JP2008280358A - Resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition that has high sensitivity to light and exhibits excellent patterning properties, particularly a resin composition that can be suitably employable for formation of a spacer attachedly provided on the functional face side of a semiconductor element to establish the gap to be formed on the functional face side of the semiconductor element, or formation of a protecting film or an insulation film for semiconductor elements and the like. <P>SOLUTION: The resin composition comprises a norbornene polymer having an epoxy group and a photosensitizer represented by general formula (I). The norbornene polymer is preferably an addition polymer. The content of the photosensitizer is 0.1-10 pts.wt. based on 100 pts.wt. of the norbornene polymer. Preferably, the resin composition further contains an acid-trapping agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition.

  Conventionally, a photosensitive resin composition has been used to form a protective film, an insulating film of a semiconductor element, a spacer installed on the functional surface side of the semiconductor element, and the like (Patent Document 1).

  However, since protective films and insulating films of semiconductor elements in recent years tend to be thicker, conventional resin compositions have poor sensitivity to light in order to pattern such a relatively thick film with high accuracy. It was enough. In particular, when a thick member such as a spacer is formed, the above-described problem is remarkable.

JP 2004-31939 A

  An object of the present invention is to provide a resin composition having high sensitivity to light and excellent patterning properties. Particularly suitable for forming spacers, which are provided on the functional surface side of the semiconductor element, and for defining a gap formed on the functional surface side of the semiconductor element, and for forming a protective film, an insulating film, etc. of the semiconductor element It is providing the resin composition which can be used for.

Such an object is achieved by the present inventions (1) to (9) below.
(1) A resin composition comprising a norbornene-based polymer having an epoxy group and a photosensitizer represented by the following general formula (I).

  (2) The resin composition according to (1), wherein the norbornene-based polymer is an addition polymer.

［式中、ａ、ｂ、ｃは１以上の整数である。また、Ｒ^１、Ｒ^２は、Ｈ、Ｃ_１〜Ｃ_２５直鎖、分枝鎖、および環状アルキル、アリール、アラルキル、アルケニルおよびアルキニルから選択される側基であり、ここで、いずれの側基も、Ｏ、ＮおよびＳｉから選ばれる１以上のヘテロ原子を含んでよい。］ (3) The resin composition according to (1) or (2), wherein the addition polymer is a compound represented by the following general formula (II).

[Wherein, a, b and c are integers of 1 or more. R ¹ and R ² are side groups selected from H, C ₁ -C ₂₅ linear, branched, and cyclic alkyl, aryl, aralkyl, alkenyl, and alkynyl, where any side group May also contain one or more heteroatoms selected from O, N and Si. ]

  (4) The resin composition according to any one of (1) to (3), wherein the content of the photosensitive agent is 0.1 to 10 parts by weight with respect to 100 parts by weight of the norbornene polymer.

  (5) The resin composition according to any one of (1) to (4), further including an acid scavenger.

［式中、Ｒ^７は、Ｈ、または、アルキル基である。］

［式中、Ｒ^１０〜Ｒ^１４は、Ｈ、または、任意の２つがメチル基で残りがＨである。］ (6) The acid scavenger is at least one selected from the group consisting of a compound represented by the following general formula (III) and a compound represented by the following general formula (V). Resin composition.

[Wherein, R ⁷ represents H or an alkyl group. ]

[In formula, R < ¹⁰ > -R < ¹⁴ > is H or arbitrary two are methyl groups, and the remainder is H. ]

  (7) The resin composition according to (5) or (6), wherein the content of the acid scavenger is 0.01 to 2 parts by weight with respect to 100 parts by weight of the photosensitive agent.

  (8) Any one of the above (1) to (7) used for forming a spacer that is provided on the functional surface side of the semiconductor element and is used to define a gap formed on the functional surface side of the semiconductor element. The resin composition as described.

  (9) The resin composition according to any one of (1) to (7), which is used as one or more of a protective film and an insulating film of a semiconductor element.

  According to this invention, the sensitivity with respect to the light of a resin composition can be made high, and patterning property can be improved. In particular, when the resin composition of the present invention is applied to, for example, a spacer as described later, patterning can be performed with high accuracy. In addition, since the material obtained by curing such a resin composition has a small shrinkage rate and a uniform composition, it is formed on the functional surface side of the semiconductor element when used as a spacer as described later. Can be regulated with high accuracy.

Hereinafter, the resin composition of the present invention will be described in detail.
The resin composition of the present invention contains a norbornene polymer and a photosensitizer as described later. The resin composition of the present invention is a negative resin composition that cures a portion irradiated with light.

