KR20130087430A - Silicone structure-bearing polymer, resin composition, and photo-curable dry film - Google Patents

Abstract

PURPOSE: A silicon skeleton-containing polymer compound is provided to alleviate a separation problem on a metal wire such as Cu and Al, an electrode, a substrate, or SiN substrate and to form micropatterns in a wide wavelength region. CONSTITUTION: A silicon skeleton-containing polymer compound is a resin including a silicone skeleton having a crosslinkable group or a reaction point deriving a crosslinking reaction, is formed by coupling an isocyanuric acid skeleton with a terminal of the molecule, and has a weight average molecular weight of 3,000-500,000. A resin composition comprises the silicon skeleton-containing polymer compound; a crosslinking agent; a photoacid generator generating acids by being decomposed by a light with a wavelength of 190-500 nm; and a solvent.

Description

Silicone skeleton-containing polymer compound, resin composition, photocurable dry film {SILICONE STRUCTURE-BEARING POLYMER, RESIN COMPOSITION, AND PHOTO-CURABLE DRY FILM}

This invention consists of a silicone skeleton containing polymer compound, its manufacturing method, the resin composition containing the said polymer compound, and the said resin composition, and the ultraviolet-ray of wavelength 500nm or less (near ultraviolet and an ultraviolet region), such as i line | wire and g line | wire, Chemical amplification-type negative resist material which can be patterned by exposure, the photocurable dry film and its manufacturing method, the laminated body formed using the photocurable dry film, the pattern formation method, and wiring, a circuit, a board | substrate, etc. It is related with the film for electronic component protection.

Although the pattern of the negative resist material formed is used for the purpose of the protective film which covers a wiring, a circuit, a board | substrate, etc., the pattern of a negative resist material coats on the wiring, the metal layer of Cu of a circuit, or a board | substrate. Since the adhesion to Al metal electrode existing or SiN substrate which is an insulated substrate of a wiring and a circuit to cover is inferior, peeling problem is frequently encountered.

However, the pattern formed by the chemically amplified negative resist material or the dry film using the material of the present invention can greatly improve substrate adhesion.

Moreover, since the said protective film of this invention has heat resistance, chemical-resistance, insulation, and flexibility, it is an insulating film for semiconductor elements, an insulating film for multilayer printed circuit boards, an insulating film for multilayer printed circuit boards, a solder mask, a coverlay film, and the penetration of a silicon substrate including redistribution use. In addition to the insulating film for embedding the wiring TSV, it is effective for substrate bonding applications and the like.

BACKGROUND ART With the miniaturization and high performance of various electronic devices such as PCs, digital cameras, and cellular phones, the demand for further miniaturization, thinning, and high density in semiconductor devices is rapidly increasing. Therefore, in the high-density mounting technique such as chip size package or chip scale package (CSP) or three-dimensional lamination, which can cope with an increase in substrate area in productivity improvement, fine and high aspect ratio irregularities are formed on the substrate. The development of the photosensitive insulating material which can respond to a structure is calculated | required.

As the photosensitive insulating material described above, it can be applied over a wide film thickness by a spin coating method commonly used in semiconductor device manufacturing processes, and fine patterns can be formed in a wide wavelength range, Photocurable resin composition which provides a coating for protecting electrical and electronic parts with excellent flexibility, heat resistance, electrical properties, adhesion, reliability and chemical resistance by postcure (Patent Document 1: Japanese Patent Application Laid-Open No. 2008-184571) Has been proposed. This spin coat method has an advantage of easily forming a film on a substrate.

On the other hand, although the photocurable resin composition which provides the said film for electrical / electronic component protection is used by the film thickness of 1-100 micrometers on a board | substrate, the viscosity of the photocurable resin composition from the time when film thickness exceeds 30 micrometers Since is very high, the film-forming on the board | substrate by a spin coat method is practically limited and becomes difficult.

