JP2007226209A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having a siloxane structure that is useful for manufacturing electric/electronic materials such as semiconductor devices and multilayer wiring boards, in particular, suitable as a buffer coating material of LSI chips and that is excellent in thick film property, low shrinkage and low stress and improved in adhesion strength with underlay metal wiring and in elongation, and to provide a film obtained by hardening the photosensitive resin. <P>SOLUTION: The photosensitive resin composition is prepared in a process including steps of condensation-polymerizing a compound containing a specified organic silane in the presence of tertiary butoxy titanium at a temperature of 40°C to 150°C for 0.1 to 10 hours to obtain a liquid resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards, and a resin film obtained from the photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition suitable for an insulating material for forming a buffer coat material and a rewiring layer of an LSI chip, and a resin insulating film obtained from the photosensitive resin composition. Is.

The performance requirements for the insulating material for forming the buffer coat material and the redistribution layer of the LSI chip are becoming stricter with the miniaturization of the LSI. Specifically, high resolution, low temperature cure, low stress, etc. are required. In particular, the stress resistance and heat resistance of the low K material used before the buffer coat material are becoming weaker, and the copper of the rewiring is also becoming thicker due to an increase in current density. For this reason, it is necessary to use a material that satisfies thick film, flatness, low stress, and low-temperature curing in addition to conventional high resolution, chemical resistance, temperature stress resistance, and the like as the upper layer buffer coating material. .
Conventionally, as a buffer coating material, for example, as shown in Patent Documents 1 to 5, photosensitive polyimide has been used as one of representative examples. However, the photosensitive polyimide has many problems, and in particular, has a great disadvantage that it is inferior in flatness after curing, and a buffer coating material that alone satisfies all the above requirements is not known.

A method of using photosensitive polyimide as a buffer coating material will be briefly described. First, a polyamide having a double bond in a side chain is used as a photosensitive polyimide precursor, and this is spin-coated on an LSI wafer. Next, only the double bonds of the side chain are photocrosslinked by exposure, and further development is performed to form a desired pattern. Thereafter, heat treatment is performed to change the polyamide in the pattern into a polyimide structure by a dehydration reaction, thereby obtaining a buffer coating material having excellent heat resistance. Incidentally, the crosslinked chain is also decomposed and volatilized by the heat treatment.
The photosensitive polyimide can form strong adhesion with the base in the course of the dehydration reaction. Since the photosensitive polyimide has a strong molecular structure, it has excellent chemical resistance against an organic alkaline solution, for example, a mixed solvent of dimethyl sulfoxide (DMSO) and tetramethylammonium hydride (TMAH).
However, when photosensitive polyimide is used as the buffer coating material, there is a problem that the film changes in the direction of densification due to the dehydration reaction in the heat treatment and the decomposition and volatilization of the crosslinked chain, and the thickness shrinks by nearly 40%. .

Patent Document 6 discloses a coating material manufactured by Fraunhofer ISC, Germany, which comprises an organic silane having a polymerizable group and an organic silane having a hydrolysis reaction point using Ba (OH) ₂ (barium hydroxide) as a catalyst, There is a disclosure of ORMOCER® ONE. ORMOCER (registered trademark) ONE can be cured at a low temperature of 150 ° C., and its cured product has excellent characteristics such as heat resistance of 300 ° C. or higher, residual low stress of 10 Mpa or lower, and flatness within 3%. Have. However, as shown in a comparative example to be described later, a cured product of ORMOCER (registered trademark) ONE is inferior in adhesion to a metal.
In addition, Patent Document 7 discloses a buffer coat material composed of an organic silane having a polymerizable group and an organic silane having a hydrolysis reaction site, using Ti (O-iPr) ₄ (tetraisopropoxytitanium) as a synthesis catalyst. .
As a problem in the material disclosed in Patent Document 7, since Ti (O-iPr) ₄ is an unstable compound, it gradually decomposes and deteriorates in the middle of the polycondensation reaction and generates another side reaction. The three-dimensional network bonding structure of the obtained photosensitive resin is in an insufficient bonding state and has a low elongation. When a local tensile stress from outside such as upper and lower Cu wirings is applied after pattern formation, the elongation is only about 2%, and local cracks are generated, resulting in poor reliability.