First, the norbornene polymer will be described.
The norbornene-based polymer used in the present invention has an epoxy group. In other words, the norbornene-based polymer used in the present invention has at least one repeating unit having an epoxy group (for example, a repeating unit represented by Chemical Formula 1 described later and having an epoxy group). . By having an epoxy group, the moldability and heat resistance are particularly excellent.

  The norbornene-based polymer is not particularly limited as long as it has at least one repeating unit having an epoxy group, has a single repeating unit (homopolymer), and has two or more norbornene-based repeating units. Any of those (copolymers) may be used.

  Examples of such norbornene-based polymers include (1) addition (co) polymers of norbornene monomers obtained by addition (co) polymerization of norbornene monomers, and (2) norbornene monomers and ethylene or α- Addition copolymers with olefins, (3) addition polymers such as addition copolymers with norbornene type monomers and non-conjugated dienes, and other monomers as required, (4) ring opening of norbornene type monomers (Co) polymer, and optionally hydrogenated resin of (co) polymer, (5) ring-opening copolymer of norbornene type monomer and ethylene or α-olefin, and (Co) polymer hydrogenated resin, (6) a ring-opening copolymer of a norbornene-type monomer and a non-conjugated diene, or other monomer, and, if necessary, the (co) polymer And a ring-opening polymer such as a polymer obtained by hydrogenation. Examples of these polymers include random copolymers, block copolymers, and alternating copolymers.

  These norbornene polymers include, for example, ring-opening metathesis polymerization (ROMP), combination of ROMP and hydrogenation reaction, polymerization by radical or cation, polymerization using cationic palladium polymerization initiator, other polymerization initiators It can be obtained by all known polymerization methods such as polymerization using (for example, polymerization initiators of nickel and other transition metals).

  Among these, as the norbornene-based polymer, one having at least one repeating unit represented by the following chemical formula 5 (Structural Formula B), that is, an addition (co) polymer is preferable.

  Such a norbornene-based polymer is suitably synthesized by using, for example, a norbornene-based monomer described later (a norbornene-based monomer represented by Chemical Formula 7 described below or a crosslinkable norbornene-based monomer).

  As the norbornene-based polymer, those containing a repeating unit of aralkylnorbornene are preferable. Thereby, physical characteristics such as mechanical characteristics are improved. For example, when applied to a spacer as described later, high reliability can be obtained.

  Examples of the aralkyl group (arylalkyl group) of the repeating unit of aralkylnorbornene include, for example, benzyl group, phenylethyl (phenethyl) group, phenylpropyl group, phenylbutyl group, naphthylethyl group, naphthylpropyl group, fluorenylethyl group A fluorenylpropyl group, and the like, and a phenylethyl group is particularly preferable.

  Further, the norbornene-based polymer preferably contains an alkylnorbornene repeating unit. Thereby, after hardening by light, it can thermoform easily. Furthermore, since the internal stress of the resin after molding is remarkably reduced, it becomes possible to improve the reliability of a semiconductor element using such a resin.

  Examples of the alkyl group contained in the alkylnorbornene repeating unit include a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. preferable. These alkyl groups may be either linear or branched.

  By including the repeating unit of decylnorbornene, the norbornene-based polymer has moderate heat resistance, moderate thermoformability and low stress.

  In particular, the norbornene-based polymer of the present invention is preferably an addition polymer represented by the following general formula (II).

［式中、ａ、ｂ、ｃは１以上の整数である。また、Ｒ^１、Ｒ^２は、Ｈ、Ｃ_１〜Ｃ_２５直鎖、分枝鎖、および環状アルキル、アリール、アラルキル、アルケニルおよびアルキニルから選択される側基であり、ここで、いずれの側基も、Ｏ、ＮおよびＳｉから選ばれる１以上のヘテロ原子を含んでよい。］

[Wherein, a, b and c are integers of 1 or more. R ¹ and R ² are side groups selected from H, C ₁ -C ₂₅ linear, branched, and cyclic alkyl, aryl, aralkyl, alkenyl, and alkynyl, where any side group May also contain one or more heteroatoms selected from O, N and Si. ]

  By using such a norbornene polymer, it has appropriate heat resistance and mechanical properties, and can be more easily thermoformed after being cured by light. Furthermore, the reliability of the semiconductor element can be improved.

  The norbornene-based polymer as described above can be obtained using a norbornene-based monomer.

  Here, the norbornene-based monomer is a generic term for monomers containing at least one norbornene skeleton represented by the following chemical formula 7 (structural formula A), and examples thereof include compounds represented by the following chemical formula 8 (structural formula C). .

