TWI663195B - Insulating film and semiconductor device - Google Patents

Abstract

The object of this case is to provide an insulating film which has excellent film characteristics and excellent heat resistance after curing, and has a thermal conductivity of 3.0 W / mK or more.

The solution to this case is to provide an insulating film containing (A) a novolac epoxy resin, (B) a butadiene acrylonitrile copolymer, (C) an aralkylphenol resin, (D) a hardening catalyst, and (E) An insulating filler having a thermal conductivity of 20 W / mK or more, in which the component (B) is 10 to 20 parts by mass based on 100 parts by mass of the total of the components (A) to (C), and the component (E) is It is 60 to 85% by volume based on 100% by volume of the insulating film.

Description

Insulation film and semiconductor device

The present invention relates to an insulating film and a semiconductor device, and more particularly to an insulating film having excellent heat resistance and thermal conductivity after curing, and a semiconductor device having a high reliability of a cured product containing the insulating film.

In the field of semiconductor devices such as power devices, high thermal conductivity insulating materials are increasingly required. On the other hand, in the manufacturing process of semiconductor devices, semiconductor devices in manufacture may be exposed to high temperatures due to soldering. In addition, in order to improve the reliability of the heat resistance of semiconductor devices, the semiconductor adhesive used in semiconductor devices requires heat resistance. . As a material for improving this heat resistance, there has been disclosed a sealing agent for a protective film layer, which contains a cresol novolac type epoxy resin, a phenol aralkyl resin, and a phenol modified xylene resin (Patent Document 1) ).

On the other hand, in recent years, because of the ease of handling, an adhesive film is increasingly used instead of an adhesive. At this time, the adhesive film is coated on a substrate film such as polyethylene terephthalate (PET), and is supplied as a dried coating film in an uncured state. Therefore, the adhesive film must be flexible and can be used. Film properties such as flexibility.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-91424

However, since it is used for high thermal conductivity, it is highly filled with high thermal conductivity in the sealant for protective film layers containing the above-mentioned cresol novolac epoxy resin, phenol aralkyl resin, and phenol modified xylene resin. In the case of a filler, there is a problem that the dried coating film becomes hard and brittle and cannot be thinned.

Therefore, an object of the present invention is to provide an insulating film which has excellent film characteristics and excellent heat resistance after curing, and has a thermal conductivity of 3.0 W / mK or more.

The present invention relates to an insulating film and a semiconductor device which have the following constitutions to solve the above-mentioned problems.

[1] An insulating film containing (A) a novolac epoxy resin, (B) a butadiene acrylonitrile copolymer, (C) an aralkylphenol resin, (D) a hardening catalyst, and (E) Insulating fillers with a thermal conductivity of 20 W / mK or more, wherein (B) component is 10 to 20 parts by mass with respect to 100 parts by mass of the total of (A) to (C) ingredients, and (E) is relative to the insulator The film 100% by volume is 60 to 85% by volume.

[2] The insulating film according to the above [1], wherein the component (D) is an imidazole-based hardening catalyst.

[3] The insulating film according to the above [1] or [2], wherein the component (E) is At least one selected from the group consisting of alumina, magnesia, and boron nitride.

[4] The insulating film according to any one of the above [1] to [3], wherein the (E) component contains an insulating filler (E1) having an average particle diameter of 0.1 to 0.8 μm, and the average particle diameter is An insulating filler (E2) of 2 to 6 μm and an insulating filler (E3) having an average particle diameter of 7 to 30 μm.

[5] The insulating film according to the above [4], wherein the average particle diameter of the (E3) component is 15 to 30 μm.

[6] A semiconductor device comprising the cured product of the insulating film according to any one of the above [1] to [5].

According to the present invention [1], it is possible to provide an insulating film which has excellent film characteristics and excellent heat resistance after hardening, and has a thermal conductivity of 3.0 W / mK or more.

According to the present invention [6], a highly reliable semiconductor device can be provided by a hardened body of an insulating film excellent in heat resistance and thermal conductivity.

Figures 1 (A) to (E) are schematic diagrams for explaining the method of blade coating.