Japanese Patent Laid-Open No. 06-053520 Japanese Patent Laid-Open No. 06-240137 JP 09-017777 A Japanese Patent Laid-Open No. 11-297684 JP 2002-203851 A Canadian Patent No. 238756 US Patent Publication No. 20050222697

  The present invention is useful for the manufacture of electrical / electronic materials such as semiconductor devices and multilayer wiring boards, and is particularly suitable as a buffer coating material for LSI chips. An object of the present invention is to obtain a photosensitive resin film having a siloxane structure with improved adhesion and elongation.

In order to solve the above-mentioned problems, the present inventor has studied a photosensitive resin containing siloxane as a new material, and in the polycondensation reaction of the resin, the catalyst is Ti (O—C (CH ₃ ) ₃ ) , Ti (O-tBu) ₄ or tetraterbutoxytitanium), it is found that a photosensitive resin with excellent elongation can be obtained, and epoxy resin is obtained from the polycondensation reaction. It has been found that a photosensitive resin having excellent adhesion and elongation can be obtained by adding a silane compound having a methacryl group or a methacryl group, and the present invention has been completed.

That is, the present invention is as follows.
1. A liquid resin obtained by polycondensing a compound containing the following a) and b) in the presence of Ti (O—C (CH ₃ ) ₃ ) ₄ at a temperature of 40 ° C. to 150 ° C. for 0.1 to 10 hours; A photosensitive resin composition containing a photopolymerization initiator.
a) At least one organosilane represented by the following general formula (I): R ″ m (R ′ ″ Y ′) nSi X _(4-mn) (I)
(In the general formula (I), R ″ is one or more groups selected from alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl,
R ′ ″ is one or more groups selected from alkyl, alkylene, alkenylene, arylene, alkyl-arylene, aryl-alkylene, alkenyl-arylene, arylalkenylene having a substituent Y ′;
R ″ and R ′ ″ may be optionally intervened with oxygen, sulfur, or —NH—,
Y ′ is one or more groups selected from methacryloxy, acryloxy, or vinyl,
X is one or more groups selected from hydrogen, halogen, hydroxy, alkoxy, acyloxy, —NR ′ ₂ (where R ′ is H or alkyl),
m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n is 1 to 3. )
b) At least one organosilane represented by the following general formula (II) R ″ _p Si X _(4-p) (II)
(In the general formula (II), R ″ and X represent the meanings in the general formula (I), and p is an integer of 1 to 3).

2. A) the organosilane is
R ¹ _a R ² _b Si (OR ³ ) _4-ab
(Here, R ¹ is a group having 2 to 17 carbon atoms containing at least one group selected from the group consisting of an epoxy group and a carbon-carbon double bond group. R ² and R ³ are And each independently represents a methyl group or an ethyl group, a is an integer selected from 1 and 2. b is an integer selected from 0 and 1. a + b does not exceed 2.)
A compound represented by
The above b) organosilane is
R ₂ Si (OH) ₂
(Here, R is at least one group selected from the group consisting of an aryl group having 6 to 20 carbon atoms and an alkylaryl group having 6 to 20 carbon atoms.)
It is a compound represented by 1. The photosensitive resin composition as described.

3. 1. The mixed addition amount of Ti (O—C (CH ₃ ) ₃ ) ₄ is 1 to 10 mol% with respect to b) organosilane. Or 2. The photosensitive resin composition as described in 2.
4). 1. a) the organosilane is 3-methacryloxypropyltrimethoxysilane, and b) the organosilane is diphenylsilanediol. ~ 3. The photosensitive resin composition as described in any one of these.
5.1. ~ 4. A method for producing a resin film having a siloxane structure, comprising: applying a photosensitive resin according to any one of the above to a silicon wafer surface, exposing, developing, and curing.
6.5. The resin laminated body obtained by laminating | stacking a resin film on the silicon wafer surface by the manufacturing method of the resin film of description.