［式中、Ｘは−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−、または−Ｏ−を表す。］

[Wherein, X represents —CH ₂ —, —CH ₂ —CH ₂ —, or —O—. ]

［式中、Ｘは−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−および−Ｏ−から選択され；そしてｍは０〜５の整数であり；Ｒ^３〜Ｒ^６は、それぞれ独立して、水素原子、置換基を表す。］

[Wherein, X is _{-CH 2 -, - CH 2 -CH} 2 - is selected from and -O-; and m is an integer of ^0~5; R 3 ~R ⁶ are each independently hydrogen Represents an atom or a substituent. ]

  In the present invention, the norbornene-based polymer can be obtained by using at least a monomer having an epoxy group as a substituent among the norbornene-based monomers as described above.

  In addition, the norbornene polymer may be obtained by combining a norbornene monomer having an epoxy group and a norbornene monomer having a substituent other than the epoxy group.

  The norbornene monomer having a substituent other than an epoxy group includes a norbornene monomer having an alkyl group, a norbornene monomer having an aryl group, a norbornene monomer having an aralkyl group, a norbornene monomer having an alkenyl group, and an alkynyl group. And norbornene-based monomers.

  Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group. , Nonyl and decyl groups, but are not limited thereto.

  Specific examples of the aryl group include, but are not limited to, a phenyl group, a naphthyl group, and an anthracenyl group.

  Specific examples of the aralkyl group include, but are not limited to, a benzyl group and a phenylethyl (phenethyl) group.

  Specific examples of the alkenyl group include, but are not limited to, a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

Specific examples of the alkynyl group include, but are not limited to, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group and 2-butynyl group.
The resin composition of the present invention contains a photosensitizer represented by the following general formula (I).

  In general, a photosensitizer generates an acid in response to energy rays such as light. The above-described norbornene-based polymer is cured by the action of the generated acid.

  The photosensitizer represented by the above general formula (I) is a compound having a very high acid generation efficiency upon irradiation with energy rays, that is, acid generation sensitivity, as compared with a conventional photosensitizer.

  The resin composition of the present invention is characterized in that it contains the norbornene-based polymer as described above and the photosensitive agent represented by the above general formula (I).

  By setting it as the above structures, the sensitivity with respect to the light of a resin composition can be made high, and patterning property can be improved. In particular, when the resin composition of the present invention is applied to, for example, a spacer as described later, patterning can be performed with high accuracy. In addition, since the material obtained by curing such a resin composition has a small shrinkage rate and a uniform composition, it is formed on the functional surface side of the semiconductor element when used as a spacer as described later. Can be regulated with high accuracy.

  In addition, by using the photosensitizer of the above general formula (I) and a norbornene polymer having an epoxy group (particularly, an addition polymer of a norbornene polymer having an epoxy group), sensitivity to light (here, sensitivity) Means the presence or absence of patterning at the time of patterning and the adhesion after patterning) is not yet clear, but it is considered as follows, for example.

  In the above photosensitizer, a naphthalene-containing sulfur compound is generated as one of decomposition products by energy ray irradiation, and this naphthalene-containing sulfur compound promotes the reaction of the epoxy group of the norbornene-based polymer having an epoxy group, This is because the sulfur part of the naphthalene-containing sulfur compound interacts with a semiconductor wafer, a transparent substrate, and the like, and the naphthalene side part interacts with a norbornene polymer, thereby acting as a coupling agent.

  In addition, the above photosensitive agent has good compatibility with the norbornene polymer, thereby being excellent in dispersibility in the norbornene polymer and improving the reactivity, workability, and the like.

  The content of the photosensitive agent represented by the general formula (I) is preferably 0.1 to 10 parts by weight, and 1 to 5 parts by weight with respect to 100 parts by weight of the norbornene polymer. More preferred. By making content of the said photosensitive agent into such a range, the sensitivity with respect to the light of a resin composition can be made higher, and patterning property can be improved more. On the other hand, if the content of the photosensitizer is less than the lower limit, sufficient sensitivity may not be obtained depending on the composition of the norbornene-based polymer. When the content of the photosensitizer exceeds the upper limit, the substance obtained by curing the resin composition may not have sufficient mechanical strength depending on the composition of the norbornene polymer.

As described above, the resin composition of the present invention has high sensitivity to light, but a sensitizer can be added as necessary depending on the application and molding conditions. A sensitizer is a component having a function of developing or increasing the reactivity of a photosensitizer to light of a specific type or wavelength. Examples of such sensitizers include anthracene, phenanthrene, chrysene, benzpyrene, fluoranthene, rubrene, pyrene, xanthone, indanthrene, thioxanthen-9-one, and 2-isopropyl-9H-thioxanthen-9-one. 4-isopropyl-9H-thioxanthen-9-one, 1-chloro-4-propoxythioxanthone, and mixtures thereof. The content of such a sensitizer is preferably 100 parts by weight or less and more preferably 20 parts by weight or less with respect to 100 parts by weight of the above-described photosensitive agent.
Moreover, the resin composition of this invention may contain the acid scavenger other than the said component, for example.

