KR100451576B1 - Adhesive compositons and adhesive tapes comprising the same - Google Patents

Abstract

The present invention relates to an adhesive composition and an adhesive tape for a semiconductor used as a substrate for tape automated bonding (TAB).

The present invention for this purpose, in the adhesive resin composition, the amine value is in the range of 1 to 20, the polyamide resin having a weight average molecular weight of 50,000 to 500,000, the amine value is in the range of 20 to 50, the weight average molecular weight is 5,000 to 10,000 An adhesive composition comprising a polyamide resin in a range, a resol-type phenol resin having two or more methylol groups in a skeleton, and an adhesive tape using the same are provided.

The adhesive composition of this invention contains methylol group in frame | skeleton, and the resin composition which hardened-reacted the polyamide resin which has the amine group which can react with the resol type phenol resin which has the property of self-curing, and the methylol group of resol type phenol resin. Say

The adhesive tape of this invention relates to the adhesive agent used by a semiconductor device assembly process, and is used for TAB and other semiconductor adhesive components.

The adhesive tape of the present invention constitutes an adhesive tape composed of a three-layer structure of a protective film, an adhesive, and an organic insulating film.

Description

Adhesive composition and adhesive tape containing it TECHNICAL FIELD

The present invention relates to an adhesive composition and an adhesive tape for a semiconductor used as a substrate for tape automated bonding (TAB).

Conventional adhesive compositions for semiconductors have a polyamide resin having an amine value in the range of 20 to 60, a weight average molecular weight in the range of 1,000 to 5,000, a weight average molecular weight in the range of 2,000 or less, and having two or more methylol groups in the skeleton. It was reacted with a resol type phenolic resin. In such a composition, since the polyamine resin having a high amine value and a low molecular weight was used, the adhesive was easily broken, and an excess polyamide resin was added to solve this problem. In this case, the Tg is lowered, and the punching property is poor when processing the TAB tape because it does not have sufficient tensile strength and elastic modulus, and a problem arises in that wire bonding is not performed in semiconductor packaging. To overcome this limitation, a polyamide resin having an amine value ranging from 1 to 20, a weight average molecular weight ranging from 50,000 to 500,000, and a polyamide resin having an amine value ranging from 20 to 50 and a weight average molecular weight ranging from 5,000 to 10,000 are simultaneously used. By using it, it does not break easily even with a small amount of polyamide resin, has high Tg and heat resistance, has adequate tensile strength in TAB tape processing and wire bonding, and has sufficient adhesive strength under high temperature and high humidity treatment (PCT) conditions. Provide adhesive tape.

In consideration of the problems of the prior art, the present invention has a polyamide resin having an amine value in the range of 1 to 20, a weight average molecular weight in the range of 50,000 to 500,000, and an amine value in the range of 20 to 50, and a weight average molecular weight of 5,000 to 10,000. The simultaneous use of polyamide resins in the range provides adhesive tapes having high Tg and heat resistance, adequate tensile strength in TAB tape processing and wire bonding, and sufficient adhesion under high temperature and high humidity treatment (PCT) conditions.

In general, the resol-type phenol resin has a methylol group in addition to the phenolic hydroxyl group substituted at the benzene position, thereby allowing the curing reaction to itself without a curing agent, and at the same time react with the amine group of the polyamide resin. When the resol type phenol resin is reacted with a low molecular weight polyamide resin, an excessive amount of polyamide resin should be used because the adhesive breaks well, and in this case, it is difficult to have sufficient tensile strength, and the low molecular weight polyamide resin alone It is difficult to have sufficient adhesion. In addition, when reacted with a polyamide resin having a high molecular weight, it is difficult to form a dense hardening network, and thus, Tg is lowered, and tensile strength and elastic modulus are reduced, so that punching workability is poor when processing TAB tape, and wire bonding is not possible in semiconductor packaging process. Is generated. When using a polyamide resin having a weight average molecular weight of 5,000 or less and an amine value of 20 or less, it is difficult to fully advance the semi-hardening, which causes serious bleed-out phenomenon in which the adhesive flows around the via hole. The heat resistance is also significantly reduced. If the amine value is more than 50, the semi-curing proceeds too rapidly, causing a problem that the adhesive does not adhere well to the copper foil. Therefore, in order to control the semi-cured state of the adhesive well, a polyamide resin having an amine value in the range of 20 to 50 and a weight average molecular weight in the range of 5,000 to 10,000 is suitable. However, when only this is used alone, sufficient adhesive strength is not obtained, in particular, the water absorption rate is increased, so that the adhesive strength after high temperature and high humidity treatment (PCT) is not good. In addition, since the adhesive is brittle, an excessive amount of polyamide resin should be used to solve this problem. In this case, the tensile modulus decreases, and the punching workability of the TAB tape is degraded. If polyamide resins having an amine value in the range of 20 to 50 and a weight average molecular weight of 5,000 to 10,000 are used simultaneously with a polyamide resin having an amine value in the range of 1 to 10 and a weight average molecular weight of 50,000 to 500,000, the adhesive will break easily. Since it is not supported, a small amount of polyamide resin can be used, which is suitable for TAB tape processing, exhibits tensile strength capable of wire bonding at high temperatures, and at the same time has high adhesive strength, particularly after high temperature and high humidity treatment (PCT) and at high temperatures. Could provide adhesive tape.