  According to the present invention, it is useful for the manufacture of electrical / electronic materials such as semiconductor devices, multilayer wiring boards, etc. Especially as a buffer coating material for thick film of LSI chips, it is excellent in low shrinkage and low stress and adheres to the underlying metal wiring. A photosensitive resin film having a siloxane structure with improved strength and elongation can be obtained.

(1) About photosensitive resin The photosensitive resin in the present invention is a compound containing the following a) and b) in the presence of Ti (O—C (CH ₃ ) ₃ ) ₄ at 40 ° C. to 150 ° C. or less. A photosensitive resin obtained by a process including a step of polycondensation at a temperature for 0.1 to 10 hours to obtain a liquid resin. The temperature is preferably 50 to 90 ° C, more preferably 70 to 90 ° C. The time is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours.
This step may be followed by a process that further includes the step of adding a compound comprising c) below. In the step, only the compound containing the following c) may be added in advance after being heated at a temperature of 50 to 150 ° C. for 0.1 to 10 hours to form an oligomer polymer having a polymerization degree of 2 to 15 by a self-addition reaction. . When added as an oligomer, the adhesion is not improved compared to the addition of a monomer alone, but the effect of further improving the elongation can be obtained.
Here, the molar ratio of the following a) organosilane and b) organosilane is 60 mol% / 40 mol% to 40 mol% / 60 mol%, preferably 55 mol% / 45 mol% to 45 mol% / 55. The mol%, more preferably 52 mol% / 48 mol% to 48 mol% / 52 mol%, and most preferably 50 mol% / 50 mol%.

a) At least one organosilane represented by the following general formula (I): R ″ m (R ′ ″ Y ′) nSi X _(4-mn) (I)
(In the general formula (I), R ″ is one or more groups selected from alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl,
R ′ ″ is one or more groups selected from alkyl, alkylene, alkenylene, arylene, alkyl-arylene, aryl-alkylene, alkenyl-arylene, arylalkenylene having substituent Y ′,
R ″ and R ′ ″ may be optionally intervened with oxygen, sulfur, or —NH—,
Y ′ is one or more groups selected from methacryloxy, acryloxy, or vinyl,
X is one or more groups selected from hydrogen, halogen, hydroxy, alkoxy, acyloxy, —NR ′ ₂ (where R ′ is H or alkyl),
m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n is 1 to 3. )

b) At least one organosilane R ″ _p Si X _(4-p) (II) represented by the following general formula (II)
(In the general formula (II), R ″ and X represent the meanings in the general formula (I), and p is an integer of 1 to 3).
c) At least one organosilane represented by the following general formula (III) is 1 to 30% by weight based on the total amount of addition of a), b) and Ti (O—C (CH ₃ ) ₃ ) ₄
R ″ m (R ′ ″ Y ″) n Si X _(4-mn) (III)
(In the general formula (III), R ″, R ′ ″ and X represent the meaning of the general formula (I), Y ″ represents an epoxy group, a methacryl group or an acrylic group, and m and n are And an integer of 0 to 3, m + n is 1 to 3.)

The alkyl is a linear, branched, or cyclic saturated group having 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. Examples of such are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and cyclohexyl groups.
The aryl is an aromatic group having 6 to 25, preferably 6 to 14, and more preferably 6 to 10 carbon atoms. Examples of such are a phenyl group and a naphthyl group. A preferred example is a phenyl group.
The alkenyl refers to a linear, branched, or cyclic monovalent or polyunsaturated group having 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms. Examples of such are allyl, 2-butenyl, and vinyl groups.
Specific examples of these are given below.