  The acid scavenger is a component having a function of preventing an acid generated by light irradiation from diffusing to a site not irradiated with light. That is, it is a component having a function of preventing unintentional curing of a portion not irradiated with light.

  By including such an acid scavenger, patterning accuracy can be made higher.

  Examples of such an acid scavenger include tri (n-propyl) amine, triethylamine, a compound represented by the following general formula (III), a compound represented by the following general formula (V), and the like. Amines (secondary amines, tertiary amines), and mixtures thereof.

［式中、Ｒ^７は、Ｈ、または、アルキル基である。］

[Wherein, R ⁷ represents H or an alkyl group. ]

［式中、Ｒ^１０〜Ｒ^１４は、Ｈ、または、任意の２つがメチル基で残りがＨである。］

[In formula, R < ¹⁰ > -R < ¹⁴ > is H or arbitrary two are methyl groups, and the remainder is H. ]

  Among these, it is preferable to use at least one compound selected from the group consisting of the compound represented by the general formula (III) and the compound represented by the general formula (V). It is more preferable to use a compound represented by Thereby, unintentional hardening of the site | part which is not irradiating light can be prevented more effectively, making the sensitivity with respect to the light of a resin composition high.

The content of such an acid scavenger is preferably 0.01 to 2 parts by weight and more preferably 0.02 to 1 part by weight with respect to 100 parts by weight of the above-described photosensitive agent. Thereby, the unintentional hardening of the site | part which is not irradiating light can be prevented further effectively.
Moreover, the resin composition of this invention may contain antioxidant.

  The antioxidant has a function of preventing generation of undesirable acid and natural oxidation of the resin composition.

  Antioxidants include Ciba (registered trademark, hereinafter the same) available from Ciba Fine Chemicals of Tarrytown, NY IRGANOX (registered trademark, the same shall apply hereinafter) 1076 and Ciba IRGAFOS (registered trademark, hereinafter referred to as “registered trademark”). The same applies.) 168 is preferably used.

  Other antioxidants include, for example, Ciba Irganox (registered trademark, hereinafter the same) 129, Ciba Irganox 1330, Ciba Irganox 1010, Ciba Cyanox (registered trademark, the same applies below) 1790, Ciba Irg. (Registered trademark) 3114, Ciba Irganox 3125, etc. can also be used.

The content of the antioxidant is preferably 0.1 to 10 parts by weight and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the norbornene polymer.
Moreover, the resin composition of the present invention may contain a crosslinking accelerator.

  A crosslinking accelerator is a component having a function of making the crosslinking reaction more effective by adding it to the composition and improving moldability and physical properties.

  Examples of the crosslinking accelerator include 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol vinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,2-ethylene glycol. Divinyl ether, 1,3-propylene glycol divinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 1,4-butanediol vinyl ether, 1,6 -Hexanediol vinyl ether, 1,8-octanediol vinyl ether, and mixtures thereof It is. Among these, it is particularly preferable to use 1,4-cyclohexanedimethanol divinyl ether.

The content of the crosslinking accelerator is preferably 0.1 to 50 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the norbornene polymer.
Moreover, the resin composition of the present invention may contain an adhesion assistant.

  The adhesion assistant is a component having a function of improving the bonding strength between a member obtained by curing the resin composition and a substrate on which the member is provided.

  Examples of the adhesion assistant include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, and compounds represented by the following structural unit (IV). These can be used alone or in combination of two or more.

［ここで、ｚは０、１または２であり、Ｒ^８はＣ_１〜Ｃ_２０の直鎖状、分枝鎖状、そして環状のアルキレン、２〜６個の炭素原子を含有するアルキレンオキシドおよびポリ（アルキレンオキシド）（ここで、前記反復基のアルキレン部分は２〜６個の炭素原子を含有し、そして前記ポリ（アルキレンオキシド）は５０〜１０００の分子量を有する）から選ばれる連結基であり、それぞれ存在するＲ^９の各々はＣ_１〜Ｃ_４の直鎖状の、および分枝鎖状のアルキルから独立して選ばれ、そして存在するＲ^１８の各々は、ＨおよびＣ_１〜Ｃ_４の直鎖状の、および分枝鎖状のアルキルから選ばれる。］

[Wherein z is 0, 1 or 2 and R ⁸ is a C ₁ -C ₂₀ linear, branched and cyclic alkylene, an alkylene oxide containing 2 to 6 carbon atoms and A linking group selected from poly (alkylene oxides) wherein the alkylene portion of the repeating group contains 2 to 6 carbon atoms and the poly (alkylene oxide) has a molecular weight of 50 to 1000 Each of R ⁹ present is independently selected from C ₁ -C ₄ linear and branched alkyl and each of R ¹⁸ present is selected from H and C ₁ -C _4. Selected from linear and branched alkyl. ]

  Among the above, it is particularly preferable to use 3-glycidoxypropyltrimethoxysilane.