[Insulation film]

The insulating film of the present invention contains (A) a novolac epoxy resin, (B) a butadiene acrylonitrile copolymer, (C) an aralkylphenol resin, (D) a hardening catalyst, And (E) an insulating filler having a thermal conductivity of 20 W / mK or more, wherein (B) component is 10 to 20 parts by mass with respect to 100 parts by mass of the total of (A) to (C) ingredients, and (E) ingredient It is 60 to 85% by volume with respect to 100% by volume of the insulating film.

The (A) component imparts heat resistance to an insulating film. From the viewpoint of heat resistance, the component (A) is preferably a cresol novolac type epoxy resin. The cresol novolac type epoxy resin can be specifically exemplified by the following formula (1) Novolac novolac epoxy resin.

(In the formula, n represents an average value, and is 1 to 10, preferably 1 to 5.)

The epoxy equivalent of the component (A) is preferably from 150 to 300 g / eq from the viewpoint of heat resistance after curing of the composition for an insulating film. The composition for an insulating film will be described later. Examples of commercially available products of the component (A) include cresol novolac epoxy resin (product name: N-665-EXP) made by DIC. (A) Ingredients can be used alone or in combination of two or more.

The component (B) is used for film properties such as flexibility, and can be used as a liquid at normal temperature. (B) The ingredients are liquid at normal temperature, for example Butadiene acrylonitrile copolymer with lower average molecular weight. In addition, the (B) component can be used for a butadiene acrylonitrile copolymer having a terminal that reacts with an epoxy group at the terminal. The component (B) is particularly carboxyl-terminated butadiene acrylonitrile copolymer from the viewpoint of reactivity with (A) novolac epoxy resin and compatibility with (A) novolac epoxy resin, Amine-terminated butadiene acrylonitrile copolymer and epoxy-terminated butadiene acrylonitrile copolymer are preferred. The acrylonitrile content of these butadiene acrylonitrile copolymers is preferably 10 to 40% by mass, and more preferably 15 to 30% by mass. For carboxy-terminal butadiene. In the case of an acrylonitrile copolymer, the carboxyl ratio is preferably 1.8 to 3.0%. The component (B) is preferably one having a weight average molecular weight of 3,000 to 5,000. The weight average molecular weight is obtained by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. Examples of commercially available products of the component (B) include butadiene acrylonitrile rubber (product name: HYCAR CTBN1300) manufactured by Ube Industries. (B) Ingredients can be used alone or in combination of two or more.

Examples of the component (C) include an aralkylphenol resin represented by the following formula (2).

(Wherein R ₁ independently represents a halogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a phenyl group, and r represents 0 to 3 For integers, r is preferably 0, and m represents the average value, which is 1 to 10, preferably 1 to 5, and more preferably 1.)

By adding the (C) component, it is possible to improve the heat resistance and crack resistance of the cured insulating film. Examples of the commercially available product of the component (C) include an aralkylphenol resin (product name: XLC4L) manufactured by Mitsui Chemicals.

The component (D) is only required to have a hardening ability with an insulating film. With the (D) component, the curing time of the insulating film can be shortened, and the curing step can be shortened. In addition, with the (D) component, the hardenability of the insulating film is improved, and the cured insulating film has good characteristics. Examples of the component (D) include imidazole-based hardening catalysts, amine-based hardening catalysts, and carboxylic acid dihydrazide hardening catalysts. From the viewpoint of the hardenability of the insulating film, an imidazole-based hardening catalyst is more preferable.

Examples of the imidazole curing catalyst include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 2,4-diamine-6- [2'-methylimidazole- (1 ')] ethyl-s-tri , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a ] Benzimidazole and the like, from the viewpoint of the curing speed of the insulating film, 2-ethyl-4-methylimidazole, 2,4-diamine-6- [2'-methylimidazole- (1 ') ] Ethyl-s-tri And so on.

Examples of the amine-based curing catalyst include a chain aliphatic amine, a cyclic aliphatic amine, a fatty aromatic amine, and an aromatic amine, and an aromatic amine is preferred. Examples of the carboxylic acid dihydrazide curing catalyst include dihydrazide adipate, dihydrazide isophthalate, dihydrazide sebacate, dihydrazide dodecanate, and the like. Halohydrazine is preferred.