Moreover, when apply | coating the said photocurable resin composition to the board | substrate with an unevenness | corrugation on the surface by the said spin coat method, it is difficult to coat | cover the said board | substrate substantially uniformly. Therefore, the gap of the photocurable resin layer is easily formed in the stepped portion on the substrate, and the situation is waiting for further improvement in flatness and step coverage. Moreover, as another coating method which replaces the said spin coat method, the spray method (patent document 2: Unexamined-Japanese-Patent No. 2009-200315) is proposed. However, due to the principle, defects such as high and low differences resulting from irregularities of the substrate, or film breaks at the pattern edges and pinholes at the bottom of the recesses occur, and problems with flatness and step coverage are still not sufficiently solved.

In recent years, in high-density mounting techniques such as chip size packages or chip scale packages (CSPs) or three-dimensional stacking, fine patterns having a high aspect ratio are formed on a substrate, and metals such as copper are formed on the obtained patterns. The technique of redistributing from a chip | tip by laminating | stacking is actively performed. Due to the higher density and higher integration of chips, there is a strong demand for the pattern line width in the redistribution technology and the miniaturization of the contact hole size for connecting the substrates. As a method of obtaining a fine pattern, a lithography technique is common, and among these, a chemically amplified resist material is suitable for obtaining a fine pattern. In addition, the pattern used for redistribution permanently exists between the device chip and the chip, and has a characteristic of hardening, and is an excellent film for protecting electrical and electronic parts having excellent flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance. Since it is necessary to act as a resist, the resist material which obtains a pattern is considered to be suitable for negative type (patent document 3: Unexamined-Japanese-Patent No. 2003-114531).

Therefore, a chemically amplified negative resist material can be mentioned as a pattern forming material which can process fine redistribution, and an electrical / electronic component protection film excellent in flexibility, heat resistance, electrical characteristics, adhesiveness, reliability, and chemical resistance.

On the other hand, chemically amplified negative resist materials which can be used to form fine patterns used when processing redistribution and are useful for the protective film for electric and electronic components can be coated on the substrate or previously present on the substrate. The Al electrode may be coated, and the substrate on which the wiring and the electrode are formed may have an insulating substrate such as SiN, and the SiN substrate may be widely covered, but the coating film layer of the chemically amplified negative resist material and the substrate Adhesion is still not enough, and often faces the problem that the coating layer of resist material peels from a board | substrate.

Therefore, a high-density chip and a high-integration chip are required to reduce the size of the pattern in the redistribution technology, and to be a chemically amplified negative resist material useful for a protective film for electrical and electronic parts, and to improve the adhesion on the substrate. It is becoming.

Japanese Patent Application Publication No. 2008-184571 Japanese Patent Application Publication No. 2009-200315 Japanese Patent Application Publication No. 2003-114531

This invention is made | formed in view of the said situation, The negative type which can form a fine pattern, and can solve the peeling problem facing on the metal wiring like Cu and Al, the board | substrate with electrodes, or the board | substrate like SiN. An object of the present invention is to provide a silicon skeleton-containing polymer compound, a method for producing the same, a resin composition containing the polymer compound, and a chemically amplified negative resist material comprising the resin composition.

Moreover, another object of this invention is to provide the photocurable dry film using the said resin composition, its manufacturing method, and the laminated body formed using this photocurable dry film.

In addition, the present invention provides a wide film even on a substrate having irregularities by using a pattern forming method of simply applying a negative resist material on a substrate by spin coating and forming a fine pattern, and the photocurable dry film. Electrical, such as wiring, a circuit, a board | substrate, etc. using the pattern forming method which can form a resist layer over thickness, and the pattern obtained by the said pattern formation method, and the hardened film obtained by carrying out postcure at low temperature. Another object is to provide an electronic component protective film.