The present invention to achieve the above object,

a) polyamide resin having an amine value in the range of 1 to 20 and a weight average molecular weight in the range of 50,000 to 500,000;

b) polyamide resins having an amine value ranging from 20 to 50 and a weight average molecular weight ranging from 5,000 to 10,000; And

c) resol type phenolic resin

It provides an adhesive composition for a semiconductor comprising a.

The present invention also relates to an adhesive tape obtained by laminating an adhesive layer made of the adhesive composition of the present invention in a sheet form between a protective film and an organic insulating film. Provided is a semiconductor adhesive and adhesive tape capable of packaging TAB and wire bonding using a tape automated bonding (TAB) tape manufactured using the adhesive composition.

Hereinafter, the present invention will be described in detail.

To this end, a) polyamide resin having an amine value in the range of 1 to 20 and a weight average molecular weight in the range of 50,000 to 500,000; b) A polyamide resin having an amine value in the range of 20 to 50 and a weight average molecular weight in the range of 5,000 to 10,000, and c) an adhesive composition obtained by curing the resol type phenol resin having two or more methylol groups in the skeleton.

The high molecular weight polyamide resin (a) used for this purpose can be dissolved in a mixed solvent of an aromatic solvent such as toluene, xylene, and alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, and has an amine value of 1-20. It is a range, and it is suitable that a weight average molecular weight exists in the range of 50,000-500,000. In particular, it is preferable that an amine value is the range of 5-10, and a weight average molecular weight exists in the range of 80,000-200,000. If the amine value of the high molecular weight polyamide resin (a) is less than or equal to 1, the compatibility with the low molecular weight polyamide resin (b) is insufficient, and layer separation occurs. If the amine value is more than 20, the water absorption rate is increased and the adhesion strength is significantly decreased after PCT. do. If the weight average molecular weight is 50,000 or less, the bleed out is increased and does not exhibit sufficient adhesion. On the other hand, if the weight average molecular weight is more than 500,000, compatibility with the low molecular weight polyamide resin is lowered, and the varnish viscosity may increase rapidly and cause gelation.

As the low molecular weight polyamide resin (b), like the polymer polyamide resin (a), it can be dissolved and used in a mixed solvent of an aromatic solvent such as toluene and xylene and an alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol. It is appropriate that the value is in the range of 20 to 50 and the weight average molecular weight is in the range of 5,000 to 10,000. If the amine value is 20 or less, it is difficult to proceed the semi-curing sufficiently, and the bleed-out phenomenon that the adhesive is pushed around the via hole becomes serious. If the amine value is 50 or more, the semi-curing progresses too rapidly, and the adhesive does not adhere to the copper foil. Does not cause problems. When the weight average molecular weight is 5,000 or less, bleed-out also occurs severely, and compatibility with the high molecular weight polyamide resin (a) is also inferior. When the weight average molecular weight is 10,000 or more, it is difficult to form a dense network during curing, and it becomes difficult to secure sufficient Tg and heat resistance.

The high molecular weight polyamide resin (a) / low molecular weight polyamide resin (b) ratio is preferably in the range of 0.1 to 10, and particularly preferably in the range of 0.2 to 5. When the high molecular weight polyamide resin (a) / low molecular weight polyamide resin (b) ratio is 0.1 or less, the adhesive force is not sufficient, the adhesive is broken well, and a lot of burrs are generated during the punching operation, and the adhesive force after high temperature and high humidity treatment This is significantly lowered. On the other hand, when the ratio of high molecular weight polyamide resin (a) / low molecular weight polyamide resin (b) is 10 or more, the tensile strength is low and the punching workability is lowered, and the adhesion and tensile strength at Tg and high temperature are significantly reduced. .