Examples of commercially available products of the component (D) include 2-ethyl-4-methylimidazole (product name: 2E4MZ) manufactured by Shikoku Kasei and 2,4-diamine-6- [2 manufactured by Shikoku Kasei '-Methylimidazole- (1')]-ethyl-s-tri (Product name: 2MZ-A), Nippon Kasei amine hardener (Product name: KAYAHARD AA), Japan FINECHEM adipic acid dihydrazide (Product name: ADH), etc., but the (D) component is not limited to these. (D) Ingredients can be used alone or in combination of two or more.

Examples of the (E) component include alumina (Al ₂ O ₃ ), magnesium oxide (MgO), lead hafnium oxide (ZnO), boron nitride (BN), silicon carbide (SiC), and aluminum nitride. (AlN), silicon nitride (Si ₃ N ₄ ), diamond, etc. The (E) component is preferably at least one selected from the group consisting of aluminum oxide, magnesium oxide, and boron nitride from the viewpoint of durability to thermal conductivity and humidity. An example of the measurement results of the thermal conductivity of each material is (unit: W / mK) Al ₂ O ₃ is 20 to 40, MgO is 45 to 60, ZnO is 54, BN is 30 to 80, SiC is 140 to 170, and AlN is 150 to 250, Si ₃ N ₄ is 30 to 80, and diamonds are 1000 to 2000. As for the commercially available product of the (E) component, spherical alumina (Al ₂ O ₃ ) powder (product name: ASFP-20, DAM-03, DAM-05, DAM-07) manufactured by the Denka Chemical Industry, and Showa Spherical alumina (Al ₂ O ₃ ) powder (product name: CB-A20S) manufactured by Denko, and magnesium oxide powder (product name: SMO-05) manufactured by Sakai Chemical Industry.

(E) The composition is composed of an insulating filler (E1) having an average particle diameter of 0.1 to 0.8 μm, an insulating filler (E1) having an average particle diameter of 2 to 6 μm, and an insulating filler having an average particle diameter of 7 to 30 μm. (E3) is preferred. By using these fillers in combination, the insulating filler will be more densely distributed in the insulating film, so even if it is the same insulating filler, The thermal conductivity of the cured insulating film is higher. Here, the average particle diameter of the (E) component is measured with a laser analytical particle size analyzer. (E) Ingredients can be used alone or in combination of two or more.

From the viewpoint of thermal conductivity, the average particle diameter of the (E3) component is more preferably 15 to 30 μm. Since the component (E) contains a filler having a coarse particle diameter, a higher thermal conductivity can be imparted to the cured insulating film. However, if it contains an insulating filler with an average particle size of more than 30 μm, coarse particles can easily cause the coating film surface of the insulating film composition to be rough, damage the appearance of the coating film, and cause streaks and damage during the coating of the insulating film composition. Problems such as the insulation properties of the cured insulating film make it difficult to obtain an insulating film with a thin film thickness.

The component (A) is preferably 30 to 50 parts by mass based on 100 parts by mass of the total of the components (A) to (C).

(B) The component is 10 to 20 parts by mass with respect to 100 parts by mass of the total of the components (A) to (C). When the amount is less than 10 parts by mass, the insulating film becomes hard, and problems such as cracking easily occur, which cannot be obtained. Film characteristics. On the other hand, when the component (B) exceeds 20 parts by mass, the resin component becomes too soft, and the contact of the insulating filler of the component (E) becomes weak, so the thermal conductivity decreases.

The phenol equivalent of the component (C) is preferably 1.0 to 1.6 times the epoxy equivalent of the (A) component, and more preferably 1.2 to 1.4 times. When it is less than 1.0 times, there is no lack of sufficient heat resistance. On the other hand, if the phenol equivalent of the component (C) exceeds 1.6 times, the hardened material becomes hard and brittle, and becomes easily broken.

(D) component, from the viewpoint of storage stability and hardenability of the insulating film, with respect to 100 parts by mass of the total of (A) to (D) component, It is preferably from 0.1 to 5 parts by mass.