The content of the adhesion assistant is preferably 0.1 to 50 parts by weight and more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the norbornene polymer.
Moreover, the resin composition of this invention may contain the solvent.

A solvent is a component which has a function which improves the applicability | paintability of a resin composition.
Examples of the solvent include hydrocarbon solvents, aromatic solvents, alicyclic cyclic ethers, cyclic ethers, acetates, esters, lactones, ketones, amides, aliphatic mono- and aliphatic multivinyl ethers, alicyclic mono- and multi Examples thereof include vinyl ethers, aromatic mono- and multivinyl ethers, cyclic carbonates, and mixed liquids containing these.

  The content of the solvent is preferably 50 to 1000 parts by weight and more preferably 100 to 300 parts by weight with respect to 100 parts by weight of the norbornene polymer.

Next, an example of a semiconductor device to which the resin composition of the present invention is suitably applied will be described.
FIG. 1 is a longitudinal sectional view showing an example of a semiconductor device to which the resin composition of the present invention is suitably applied. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

  A semiconductor device 10 shown in FIG. 1 is a CMOS image sensor, and includes a semiconductor chip (semiconductor element) 20, an interposer (substrate) 30 that supports the semiconductor chip 20, a spacer 40 bonded on the interposer 30, A transparent substrate 50 supported by the spacer 40 and a plurality of conductive bonding wires 70 are provided.

  The interposer 30 is an insulating substrate and is made of various resin materials such as polyimide, epoxy, cyanate, and BT resin. The plan view shape of the interposer 30 is usually a square such as a square or a rectangle.

  A wiring pattern (not shown) made of a conductive metal material such as copper is provided in a predetermined shape on the upper surface (one surface) of the interposer 30.

Each of the bonding wires 70 is electrically connected to a part of the wiring pattern, and the other end (lower end) protrudes from the side surface of the interposer 30.
A semiconductor chip 20 is installed on the interposer 30.

  The semiconductor chip 20 has a light receiving surface (functional surface) 21, and has a function of receiving light incident from above the semiconductor device 10 by the light receiving surface 21 and changing it into an electrical signal.

  Each bonding wire 80 is conductively connected from the bonding wire bonding portion (not shown) of the semiconductor chip 20 toward the bonding wire bonding portion (not shown) of the wiring pattern on the interposer 30.

  Further, a spacer 40 is bonded on the interposer 30 (a portion where no wiring pattern is formed).

This spacer 40 is comprised by the block body formed using the resin composition of this invention mentioned above.

  The spacer 40 constituted by this block body is formed with a hollow portion 41 that penetrates the spacer 40 in the vertical direction (thickness direction) in FIG. Further, the hollow portion 41 includes a wiring pattern (not shown) on the interposer 30, the semiconductor chip 20, and the bonding wires 80 inside thereof.

  A transparent substrate 50 is joined to the upper end of the spacer 40. Thereby, both ends of the hollow portion 41 are sealed with the interposer 30 and the transparent substrate 50. In other words, a closed space (gap) is formed by the inner wall surface of the spacer 40, the upper surface of the interposer 30, and the lower surface of the transparent substrate 50. By forming such a closed space, foreign matter is prevented from adhering to the semiconductor chip 20 (particularly, the light receiving surface 21).

  As described above, since the spacer 40 is formed using the resin composition of the present invention, the closed space (gap) on the light receiving surface 21 side of the semiconductor element 20 is regulated with high accuracy.

  In addition, such a spacer 40 becomes the spacer 40 by, for example, applying the resin composition of the present invention on the interposer 30 with a predetermined thickness, and then irradiating light on a portion to be the spacer 40. After the part to be cured is cured, it can be formed by removing the uncured resin composition. Since the resin composition of the present invention has high sensitivity to light and excellent patterning properties, the spacer 40 having a desired shape can be easily formed.

  In addition, as a method of joining the upper end of the spacer 40 formed using the resin composition of the present invention and the transparent substrate 50, for example, an adhesive is applied to the upper end of the spacer 40 after patterning to join the transparent substrate 50. And a method of adding a component (for example, an epoxy compound, an oxetanyl compound, etc.) that can be thermocompression-bonded after photocuring to the resin composition and thermocompression-bonding the transparent substrate 50 after photocuring.

  The resin composition of the present invention has been described above, but the present invention is not limited to these.