In the general formula (I),
X is CH ₃ O—, Y is —O—CO—C (CH ₃ ) ═CH ₂ , and R ′ ″ is — (CH ₂ ) ₃ —.
, M = a _{0, n = 1 (CH 3} O) 3 -Si- (CH 2) 3 -O-CO-C (CH 3) = CH 2,
X is CH ₃ O—, Y is —O—CO—CH═CH ₂ , R ′ ″ is — (CH ₂ ) ₃ —, m = 0, n = 1 (CH ₃ O) ₃ —Si—. _{(CH 2) 3 -O-CO} -CH = CH 2,
X is CH ₃ O—, Y is —CH═CH ₂ , R ′ ″ is — (CH ₂ ) _X —, m = 0, n = 1 (CH ₃ O) ₃ —Si— (CH ₂ ) _{X -CH = CH 2 X = 1} or 2

Among the organosilanes represented by the above general formula (I) as the a) organosilane,
R ¹ _a R ² _b Si (OR ³ ) _4-ab
(Here, R ¹ is a group having 2 to 17 carbon atoms containing at least one group selected from the group consisting of an epoxy group and a carbon-carbon double bond group. R ² and R ³ are And each independently represents a methyl group or an ethyl group, a is an integer selected from 1 and 2. b is an integer selected from 0 and 1. a + b does not exceed 2.)
The compound represented by these is preferable. Examples of R ¹ include a vinyl group, 2- (3,4-epoxycyclohexyl) group, 3-glycidoxypropyl group, styryl group, 3- (meth) acryloxypropyl group, and 2- (meth) acryloxy. Examples thereof include an ethyl group and a (meth) acryloxymethyl group. Here, (meth) acryl refers to an acryl group and a methacryl group.
Of these, 3-methacryloxypropyltrimethoxysilane (hereinafter sometimes referred to as MEMO) is most preferable.

上記ｂ）有機シランとしては、
Ｒ_２ Ｓｉ （ＯＨ）_２
（ここで、Ｒは炭素数６〜２０のアリール基、及び炭素数６〜２０のアルキルアリール基からなる群より選ばれる１種以上の基である。）で表される化合物が好ましい。具体例を以下に挙げる。
ＣＨ_３−Ｓｉ−Ｃｌ_３， ＣＨ_３−Ｓｉ−（ＯＣ_２Ｈ_５）， （Ｃ_６Ｈ_５）_２−Ｓｉ−（ＯＨ）_２
このうち、最も好ましくは、ジフェニルシランジオール（以下、ＤＰＤと表示する場合もある）である。

As the above b) organosilane,
R ₂ Si (OH) ₂
(Here, R is one or more groups selected from the group consisting of an aryl group having 6 to 20 carbon atoms and an alkylaryl group having 6 to 20 carbon atoms). Specific examples are given below.
_{CH 3 -Si-Cl 3, CH} 3 -Si- (OC 2 H 5), (C 6 H 5) 2 -Si- (OH) 2
Of these, diphenylsilanediol (hereinafter sometimes referred to as DPD) is most preferable.

上記ｃ）有機シランとして、上記一般式（ＩＩＩ）で示される有機シランの例を以下に挙げる。

Examples of the organic silane represented by the above general formula (III) as c) the organic silane are given below.

３−グリシジルオキシプロピルトリメトキシシラン（以下、ＧＬＹＭＯと表示する場合もある）又は３−メタクリルオキシプロピルトリメトキシシラン（以下、ＭＥＭＯと表示する場合もある）が最も好ましい。

Most preferred is 3-glycidyloxypropyltrimethoxysilane (hereinafter sometimes referred to as GLYMO) or 3-methacryloxypropyltrimethoxysilane (hereinafter sometimes referred to as MEMO).

In the present application, the mixed addition amount of Ti (O—C (CH ₃ ) ₃ ) ₄ is preferably 1 to 10 mol%, and preferably 1 to 3 mol% with respect to the above b) organosilane. More preferably, 2.2 mol% is most preferable.
Compared with Ti (O—C (CH ₃ ) ₃ ) ₄ in the present application, when barium hydroxide or tetratertiary isopropoxide is used, the reaction proceeds sufficiently with an addition amount of 1 mol% or less (patent) References 6 and 7) show that Ti (O—C (CH ₃ ) ₃ ) ₄ in this application is a more stable compound than barium hydroxide and tetratertiary isopropoxide, and has the effect of reducing side reactions. .