(E) The composition is 60 to 85% by volume with respect to 100% by volume of the insulating film. If it is less than 60% by volume, the required thermal conductivity cannot be obtained. If it exceeds 85% by volume, the film characteristics of the composition for the insulating film are deteriorated 3. The insulation film becomes brittle, and the bonding strength of the insulation film after hardening is reduced. In addition, it is preferable to contain (E1) 5 to 15 mass%, (E2) 5 to 55 mass%, and (E3) 35 to 85 mass% with respect to the entire mass of the insulating filler. From the viewpoint of thermal conductivity, (E3) is preferably an average particle diameter of 15 to 30 μm, and at this time (E3) is preferably 30 to 50% by mass based on the entire mass of the insulating filler.

[Composition for insulating film]

The composition for an insulating film (hereinafter also referred to as a composition) for forming an insulating film contains the above components (A) to (E). In addition, the composition for an insulating film may contain additives such as a silane coupling agent, an adhesion-imparting agent, a defoaming agent, a flow modifier, a film-forming aid, and a dispersant, and an organic solvent so long as the effects of the present invention are not impaired.

Examples of the organic solvent include aromatic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone (MEK) and methyl isobutyl ketone. The organic solvents may be used alone or in combination of two or more. In addition, the use amount of the organic solvent is not particularly limited, and it is preferable to use it so that the solid content becomes 20 to 50% by mass. From the viewpoint of workability, the composition for an insulating film is 200 to 3000 mPa. The range of viscosity of s is preferable. Viscosity is based on E-type viscometer at 10 rpm, 25 Measured at ℃.

This composition is obtained by dispersing the component (E) due to a liquid raw material containing the components (A) to (D) dissolved in an organic solvent. There is no particular limitation on the device for dissolving or dispersing such raw materials, but a dissolver, a planetary mixer, a grinder, a three-roll mill, a ball mill, a bead mill, or the like can be used. These devices may also be provided with heating devices. These devices can also be used in appropriate combination.

The insulating film is obtained by applying the composition to a desired support and then drying it. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, polyester resins, polyethylene resins, and organic films such as polyethylene terephthalate resins. The support system can be demolded with silicon compounds.

The method of coating the composition on a support is not particularly limited, and from the viewpoints of thin film formation and film thickness control, a micro gravure method, a slot die method, and a doctor blade method are preferred. By the slit die method, an insulating film having a thickness of 10 to 300 μm after heat curing can be obtained.

The drying conditions can be appropriately set depending on the type or amount of the organic solvent used in the composition, the coating thickness, and the like, and can be set at, for example, 50 to 120 ° C. for about 1 to 30 minutes. The insulating film thus obtained has good storage stability. The insulating film can be peeled from the support at a desired time.

The insulating film can be thermally cured at 130 to 220 ° C. for 30 to 180 minutes, and then be adhered. When the adherend of the heating body and the adherend of the heating body are next, the hardened insulation film The heat from the adherend of the heating body is transferred to the adherend side of the heat-receiving body, and the heat is released from the adherend side of the heat-receiving body. Further, the hardened insulating film plays a role of reducing the stress caused by the difference in thermal expansion coefficient between the adherend of the heating element and the adherend of the heating element.

The thickness of the insulating film is preferably 10 μm to 300 μm, and more preferably 20 μm to 150 μm. If it is less than 10 μm, the desired insulation properties may not be obtained. If it exceeds 300 μm, the adherend which generates heat may not be able to sufficiently radiate heat.

In addition, a hardened insulating film is more preferable if it has a thermal conductivity of 3 W / mK or more. In addition, if the thermal conductivity of the hardened insulating film is less than 3 W / mK, the heat transfer from the heating element to the receiver may be insufficient. The thermal conductivity of the hardened insulating film can be controlled by the type and content of the (E) component.

The hardened insulating film has a volume resistivity of 1 × 10 ¹⁰ Ω. Above cm is preferred. If the volume resistivity of the high thermal conductivity layer is 1 × 10 ¹² Ω. Above cm is even better, 1 × 10 ¹³ Ω. Above cm is even better. The volume resistivity of the hardened insulating film has not reached 1 × 10 ¹⁰ Ω. cm, it may not be able to meet the insulation required by semiconductor devices.