MEANS TO SOLVE THE PROBLEM The present inventors examined repeatedly, in order to achieve the said objective,

(A) A resin containing a silicone skeleton having a reaction point at which a crosslinking group or a crosslinking reaction occurs in a molecule, wherein the isocyanuric acid skeleton is bonded to a molecule or a terminal group and contains a silicone skeleton having a weight average molecular weight of 3,000 to 500,000. A high molecular weight compound, especially the silicone skeleton containing high molecular weight compound which has a weight average molecular weight of 3,000-500,000 which has a repeating unit represented by following General formula (1),

[Formula 1]

(Wherein among, R ¹ ~R ⁴ will be the same and represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, which may be different. M is an integer of 1~100. A, b, c, d is 0 or a positive number, e and f are positive, and a, b, c, and d are not simultaneously 0. However, a + b + c + d + e + f is 1. In addition, X is a divalent organic group represented by the general formula (2), and Y is general. Divalent organic group represented by formula (3), and W is a divalent organic group represented by general formula (4-1) and / or monovalent organic group represented by general formula (4-2))

[Formula 2]

(Wherein Z is

(3)

It is a divalent organic group chosen from either, n is 0 or 1. R <^5> and R <^6> is a C1-C4 alkyl group or alkoxy group, respectively, and may mutually differ or may be the same. k is any one of 0, 1, 2)

[Formula 4]

Where V is

[Chemical Formula 5]

It is a divalent organic group chosen from either, and p is 0 or 1. R <^7> and R <^8> is a C1-C4 alkyl group or alkoxy group, respectively, and may mutually differ or may be the same. h is any one of 0, 1, 2)

[Formula 6]

(Wherein T ¹ and T ² may be the same or different,

[Formula 7]

Of a monovalent group selected from any one, R ⁹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ¹⁰ is an alkyl group or an alkoxy group of a hydrogen atom, a group having 1 to 4 carbon atoms, or - (CH _{2) s} OH ( s = 0 to 3))

(B) an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, or a compound in which a hydroxyl group of a polyhydric phenol is substituted with a glycidoxy group One or two or more crosslinking agents selected from

(C) a photoacid generator which is decomposed by light having a wavelength of 190 to 500 nm and generates an acid,

(D) Solvent

A fine pattern can be formed by a chemically amplified negative resist material composed of a resin composition comprising a metal composition, and can greatly improve the peeling problem faced on a metal wiring such as Cu or Al, an electrode, a substrate, or a substrate such as SiN. I found it possible.

Moreover, it discovered that the cured film obtained by the said pattern formation method was excellent as a film for electrical and electronic component protection, and came to complete this invention.

Therefore, this invention provides the following matters.

[One]

A resin comprising a silicone skeleton having a reaction point at which a crosslinking group or a crosslinking reaction occurs in a molecule, wherein the isocyanuric acid skeleton is bonded to a molecule or a terminal group, and has a weight average molecular weight of 3,000 to 500,000. Containing high molecular compounds.

[2]

The isocyanuric acid skeleton is a divalent organic group represented by the following general formula (4-1) and / or a monovalent organic group represented by the following general formula (4-2). Polymer compounds.

[Formula 8]

(Wherein T ¹ and T ² may be the same or different,

[Chemical Formula 9]

Of a monovalent group selected from any one, R ⁹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ¹⁰ is an alkyl group or an alkoxy group of a hydrogen atom, a group having 1 to 4 carbon atoms, or - (CH _{2) s} OH ( s = 0 to 3))

[3]

Silicone skeleton containing high molecular compound as described in [1] or [2] which has a repeating unit represented by following General formula (1).

[Formula 10]

(Wherein among, R ¹ ~R ⁴ will be the same and represents a monovalent hydrocarbon group having 1 to 8 carbon atoms, which may be different. M is an integer of 1~100. A, b, c, d is 0 or a positive number, e and f are positive, and a, b, c, and d are not simultaneously 0. However, a + b + c + d + e + f is 1. In addition, X is a divalent organic group represented by the general formula (2), and Y is general. Divalent organic group represented by formula (3), and W is a divalent organic group represented by general formula (4-1) and / or monovalent organic group represented by general formula (4-2))

[Formula 11]

(Wherein Z is

[Chemical Formula 12]

It is a divalent organic group chosen from either, n is 0 or 1. R <^5> and R <^6> is a C1-C4 alkyl group or alkoxy group, respectively, and may mutually differ or may be the same. k is any one of 0, 1, 2)

[Chemical Formula 13]

Where V is

[Formula 14]