The addition amount of the above-mentioned c) organosilane, from 1 to 30 wt% with respect to the a) organic silane, b) above organosilane and _{Ti (O-C (CH 3} ) 3) Total amount of _4.
Preferably it is 2 to 20 weight%, More preferably, it is 3 to 7 weight%. If c) is 30% by weight or less, the stability of the resin liquid is high and the quality variation is small, which is preferable. As the photopolymerization initiator in the present application, a known photopolymerization initiator having absorption at 365 nm, for example, 2-benzyl-2-dimethylamino-4′-morpholinobutyrophenone (IRGACURE 369) is preferably used. Other known initiators include, for example, benzophenone, 4,4′-diethylaminobenzophenone, diethylthioxanthone, ethyl-p- (N, N-dimethylaminobenzoate), 9-phenylacridine. The addition amount of the photopolymerization initiator is preferably 0.01 to 5 parts by weight, more preferably 0.3 to 3 parts by weight, and particularly preferably 0.5 to 2 parts by weight with respect to 100 parts by weight of the polycondensate. Part.

(2) Method for producing resin film having siloxane structure A photosensitive resin layer made of a photosensitive resin composition is formed on a substrate such as a silicon wafer, for example, a spin coater, a bar coater, a blade coater, a curtain coater, or screen printing. It can form by the method of apply | coating with a machine etc. or spray-coating with a spray coater etc.
The obtained photosensitive resin layer may be pre-baked by air drying, heating with an oven or hot plate, vacuum drying, or the like.
The obtained photosensitive resin layer is exposed with an ultraviolet light source or the like through a mask using an exposure apparatus such as a contact aligner, a mirror projection, or a stepper. In view of the resolution and handleability of the cured pattern of the resin layer after exposure, the light source wavelength is preferably i-line, and the apparatus is preferably a stepper.

Subsequently, development is performed. The unexposed part of the photosensitive resin layer is removed by development. Thereby, a hardening pattern can be obtained. The development can be carried out by selecting an arbitrary method from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment.
The developer used is preferably a combination of a good solvent and a poor solvent for the polymer precursor. As this good solvent, N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N′-dimethylacetamide, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like are used. Moreover, toluene, xylene, methanol, ethanol, isopropyl alcohol, water, etc. are used as a poor solvent. The ratio of the poor solvent to the good solvent is adjusted by the solubility of the photosensitive resin composition having a siloxane structure. Combinations of the solvents can also be used.

The cured pattern of the resin having a siloxane structure thus obtained is cured to bond unreacted methacryl groups to obtain a resin film having a siloxane structure.
The curing can be performed by, for example, a hot plate, an oven, and a temperature rising oven in which a temperature program can be set. Air may be used as the atmosphere gas for curing, and an inert gas such as nitrogen or argon may be used. The curing temperature is preferably 150 to 250 ° C. The curing time is preferably 2 to 4 hours.
Although the thickness of the resin film which has a siloxane structure changes with uses, Preferably it is 10-100 micrometers, More preferably, it is 10-50 micrometers, More preferably, it is 20-40 micrometers.

EXAMPLES Next, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited by these.
[Example 1]
1) In a 00 ml eggplant-shaped flask, 0.1 mol (21.63 g) of DPD, 0.1 mol (23.74 g) of MEMO, and 2.2 mol% (0.748 g) of tetra-tert-butoxy titanium with respect to DPD ), Charged into an eggplant-shaped flask, attached to a cooler, and gradually heated from room temperature to 80 ° C. in an oil bath. After confirming the start of reflux by the generated methanol at 80 ° C., the reflux was continued for 1 hour at the same temperature. Thereafter, the cooler was removed and methanol was removed by vacuum distillation at the same temperature. When the degree of vacuum was gradually increased to 3 torr so as not to cause bumping, evacuation was continued for 2 hours while stirring at 80 ° C., and finally the pressure was returned to normal pressure to complete the removal of methanol. After cooling the obtained transparent polycondensate to room temperature, 1 part by weight of IRGACURE369 (manufactured by Ciba Geigy) as a photopolymerization initiator is added to 100 parts by weight of the obtained polycondensate, and a 0.2 μm mesh filter is added. And filtered. The final viscosity was 20 poise.