[Semiconductor device]

The semiconductor device of the present invention is a hardened body containing the above-mentioned insulating film. A highly reliable semiconductor device can be provided by a hardened body of an insulating film having excellent heat resistance and thermal conductivity. Examples of the semiconductor device include a heat-generating body such as a module or an electronic component and a heat-receiving body such as a substrate with an insulating film. A hardened object, a substrate that receives heat from a heating element, and a heat-releasing plate that further receives heat from this substrate, such as a hardened object, with an insulating film.

[Example]

Although the present invention is described by way of examples, the present invention is not limited thereto. In addition, in the following examples, unless otherwise specified, the part and% represent mass parts and mass%.

[Examples 1 to 9, Comparative Examples 1 to 7]

First, the (A) component, the (B) component, and the (C) component were each dissolved and diluted with MEK so that NV (non-volatile content, that is, (A) to (C) component) becomes 30% by mass. Secondly, according to the order of (A) to (C) ingredients and (D) ingredients, additives, (E) ingredients, a predetermined amount of each raw material is taken to a container for rotation. MAZERUSTAR was stirred and mixed for 5 minutes, and then dispersed using a planetary mixer, and the viscosity was adjusted to 1000 to 5000 mPa.s with MEK to prepare a composition for an insulating film.

[Evaluation method] 1. Determination of thermal conductivity

The obtained composition for an insulating film was subjected to doctor blade coating on a 50 μm-thick PET film to which a release agent was applied so that the film thickness after drying became 200 to 500 μm. FIG. 1 is a schematic diagram illustrating a method of blade coating. First, on a PET film to which a mold release agent is attached, the spacers are overlapped by two lines so as to have an appropriate thickness, and then attached with an adhesive tape (Fig. 1 (A)). Put an appropriate amount of insulating film on the PET film with release agent Use the composition (Fig. 1 (B)). A glass slide was placed on a spacer, and the composition for an insulating film was scraped off and applied (Figs. 1 (C) to (E)). Here, the coated insulating film composition is sufficiently dried, and the obtained insulating film is peeled off from the PET film, and then a vacuum press machine is used under the conditions of 200 ° C. for 60 minutes and 0.1 MPa. Its hardened. The cured insulating film was cut into 10 × 10 mm to prepare a test piece for measuring thermal conductivity. The thermal conductivity of the produced test piece for measuring thermal conductivity was measured with a thermal conductivity meter (model: LFF447Nanoflash) made by NETSCH. Tables 1 and 2 show the measurement results of the thermal conductivity.

2. Film characteristics

The obtained composition for an insulating film was applied to a 50 μm-thick PET film to which a release agent was applied, so that the film thickness was 20 cm in width and the thickness of the film after drying was 50 to 100 μm, using a coater for coating. The applied composition for an insulating film was dried at 80 ° C. for 20 minutes to obtain an insulating film. The obtained insulating film was wound on a reel having a width of 50 mm φ and a width of 40 cm, and the film characteristics were evaluated visually. When there is sufficient flexibility without cracking, it is recorded as "○", when there is cracking, it is recorded as "X". Tables 1 and 2 show the results of the film characteristics.

3. Solder heat resistance

The obtained composition for an insulating film was applied on a 50 μm-thick PET film to which a release agent was applied, so that the film thickness was 20 cm in width and the film thickness after drying was 50 to 100 μm, using a coater. The coated insulation film composition was dried at 80 ° C for 20 minutes to obtain an insulation with a PET film. film. The obtained insulating film with a PET film was peeled from the PET film, sandwiched between two pieces of copper foil of 50 mm × 100 mm × 30 μm, and hardened using a vacuum extruder at 200 ° C. for 60 minutes and 0.1 MPa. The hardened sample was cut into 30 × 30 mm, and immersed in a solder bath at 290 ° C. for 2 minutes, and evaluated visually. Here, the solder of the solder bath is a lead-free solder (product name: SN96Cl (010), tin: silver: copper: flux) made by Nihon Superior = 91.7: 4: 1.3: 3 (mass%). The hardened sample is not peeled "○" when bulging or "x" when the hardened sample peeled and / or bulging. Tables 1 and 2 show the results of solder heat resistance.