The resol type phenol resin (c) preferably has two or more methylol groups in the phenolic hydroxyl group and the skeleton, and particularly preferably has three or more methylol groups in the skeleton. It will not specifically limit, if it has a phenolic hydroxyl group and a methylol group in a molecule | numerator, Specifically, what is necessary is just what consists of a phenol type, a cresol type, an alkyl type, a bisphenol A type, and these copolymers. It is preferable that the weight average molecular weight of the resol-type phenol resin is 2,000 or less, and when the molecular weight is 2,000 or more, compatibility with the polyamide resin is lowered, and a problem that the varnish viscosity increases sharply occurs. The ratio of the resol type phenol resin (c) / polyamide resin (a) and (b) is preferably in the range of 0.5 to 2, particularly preferably in the range of 0.6 to 1.5. When the ratio of the resol-type phenol resin (c) / polyamide resin (a) and (b) is 0.5 or less, the adhesive breaks well, sufficient adhesive strength does not come out, heat resistance such as solder resistance is greatly reduced, and in particular, electrical reliability is poor. Do. When the ratio of the resol-type phenol resin (c) / polyamide resin (a) and (b) is 2 or more, the tensile strength is lowered, the punching workability is poor, and the tensile strength and the adhesive strength at high temperature are poor.

The adhesive for semiconductors of the present invention has a sheet-like shape in which an adhesive layer is laminated on a protective film or a protective film is laminated on both sides of an adhesive layer. Moreover, it can be set as the tape shape which laminated | stacked the organic insulating film and the protective film on both surfaces of the adhesive agent.

Tapes based on organic insulating films and adhesive layers are commonly referred to as TAB tapes. Next, the TAB tape manufacturing method will be described.

1) Apply adhesive on the protective film. At this time, it is dried for about 2 to 5 minutes at about 130 ~ 150 ℃ to semi-harden. After drying, the adhesive layer thickness is 12-25 μm.

2) In order to attach the formed adhesive layer and the organic insulating film, thermocompression bonding is performed under a pressure condition of about 100-120 ° C. and 1 kg / cm.

3) The dimension of the obtained TAB tape is not particularly limited, but is generally formed to be 30 to 200 mm wide and 30 to 300 m long.

As the organic insulating film, heat resistant films such as polyimide, polyether imide, polyphenylene sulfide and polyether ketone, and composite heat resistant films such as epoxy resin-glass cross and polyimide glass cross are used. The organic insulating film may be subjected to corona discharge treatment, plasma treatment, chemical etching treatment, sand blast treatment, primer treatment, electrical treatment, etc. for the purpose of improving the adhesive strength, or may use a commercially available film. The thickness of the organic insulating film is generally 12.5 ~ 150 ㎛ thickness, in particular 25 ~ 75 ㎛ is used. If the thickness of the organic insulating film is less than 12.5 μm, the resulting film is difficult to exhibit sufficient insulating properties and is too flexible to punch out. In addition, when the thickness of the organic insulating film exceeds 150 μm, the resulting film becomes too hard, and a lot of burrs are generated when punching.

The adhesive layer is generally formed in a thickness of 10-25 μm. If the thickness of the adhesive layer is less than 10 μm, sufficient adhesive strength may not be exhibited. If the thickness of the adhesive layer is more than 25 μm, punching property may be lowered and bleed out may be severe.

Polyethylene, polyethylene terephthalate, polypropylene, fluororesin film and paper are used as the protective film, and in order to improve the peeling force with the adhesive layer during use, it is preferable to perform a surface treatment of silicone or alkyl modified silicone. . Generally 10-100 μm thick is used, especially 25-38 μm thick. When the thickness of the protective film is less than 10 μm, wrinkles are severely generated when the adhesive is coated, and there is a problem of tearing well. On the other hand, when the thickness of the protective film exceeds 100 μm, there is a problem that excessive pressure is applied when thermocompression bonding with the organic insulating layer. Can be.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, the examples are only for illustrating the present invention and are not limited to these.

EXAMPLE

Example 1

Adhesive composition

40 g of a polyamide resin having an amine value of 10 and a weight average molecular weight of 150,000, 20 g of a polyamide resin having an amine value of 30 and a weight average molecular weight of 7,000 and a bisphenol A type resol type phenolic resin having a weight average molecular weight of 1,200 80 The varnish was prepared by dissolving g in a mixed solvent having a toluene / isopropyl alcohol ratio of 2/3 so that the solid content was 25%.