  For example, the semiconductor device to which the resin composition of the present invention is applied is not limited to the one having the above configuration.

  In addition, the resin composition of the present invention can be used not only for forming the spacer as described above, but also for forming a protective film, an insulating film, etc. of a semiconductor element, for example.

[1] Production of Resin Composition A resin composition was produced as follows.

Example 1
<Preparation of norbornene-based polymer>
A norbornene polymer (an addition polymer represented by the following general formula (II)) containing phenethyl, glycidyl methyl ether and decyl repeating units obtained from phenethyl norbornene, glycidyl methyl ether norbornene and decyl norbornene was prepared as follows. did.

  To a reaction vessel which was dried at 110 ° C. for 18 hours and then transferred into a nitrogen purged glove box, ethyl acetate (230 g), cyclohexane (230 g), phenethyl norbornene (14.17 g, 0.071 mol), glycidyl methyl ether norbornene ( 14.0 g, 0.100 mol) and decylnorbornene (39.50 g, 0.168 mol) were added. Oxygen was removed from the reaction medium by passing a dry N2 stream through the solution for 30 minutes. After purging was complete, 1.50 g (3.10 mmol) of bis (toluene) bis (perfluorophenyl) nickel dissolved in 8 ml of toluene was injected into the reactor. The reaction mixture was stirred at ambient temperature for 18 hours and then peracetic acid solution (50 mol equivalent based on nickel catalyst, 150 mmol, 57 ml glacial acetic acid diluted with 130 ml deionized water was diluted with approximately 100 ml deionized water. Prepared with 115 ml of 30 wt% hydrogen peroxide) and stirred for an additional 18 hours.

Stirring was stopped and the mixture was allowed to stand to separate the aqueous layer and the solvent layer. The aqueous layer was then removed, and an aliquot of water was added to the remaining solvent layer, which was washed with 500 ml of distilled water three times, stirred for 20 minutes, allowed to separate into layers, and then the aqueous layer was removed. Thereafter, excess acetone was added to the washed solvent layer to precipitate a norbornene polymer, collected by filtration, and dried overnight at 60 ° C. in a vacuum oven. After drying, 66.1 g of a dried norbornene polymer (conversion rate 92%) was obtained. The molecular weight of the norbornene polymer was measured by GPC using a polystyrene standard, and it was confirmed that Mw = 105,138, Mn = 46,439, and polydispersity (PDI) was 2.26. The composition of the norbornene-based polymer is measured using ¹ H-NMR, and 20.2 mol% phenethyl norbornene, 29.1 mol% glycidyl methyl ether norbornene and 50.7 mol% decyl norbornene are incorporated. confirmed.

<Preparation of photosensitizer>
A photosensitizer represented by the following formula (I) was prepared as follows.

  19.0 g of dimethyl (2- (4-methoxynaphthyl) -2-oxoethyl) sulfonium bromide was dissolved in 4000 ml of ion-exchanged water, and an aqueous solution of sodium tetrakis (pentafluorophenyl) borate (weight concentration 3.99%) 930. 7 g was dripped at room temperature over 40 minutes, and it stirred at room temperature after completion | finish of dripping for 2 hours. The precipitate was filtered, and the resulting solid was dissolved in 250 ml of dichloromethane and extracted and washed with water. The organic layer was dried over magnesium sulfate, and after removing the desiccant, it was cooled to 0 ° C. and 1000 ml of hexane was added dropwise. The formed crystals were filtered, washed with hexane, and dried to give dimethyl (2- (4-methoxynaphthyl) -2-oxoethyl) sulfonium tetrakis (pentafluorophenyl) borate (compound of formula (I) above) white 28.9 g of crystals were obtained (58% yield).

<Preparation of resin composition>
The obtained norbornene-based polymer: 191.25 g and 2-heptanone (MAK): 191 g were added to the brown jar. The solution was mixed until the solids were completely dissolved and then filtered through a 0.45 micron filter to remove particulates. In the solution, the obtained photosensitizer: 5.738 g, 0.0612 g of a compound represented by the following formula (VI) as an acid scavenger, and Irganox 1076 (made by Ciba) as an antioxidant: 2.869 g And 1,4-cyclohexanedimethanol divinyl ether (manufactured by Nippon Carbide Industries) as a crosslinking accelerator: 9.563 g, 3-glycidoxypropyltrimethoxysilane (manufactured by Sigma-Aldrich) as an adhesion assistant: 9.563 g was added. The solution was mixed for 18 hours to obtain a resin composition.

(Example 2)
A resin composition was prepared in the same manner as in Example 1 except that the norbornene-based polymer was prepared as follows.