1) Cresol novolac epoxy resin (product name: N-665-EXP) made by DIC

2) Butadiene acrylonitrile rubber produced by Ube (Product name: HYCAR CTBN1300)

3) Mitsubishi Chemical's bisphenol A epoxy resin (product name: JER828)

4) Aralkylphenol resin made by Mitsui Chemicals (product name: XLC4L)

5) Phenol modified xylene resin made by fudow (product name: PR-1440M)

6) New Japan Physical and Chemical Anhydride Hardener (Product Name: Rikajitto MH-700)

7) 2-Ethyl-4-methylimidazole produced by Shikoku Kasei (Product name: 2E4MZ)

8) 2,4-diamine-6- [2'-methylimidazole- (1 ')]-ethyl-s-tri (Product Name: 2MZ-A)

9) Spherical alumina powder (Product name: ASFP-20, average particle size: 0.3 μm) made by the Denki Chemical Industry

10) alumina powder manufactured by Denki Chemical Industry (product name: DAM-03, average particle size: 3.7 μm)

11) alumina powder manufactured by Denki Chemical Industry (product name: DAM-05, average particle size: 5 μm)

12) alumina powder manufactured by Denki Chemical Industry (product name: DAM-07, average particle size: 8 μm)

13) Showa Denko spherical alumina powder (product name: CB-A20S, average particle size: 21 μm)

14) Spherical magnesium oxide powder made by Sakai Chemical Industry (product name: SMO-05, average particle size: 8 μm)

15) 3-glycidoxypropyl trimethoxysilane manufactured by Shin-Etsu Chemical Industry (product name: KBM-403)

16) Dispersant manufactured by Kusumoto Chemicals, Ltd. (product name: ED152)

17) Methyl ethyl ketone (product name: MEK) manufactured by Exxon Mobil Corporation

As can be seen from Tables 1 and 2, in all Examples 1 to 9, all the results of thermal conductivity, film characteristics, and solder heat resistance were good. In comparison, Comparative Example 1 which has too much (E) component has poor film characteristics. (E) Comparative Example 2 with too little component has low thermal conductivity. (B) Comparative Example 3 with too many components also had low thermal conductivity. (B) Comparative Example 4 is a film whose composition is too small and has poor characteristics. Comparative Example 5 using phenol-modified xylene in place of the component (C) also had poor film properties. The film properties of Comparative Example 6 using the acid anhydride-based substitution (C) component were also poor. Comparative Example 7 which uses a bisphenol A type epoxy resin in place of the components (A) and (C) has poor heat resistance.

As described above, the insulating thin film of the present invention has excellent characteristics and excellent heat resistance after hardening, and has a thermal conductivity of 3.0 W / mK or more, and its hardened material can provide a highly reliable semiconductor device.

Claims (6)

An insulating film comprising (A) a novolac epoxy resin, (B) a butadiene acrylonitrile copolymer, (C) an aralkylphenol resin, (D) a hardening catalyst, and (E) a thermal conductivity 20W / mK or more insulation filler, wherein (B) component is 10 to 20 parts by mass with respect to 100 parts by mass of the total of (A) to (C) ingredients, and the phenol equivalent of the (C) ingredient is the (A) ingredient The epoxy equivalent is 1.0 to 1.6 times, and the (E) component is 60 to 85% by volume based on 100% by volume of the insulating film. The insulating film according to item 1 of the scope of patent application, wherein the (D) component is an imidazole-based hardening catalyst. The insulating film according to item 1 or 2 of the scope of patent application, wherein the (E) component is at least one selected from the group consisting of alumina, magnesia, and boron nitride. The insulating film according to item 1 or 2 of the scope of patent application, wherein (E) component contains an insulating filler (E1) having an average particle diameter of 0.1 to 0.8 μm, and an insulating filler having an average particle diameter of 2 to 6 μm (E2), and an insulating filler (E3) having an average particle diameter of 7 to 30 μm. The insulating film according to item 4 of the scope of patent application, wherein the average particle diameter of the (E3) component is 15 to 30 μm. A semiconductor device comprising a hardened body of an insulating film according to any one of claims 1 to 5 of the scope of patent application.