomer of Formula 3 and isocyanate-based monomer (Meth) acrylate copolymer. delete The method according to claim 1,
(Meth) acrylate copolymer (b) wherein the ethylenically unsaturated monomer containing a carboxyl group is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, . The method according to claim 1,
Wherein the ethylenically unsaturated monomer (b) containing a carboxyl group is used in an amount of 1 to 1.5 moles per 1 mole of the polyfunctional acrylic oligomer (a). The method according to claim 1,
(C) a benzotriazole-based (meth) acrylate copolymer wherein the ethylenically unsaturated monomer containing an epoxy group is an unsaturated carboxylic acid glycidyl ester-based compound. The method according to claim 1,
Wherein the ethylenically unsaturated monomer (c) containing an epoxy group is used in an amount of 1 to 1.5 moles per 1 mole of the polyfunctional acrylic oligomer (a). The method according to claim 1,
(D) a benzotriazole-based (meth) acrylate copolymer wherein the benzotriazole-based compound containing an ethylenically unsaturated group absorbs light having a wavelength of 300 to 360 nm. The method according to claim 1,
The benzotriazole-based compound (d) containing an ethylenically unsaturated group is preferably selected from the group consisting of 2- [3- (2H-benzotriazol-2-yl) -4- hydroxyphenyl] ethyl (meth) (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propyl (meth) acrylate, 2- [3- (Meth) acrylate, 2- [3- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] ethyl (Meth) acrylate copolymer. &Lt; Desc / Clms Page number 24 &gt; The method according to claim 1,
The benzotriazole compound (d) containing an ethylenically unsaturated group is used in an amount of 0.1 to 0.5% by weight based on the total weight of the components (a) to (d) for producing a benzotriazole-based (meth) acrylate copolymer (Meth) acrylate copolymer based on benzotriazole. The method according to claim 1,
Wherein the polymerization is carried out by photo-curing by irradiation with ultraviolet rays. An adhesive composition comprising a benzotriazole-based (meth) acrylate copolymer according to any one of claims 1, 3, 4, 5, and 7 to 14.

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