Adhesive tape manufacturers

The adhesive composition prepared in Example 1 was coated on a polyethylene terephthalate film having a thickness of 25 μm, and then dried at 140 ° C. for 3 minutes to form an adhesive layer having a thickness of 12 μm. The adhesive layer was cut to a predetermined width, and then thermally compressed by applying a pressure of 1 kg / cm at a temperature of 120 ° C. with a 50 μm thick polyimide film (UBE UPLEX 50S).

Sample Preparation for Adhesive Strength Measurement

After removing the polyethylene terephthalate film from the adhesive tape prepared above, the adhesive was thermally compressed by applying 1 kg / cm pressure at a temperature of 130 ° C. with an 18 μm thick copper foil (Mitsui Copper Foil 3EC-HTE). The sample was held at 70 ° C. for 4 hours and then cured at 180 ° C. for 7 hours. A sample for measuring adhesion was cut into 1 × 8 cm size.

Sample Preparation for Tensile Modulus and Tg Measurement

The adhesive composition prepared in Example 1 was coated on a polyethylene terephthalate film having a thickness of 25 μm so as to have a thickness of 12 μm, and then covered with a polyethylene terephthalate film having a thickness of 25 μm and a pressure of 1 kg / cm was added thereto. Pressed in. The sample was held at 70 ° C. for 4 hours and then cured at 180 ° C. for 7 hours. The sample for measuring the tensile modulus was cut to a size of 1 × 8 cm, and the sample for measuring Tg was cut to a size of 0.3 × 4 cm.

Sample preparation for punchability and bleed-out measurements

The adhesive tape prepared in Example 1 was cut to a size of 4.8 × 6 cm, and then put into a self-made mold and perforated. After the sample for bleed-out measurement was punched out, the polyethylene terephthalate film was peeled off, and the adhesive was thermally compressed by applying 1 kg / cm pressure at 130 ° C. with an 18 μm thick copper foil (Mitsui Copper Foil 3EC-HTE). The sample was held at 70 ° C. for 4 hours and then cured at 180 ° C. for 7 hours.

Example 2

20 g of polyamide resin having an amine value of 10 and a weight average molecular weight of 150,000, 40 g of a polyamide resin having an amine value of 30 and a weight average molecular weight of 7,000 and a bisphenol A type resol type phenolic resin having a weight average molecular weight of 1,200 50 The varnish was prepared by dissolving g in a mixed solvent having a toluene / isopropyl alcohol ratio of 2/3 so that the solid content was 25%.

Example 3

20 g of polyamide resin having an amine value of 5 and a weight average molecular weight of 80,000, 40 g of polyamide resin having an amine value of 50 and a weight average molecular weight of 5,000, and a bisphenol A type resol type phenolic resin having a weight average molecular weight of 1,200. The varnish was prepared by dissolving g in a mixed solvent having a toluene / isopropyl alcohol ratio of 2/3 so that the solid content was 25%.

Example 4

Bisphenol A type resol type phenol resin 50 whose polyamine resin has an amine value of 5, the weight average molecular weight is 80,000, 30 g, the amine value is 50, 30 g the polyamide resin has a weight average molecular weight of 5,000, and the weight average molecular weight is 1,200. The varnish was prepared by dissolving g in a mixed solvent having a toluene / isopropyl alcohol ratio of 2/3 so that the solid content was 25%.

Comparative Example 1

100 g of polyamide resin having an amine value of 50 and a weight average molecular weight of 5,000 and 50 g of a bisphenol A type resol type phenol resin having a weight average molecular weight of 1,200 were added to a mixed solvent having a toluene / isopropyl alcohol ratio of 2/3. The varnish was prepared by dissolving to 25%.

Comparative Example 2

90 g of a polyamide resin having an amine value of 10 and a weight average molecular weight of 150,000 and 60 g of a bisphenol A type resol type phenol resin having a weight average molecular weight of 1,200 were added to a mixed solvent having a toluene / isopropyl alcohol ratio of 2/3. The varnish was prepared by dissolving to 25%.

Adhesion test test was performed using ZWICK's tensile strength meter at room temperature and 200 ° C to measure 90 ° adhesion force at a rate of 50 mm / min. After PCT, the adhesion strength was maintained at 121 ° C and 2 atm for 24 hours and then at room temperature. Measured.

Tensile modulus was measured using ZWICK's tensile strength meter, measured at a rate of 10 mm / min at room temperature and 180 ℃.

Tg was measured using SEIKO's TMA, and measured by increasing the temperature at a rate of 20 ℃ / min.

The punching workability was evaluated by the degree of burr occurrence and the extent of the adhesive being pushed around the via hole by electron microscopy. The bleed-out was observed by measuring the degree of the adhesive is pushed out through an optical microscope, it is represented by ○ when not nearly pushed, △ when 10 ~ 15 ㎛, × × when 15 ㎛ or more.