It is a divalent organic group chosen from either, and p is 0 or 1. R <^7> and R <^8> is a C1-C4 alkyl group or alkoxy group, respectively, and may mutually differ or may be the same. h is any one of 0, 1, 2)

[Formula 15]

(Wherein T ¹ and T ² may be the same or different,

[Chemical Formula 16]

Of a monovalent group selected from any one, R ⁹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ¹⁰ is an alkyl group or an alkoxy group of a hydrogen atom, a group having 1 to 4 carbon atoms, or - (CH _{2) s} OH ( s = 0 to 3))

[4]

In the formulas (4-1) and (4-2), T ¹ or T ² is represented by the following formula: The silicone skeleton-containing polymer compound according to [2] or [3].

[Chemical Formula 17]

[5]

Hydrogensilphenylene represented by the following general formula (5)

[Chemical Formula 18]

And dihydroorganosiloxane represented by the following general formula (6):

[Chemical Formula 19]

(In formula, R <^3> , R <^4> and m are the same as the above.)

And an epoxy group-containing compound having a diallyl group represented by the following General Formula (7)

[Chemical Formula 20]

(V, R ⁷ , R ⁸ , p, h are the same as above.)

And / or a phenol compound having a diallyl group represented by the following general formula (8)

[Chemical Formula 21]

(Wherein Z, R ⁵ , R ⁶ , n, k are the same as above)

And an isocyanuric acid skeleton-containing compound having a diallyl group represented by the following General Formula (9) and / or an allyl group represented by the following General Formula (10).

[Chemical Formula 22]

(In formula, T <^1> , T <^2> is the same as the above.)

The method for producing a silicone skeleton-containing polymer compound according to [3], wherein the polymerization reaction is carried out in the presence of a catalyst.

[6]

0.1-10.0 mass% of isocyanuric acid frame | skeleton containing compound is added with respect to the silicone polymer compound raw material total amount, The manufacturing method of the silicone skeleton containing polymer compound as described in [5] characterized by the above-mentioned.

[7]

(A) The silicone skeleton-containing polymer compound according to any one of [1] to [4],

(B) an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, or a compound in which a hydroxyl group of a polyhydric phenol is substituted with a glycidoxy group One or two or more crosslinking agents selected from

(C) a photoacid generator which is decomposed by light having a wavelength of 190 to 500 nm and generates an acid,

(D) Solvent

Resin composition containing the.

[8]

The chemically amplified negative resist material which consists of a resin composition as described in [7].

[9]

The photocurable resin layer whose film thickness is 10-100 micrometers is a photocurable dry film which has a structure sandwiched between a support film and a protective film, The photocurable resin composition used for formation of a photocurable resin layer is described in said [7]. It consists of a resin composition, The photocurable dry film characterized by the above-mentioned.

[10]

(1) applying the chemically amplified negative resist material according to [8] onto a substrate,

(2) Next, after the heat treatment, a step of exposing to a high energy ray or electron beam having a wavelength of 190 to 500 nm through a photomask;

(3) The pattern formation method characterized by including the process of developing using a developing solution after heat processing.

[11]

Furthermore, the pattern formation method as described in [10] including the process of post-curing the film formed pattern by the (4) image development after image development at the temperature of 100-250 degreeC.

[12] The cured product layer of the photocurable resin composition formed of the photocurable dry film according to [9] on a substrate having a groove and / or a hole having an opening width of 10 to 100 µm and a depth of 10 to 120 µm. Laminated body formed by lamination.

[13]

(i) Process of apply | coating resin composition as described in [7] on support film,

(ii) drying the resin composition to form a photocurable resin layer on the support film;

(iii) Furthermore, the manufacturing method of the photocurable dry film containing the process of bonding a protective film on the said photocurable resin layer.

[14]

(i) Process of peeling a protective film from the photocurable dry film as described in [9], contacting the exposed photocurable resin layer to a board | substrate, and forming a film,

(ii) exposing to light having a wavelength of 190 to 500 nm through a photomask through the support film or in a state where the support film is peeled off;

(iii) performing a post-exposure heat treatment,

(iv) Process of developing with developer

Pattern forming method comprising a.