<Preparation of norbornene-based polymer>
Use ethyl acetate (200 g), cyclohexane (200 g), phenethyl norbornene (5.06 g, 0.025 mol), glycidyl methyl ether norbornene (14.0 g, 0.077 mol) and decyl norbornene (33.6 g, 0.152 mol) The procedure of Example 1 was repeated except that After the purge was complete, 1.45 g (3.00 mmol) of bis (toluene) bis (perfluorophenyl) nickel was dissolved in 8 ml of toluene and injected into the reactor. As in Example 1 above, the reaction was stirred at ambient temperature for 6 hours, then reacted with a suitable peracetic acid solution and washed. As in Example 1 above, the norbornene polymer was precipitated and recovered. After drying, 49.2 g of a dried norbornene polymer (conversion rate 90%) was obtained. The molecular weight of the norbornene polymer was measured by GPC using a polystyrene standard, and it was confirmed that Mw = 84,631, Mn = 33,762, and polydispersity index (PDI) = 2.51. The composition of the norbornene-based polymer was measured using ¹ H-NMR, and 10.2 mol% phenethyl norbornene, 31.5 mol% glycidyl methyl ether norbornene and 58.3 mol% decyl norbornene were bonded. confirmed.

(Example 3)
A resin composition was prepared in the same manner as in Example 1 except that the norbornene-based polymer was prepared as follows.

<Preparation of norbornene-based polymer>
Use ethyl acetate (200 g), cyclohexane (200 g), phenethyl norbornene (2.36 g, 0.012 mol), glycidyl methyl ether norbornene (12.63 g, 0.070 mol) and decyl norbornene (35.6 g, 0.152 mol) The procedure of Example 1 was repeated except that After purging was completed, 1.33 g (2.74 mmol) of bis (toluene) bis (perfluorophenyl) nickel was dissolved in 7 ml of toluene and injected into the reactor. As in Example 1 above, the reaction was stirred at ambient temperature for 6 hours, then reacted with a suitable peracetic acid solution and washed. In the same manner as in Example 1, the norbornene polymer was precipitated and recovered. After drying, 44.8 g of a dried norbornene polymer (conversion rate 89%) was obtained. The molecular weight of the norbornene polymer was measured by GPC using a polystyrene standard, and it was confirmed that Mw = 92,452, Mn = 37,392, and polydispersity index (PDI) = 2.47. The composition of the norbornene polymer was measured using ¹ H-NMR, and 6.5 mol% phenethyl norbornene, 30.1 mol% glycidyl methyl ether norbornene, and 63.4 mol% decyl norbornene were bonded. all right.

Example 4
A resin composition was prepared in the same manner as in Example 1 except that the norbornene-based polymer was prepared as follows.

<Preparation of norbornene-based polymer>
The procedure of Example 1 was followed except that ethyl acetate (290 g), cyclohexane (290 g), phenethyl norbornene (71.85 g, 0.364 mol) and glycidyl methyl ether norbornene (28.15 g, 0.156 mol) were used. Repeated. After the purge was complete, 3.15 g (6.51 mmol) of bis (toluene) bis (perfluorophenyl) nickel was dissolved in 18.0 ml of toluene and injected into the reactor. The reaction was stirred at ambient temperature for 18 hours, then 100 ml glacial acetic acid diluted with peracetic acid solution (50 mol equivalent based on nickel catalyst, 150 mmol, about 200 ml deionized water was diluted with about 200 ml deionized water. Prepared with 200 ml of 30 wt% hydrogen peroxide) and stirred for an additional 18 hours.

Stirring was stopped and the mixture was allowed to stand to separate the aqueous layer and the solvent layer. The aqueous layer was then removed and washed three times with 500 ml water by adding an aliquot of water to the remaining solvent layer, stirred for 20 minutes, allowed to separate into layers, and then the aqueous layer was removed. Excess methanol was added to the washed solvent layer to precipitate a norbornene polymer, collected by filtration, and dried in a vacuum oven at 60 ° C. overnight. After drying, 93.0 g of a dried norbornene polymer (conversion rate: 93%) was obtained. The molecular weight of the norbornene polymer was measured by GPC using a polystyrene standard, and it was confirmed that Mw = 61,937, Mn = 29,053, and the polydispersity index (PDI) was 2.13. The composition of the norbornene polymer was measured using ¹ H-NMR, and it was found that 67.1 mol% phenethyl norbornene and 32.9 mol% glycidyl methyl ether norbornene were incorporated.

(Example 5)
A resin composition was prepared in the same manner as in Example 1 except that the acid scavenger was not added.

(Comparative example)
The same as in Example 1 except that Rhodorsil (registered trademark) PI2074 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate: 0.184 g was used as a photosensitizer. A resin composition was prepared.