2) The obtained photosensitive resin composition was spin-coated at 1500 rpm for 40 seconds to obtain a spin-coated film having a thickness of 20 μm on the LSI wafer.
3) The spin-coated film was pre-baked at 80 ° C. for 1 minute to remove the remaining volatile components. At this time, neither the film shrinkage nor the flatness deteriorated.
4) Using a negative mask, a crosslinking reaction was performed by UV exposure (wavelength 365 nm). The amount of light is 200 mJ / cm ² .

5) Development was performed for 60 seconds using a 1: 1 mixed solution of MIBK (methyl isobutyl ketone) and IPA (isopropyl alcohol), and rinsed with IPA to form a via hole pattern having a diameter of 10 μm.
6) The film on which the via hole pattern was formed was post-baked at 80 ° C. for 1 minute, and finally cured in N ₂ for 3 hours at 150 ° C. to complete the curing.
7) Further, copper plating is performed, a resist pattern is formed on the copper plating by a known photomechanical method, an unnecessary copper plating layer is etched, and the resist is peeled off to form a second layer Cu rewiring layer Formed.

[Example 2] 1) In Example 1, the same procedure as in Example 1 was performed except that the steps were as follows.
1) In a 500 ml eggplant type flask, 0.1 mol (21.63 g) of DPD, 0.1 mol (23.74 g) of MEMO, and 2.2 mol% (0.748 g) of tetra-tert-butoxytitanium with respect to DPD. ), Charged into an eggplant-shaped flask, attached to a cooler, and gradually heated from room temperature to 80 ° C. in an oil bath. After confirming the start of reflux by the generated methanol at 80 ° C., the reflux was continued for 1 hour at the same temperature. Thereafter, the cooler was removed and methanol was removed by vacuum distillation at the same temperature. When the degree of vacuum was gradually increased to 3 torr so as not to cause bumping, evacuation was continued for 2 hours while stirring at 80 ° C., and finally the pressure was returned to normal pressure to complete the removal of methanol. After cooling the obtained transparent polycondensate to room temperature, 1 part by weight of IRGACURE369 (manufactured by Ciba Geigy) as a photopolymerization initiator is added to 100 parts by weight of the obtained polycondensate, and a 0.2 μm mesh filter is added. And filtered. Thereafter, 3 parts by weight of MEMO was added to 100 parts by weight of the obtained polycondensate at room temperature to obtain a photosensitive resin composition. The final viscosity was 15 poise.

[Example 3]
A photosensitive resin composition was obtained in the same manner as in Example 2 except that MEMO was changed to GLYMO.
[Comparative Example 1]
A photosensitive resin composition was obtained in the same manner as in Example 1 except that tetraterbutoxytitanium was changed to Ba (OH) ₂ .
[Comparative Example 2] A photosensitive resin composition was obtained in the same manner as in Example 1 except that tetraterbutoxytitanium was changed to Ti (O-iPr) ₄ .
In Examples 1 and 2, after the step 6), the step of the Via hole was measured (P-15 manufactured by Tencor Corp.) for the resin film having a siloxane structure. By measurement, a very flat film was obtained, and the shrinkage rate of the resin film was 3% or less.
In addition, after the step 7), it was confirmed that a favorable second-layer Cu rewiring layer having high flatness and no vertical undulations was formed.

The performances of the resins obtained in Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 1 below.
In addition, the measurement of “adhesion strength evaluation” and “elongation at break” in the following table was performed as follows. <Adhesion strength evaluation method>
A resin film was formed on the Si wafer with a Cu sputtered film through steps 1 to 3 and Comparative Example 1), and then a cross cut guide 1.0 was used in a cross-cut tape peeling test (JIS K 5400). Was scratched with a cutter knife so that 100 squares of 1 mm square could be made. After applying the cellophane tape from above, the film was peeled off. Adhesion was evaluated by counting the number of squares remaining on the substrate that did not adhere to the cellophane tape.