Table 1 shows the measurement results of the physical properties of Examples 1 to 4 and Comparative Examples 1 to 2 obtained by the above test.

Item unit Example Comparative example One 2 3 4 One 2 Adhesion Room temperature g / cm 680 730 710 680 480 750 200 ℃ 380 290 280 330 150 120 After PCT 680 700 690 650 200 730 The tensile strength Room temperature kg / mm2 115 125 130 125 105 50 180 ℃ 20 22 23 21 12 9 Tg ℃ 183 187 187 184 165 70 Punchability ○ ○ ○ ○ × × Bleed out ○ ○ ○ ○ × △

In the above results, in the case of the resin composition of Examples 1 to 4, an adhesive force of 600 kg / cm or more is obtained, and the adhesive force hardly decreases even after the PCT treatment. Adhesion at high temperature was also maintained at 200 kg / cm or more. On the other hand, in the case of Comparative Example 1, after the PCT treatment, the adhesion was significantly reduced, in the case of Comparative Example 2, the adhesive force at a high temperature was significantly reduced. In the case of the resin compositions of Examples 1 to 4, the tensile strength was 100 kg / mm 2 or more at room temperature, 20 kg / mm 2 or more at 180 ° C., and the punching property was also good. On the other hand, in the case of Comparative Example 1, the tensile strength at high temperature was lowered, the adhesive was pushed out a lot during punching, and burr generation was also severe. In the case of Comparative Example 2, the tensile strength was greatly reduced at room temperature and high temperature, and the adhesive was significantly pushed out during punching.

The adhesive composition of the present invention has a polyamide resin having an amine value in the range of 1 to 10, a weight average molecular weight of 50,000 to 500,000, a polyamide having a amine value in the range of 20 to 50 and a weight average molecular weight in the range of 5,000 to 10,000, and a skeleton. It is a composition obtained by hardening reaction of a resol type phenol resin containing two or more methylol groups. When the adhesive composition is used, it has high Tg and heat resistance, and has high tensile strength during TAB tape processing and wire bonding, and at the same time high temperature and high humidity treatment (PCT). Under the conditions, it is possible to form an adhesive layer having sufficient adhesion. If the adhesive is formed between the protective film and the organic insulating film, it can be applied to parts such as electric and electronic devices requiring high heat resistance and tensile strength, and it is possible to improve the reliability of the electronic parts and to extend the temperature range during work such as mounting. It can bring an effect.

Claims (11)

a) polyamide resin having an amine value in the range of 1 to 20 and a weight average molecular weight in the range of 50,000 to 500,000; b) polyamide resin having an amine value in the range of 20 to 50 and a weight average molecular weight in the range of 5,000 to 10,000; And c) resol type phenolic resin Adhesive composition comprising a. The adhesive composition according to claim 1, wherein the polyamide resin (a) is a polyamide resin having an amine value in the range of 5 to 10 and a weight average molecular weight in the range of 80,000 to 200,000. The adhesive composition of Claim 1 whose ratio of the said polyamide resin (a) / said polyamide resin (b) is 0.1-1. The phenol type, cresol type and alkyl type according to Claim 1, wherein the resol type phenol resin (c) has a weight average molecular weight of 2,000 or less, has a phenolic hydroxyl group and a methylol group, and contains two or more methylol groups in the skeleton. And a phenol resin composed of bisphenol A or a copolymer thereof. The adhesive composition according to claim 1, wherein the ratio of the phenol resin (c) / polyamide resin (a) and (b) is in the range of 0.5 to 2. i) an organic insulating film; ii) an adhesive layer made of the adhesive composition according to any one of claims 1 to 5; And iii) protective film Adhesive tape comprising a. The adhesive tape according to claim 6, wherein the organic insulating film (i) is selected from the group consisting of polyimide, polyether imide, polyphenylene sulfide, polyether ketone, epoxy resin-glass cross and polyimide glass cross. The adhesive tape according to claim 6, wherein the thickness of the organic insulating film (i) is in the range of 12.5 to 150 µm. The adhesive tape according to claim 6, wherein the thickness of the adhesive layer (ii) is in the range of 10 to 25 µm. The method of claim 6, wherein said protective film (iii) is polyethylene, polyethylene terephthalate, polypropylene, and flat base adhesive tape is selected from the group consisting of a climb resin film. The method of claim 6, Adhesive tape of the protective film (iii) is in the range of 10 ~ 100 ㎛.