[2] Evaluation <2.1> Photo-resolution (patterning) property The photo-resolution property is obtained by forming a pattern through the following steps using the resin compositions of the respective examples and comparative examples. The residue of the shape and the opening was observed and evaluated based on the following four criteria.

  As a pattern forming step, the resin composition was applied to an 8-inch wafer by spin coating, and then dried on a hot plate at 110 ° C. for 5 minutes to obtain a coating film having a thickness of about 40 μm.

This coating film was exposed to a portion (cured portion) where a dam was formed at 500 mJ / cm ² through a reticle by an i-line stepper exposure machine (manufactured by Nikon Corporation). Then, it heated for 90 minutes at 90 degreeC with a hot plate in order to accelerate | stimulate the crosslinking reaction of an exposure part.

  Next, the unexposed portion was dissolved and removed by immersing in cyclopentanone for 30 seconds, and then rinsed with propylene glycol monomethyl ether acetate for 20 seconds to form a desired pattern.

A: There was no scum and the appearance was good.
○: Some scum was generated or some appearance was poor.
Δ: Separation occurred in the dam.
X: Development was not possible.

<2.2> Measurement of Minimum Exposure Amount (Sensitivity) Required for Pattern Formation Using the resin compositions of the above Examples and Comparative Examples, the measurement of the minimum exposure amount (sensitivity) required for pattern formation is as follows. I went there.

A coating film was formed in the same manner as in <2.1> above. This coating film is divided into a plurality of regions, and exposed by an i-line stepper exposure machine (manufactured by Nikon Co., Ltd.) through the reticle in steps of 100 mJ / cm ² to 10 mJ / cm ² so that the exposure amount varies from region to region. Went. Then, it heated for 90 minutes at 90 degreeC with a hot plate in order to accelerate | stimulate the crosslinking reaction of an exposure part.

  Next, the unexposed portion was dissolved and removed by immersing in cyclopentanone for 30 seconds, and then rinsed with propylene glycol monomethyl ether acetate for 20 seconds to form a pattern.

Each area exposed at 100 mJ / cm ² to 10 mJ / cm ² increments was observed in order from the area exposed to 100 mJ / cm ^2, and the exposure amount at the site where patterning started to a desired shape was defined as the minimum exposure amount.
These results are shown in Table 1.

  As can be seen from Table 1, the resin composition of each example had high sensitivity to light and excellent patterning properties. In particular, in the Examples using the norbornene-based polymer represented by the general formula (II) described above and using the compound represented by the general formula (VI) described above as the acid scavenger, particularly excellent results were obtained. It was. On the other hand, satisfactory results were not obtained with the resin composition of the comparative example.

It is a longitudinal cross-sectional view which shows an example of the semiconductor device to which the resin composition of this invention is applied suitably.

Explanation of symbols

10 Semiconductor Device 20 Semiconductor Chip (Semiconductor Element)
21 Light-receiving surface (functional surface)
30 Interposer (substrate)
40 Spacer 41 Hollow part 50 Transparent substrate 70, 80 Bonding wire

Claims (9)

A resin composition comprising a norbornene-based polymer having an epoxy group and a photosensitizer represented by the following general formula (I).

  The resin composition according to claim 1, wherein the norbornene-based polymer is an addition polymer. The resin composition according to claim 1, wherein the addition polymer is a compound represented by the following general formula (II).

[Wherein, a, b and c are integers of 1 or more. R ¹ and R ² are side groups selected from H, C ₁ -C ₂₅ linear, branched, and cyclic alkyl, aryl, aralkyl, alkenyl, and alkynyl, where any side group May also contain one or more heteroatoms selected from O, N and Si. ]   4. The resin composition according to claim 1, wherein the content of the photosensitive agent is 0.1 to 10 parts by weight with respect to 100 parts by weight of the norbornene polymer.   The resin composition according to any one of claims 1 to 4, further comprising an acid scavenger. 6. The resin composition according to claim 5, wherein the acid scavenger is at least one selected from the group consisting of a compound represented by the following general formula (III) and a compound represented by the following general formula (V). .

[Wherein, R ⁷ represents H or an alkyl group. ]

[In formula, R < ¹⁰ > -R < ¹⁴ > is H or arbitrary two are methyl groups, and the remainder is H. ]   The resin composition according to claim 5 or 6, wherein the content of the acid scavenger is 0.01 to 2 parts by weight with respect to 100 parts by weight of the photosensitive agent.   The resin composition according to any one of claims 1 to 7, wherein the resin composition is used for forming a spacer that is bonded to a functional surface side of a semiconductor element and defines a gap formed on the functional surface side of the semiconductor element.   The resin composition according to claim 1, which is used as one or more of a protective film and an insulating film of a semiconductor element.

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