<Evaluation method of elongation at break>
A resin film is formed on the Si wafer with an Al sputtered film through steps 6 to 3 in Comparative Examples 1 and 1, and then a dicing saw (manufactured by Disco Corporation, model name DAD-2H / 6T) is used. And cut to a width of 3.0 mm. The wafer was immersed in 10% hydrochloric acid water, and the resin film was peeled off from the silicon wafer to obtain a strip-shaped film sample. The obtained film sample was set in a measuring device (ORISTEC's Tensilon, model UTM-I I-20) by a tensile breaking strain test (JIS K 7161), and measured at a distance between chucks of 50 mm and a pulling speed of 40 mm / min. .

  The photosensitive resin composition of the present invention and the resin film obtained from the photosensitive resin composition are extremely useful as electric / electronic materials such as semiconductor devices and multilayer wiring boards, particularly as buffer coating materials for LSI chips. The resin film can be used as a resin insulating film.

Claims (6)

A liquid resin obtained by polycondensing a compound containing the following a) and b) in the presence of Ti (O—C (CH ₃ ) ₃ ) ₄ at a temperature of 40 ° C. to 150 ° C. for 0.1 to 10 hours; A photosensitive resin composition containing a photopolymerization initiator.
a) At least one organosilane represented by the following general formula (I): R ″ m (R ′ ″ Y ′) nSi X _(4-mn) (I)
(In the general formula (I), R ″ is one or more groups selected from alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl, arylalkenyl,
R ′ ″ is one or more groups selected from alkyl, alkylene, alkenylene, arylene, alkyl-arylene, aryl-alkylene, alkenyl-arylene, arylalkenylene having a substituent Y ′;
R ″ and R ′ ″ may be optionally intervened with oxygen, sulfur, or —NH—,
Y ′ is one or more groups selected from methacryloxy, acryloxy, or vinyl,
X is one or more groups selected from hydrogen, halogen, hydroxy, alkoxy, acyloxy, —NR ′ ₂ (where R ′ is H or alkyl),
m is an integer of 0 to 2, n is an integer of 1 to 3, and m + n is 1 to 3. )
b) At least one organosilane represented by the following general formula (II) R ″ _p Si X _(4-p) (II)
(In the general formula (II), R ″ and X represent the meanings in the general formula (I), and p is an integer of 1 to 3). A) the organosilane is
R ¹ _a R ² _b Si (OR ³ ) _4-ab
(Here, R ¹ is a group having 2 to 17 carbon atoms containing at least one group selected from the group consisting of an epoxy group and a carbon-carbon double bond group. R ² and R ³ are And each independently represents a methyl group or an ethyl group, a is an integer selected from 1 and 2. b is an integer selected from 0 and 1. a + b does not exceed 2.)
A compound represented by
The above b) organosilane is
R ₂ Si (OH) ₂
(Here, R is at least one group selected from the group consisting of an aryl group having 6 to 20 carbon atoms and an alkylaryl group having 6 to 20 carbon atoms.)
The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is represented by the formula: _3. The photosensitive property according to claim 1, wherein a mixed addition amount of the Ti (O—C (CH ₃ ) ₃ ) ₄ is 1 to 10 mol% with respect to the b) organosilane. Resin composition.   The photosensitive resin composition according to any one of claims 1 to 3, wherein a) the organic silane is 3-methacryloxypropyltrimethoxysilane, and b) the organic silane is diphenylsilanediol.   A process for producing a resin film having a siloxane structure, comprising: applying the photosensitive resin according to claim 1 onto a silicon wafer surface, exposing, developing, and curing the photosensitive resin. Method.   A resin laminate obtained by laminating a resin film on a silicon wafer surface by the method for producing a resin film according to claim 5.