[15]

Furthermore, the pattern formation method as described in [14] including the process of post-curing the film patterned by (v) image development at the temperature of 100-250 degreeC after image development.

[16]

The pattern formation method as described in [14] or [15] whose board | substrate is a board | substrate which has a groove | channel and / or a hole whose opening width is 10-100 micrometers, and whose depth is 10-120 micrometers.

[17]

The film for electrical and electronic component protection which consists of a hardened film obtained by the pattern formation method as described in [15].

According to the present invention, it is possible to drastically improve the peeling problem faced on metal wirings such as Cu and Al, electrodes, substrates, or substrates such as SiN, so that fine patterns can be formed in a wide wavelength range. According to the densification and high integration of the chip, the pattern in the redistribution technology can be refined, and a chemically amplified negative resist material, a photocurable dry film, and a pattern forming method using the same can be provided which are useful for the film for protecting electrical and electronic components. have.

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing which shows the adhesiveness measuring method in an Example.

[Silicon Skeleton-Containing Polymer Compound]

The silicone skeleton-containing polymer compound of the present invention is a resin containing a silicone skeleton having a reaction point at which a crosslinking group or a crosslinking reaction occurs in a molecule, and is obtained by binding an isocyanuric acid skeleton in a molecule or a terminal group, and having a weight average molecular weight It is 3,000-500,000.

In this case, it is preferable that the isocyanuric acid skeleton is a divalent organic group represented by General Formula (4-1) and / or a monovalent organic group represented by General Formula (4-2).

(23)

(Wherein T ¹ and T ² may be the same or different,

&Lt; EMI ID =

Of a monovalent group selected from any one, R ⁹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ¹⁰ is an alkyl group or an alkoxy group of a hydrogen atom, a group having 1 to 4 carbon atoms, or - (CH _{2) s} OH ( s = 0 to 3))

Specifically, what has a repeating unit represented by following General formula (1) is mentioned.

(25)

In formula, R ¹ ~R ⁴ represents a group which may be the same or different, a group having 1 to 8 carbon atoms, preferably one of 1 to 6 hydrocarbons. Specific examples thereof include a straight chain, branched or cyclic alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group and cyclohexyl group, vinyl group, allyl group, Branched or cyclic alkenyl groups such as a methyl group, an ethyl group, a n-butyl group, a hexyl group, and a cyclohexenyl group, an aryl group such as a phenyl group or a tolyl group, an aralkyl group such as a benzyl group or a phenylethyl group.

In addition, m is an integer of 1-100, Preferably it is an integer of 1-80 from a viewpoint of compatibility with a crosslinking agent and a photo-acid generator mentioned later, and photocurability. In addition, a, b, c and d are zero or positive, e and f are positive, and a, b, c and d are not zero at the same time from the viewpoint of adhesion to the substrate, electrical characteristics and reliability. In this case, a is preferably 0 ≦ a ≦ 0.8, more preferably 0.2 ≦ a <0.8, particularly preferably 0.2 ≦ a ≦ 0.7, and b is preferably 0 ≦ b <1.0, Preferably 0.1 ≦ b <0.8, particularly preferably 0.1 ≦ b ≦ 0.5, c is preferably 0 ≦ c ≦ 0.5, particularly preferably 0 ≦ c ≦ 0.4, and d is preferably 0 ≤ d ≤ 0.3, particularly preferably 0 ≤ d ≤ 0.2, e is preferably 0 <e ≤ 0.3, particularly preferably 0 <e ≤ 0.2, f is preferably 0 <f ≤ 0.3 Especially preferably, it is 0 <f <= 0.2. However, a + b + c + d + e + f = 1.

Especially for said a, b, c, d, e, f

i. 0.2≤a <0.8, 0.1≤b <0.8, c and d are 0, 0 <e≤0.3, 0 <f≤0.3,

ii. It is very suitable that 0.2 <a <0.7, 0.1 <b <0.5, 0 <c <0.4, 0 <d <0.2, 0 <e <0.2, and 0 <f <0.2.

X is a divalent organic group represented by General Formula (2), Y is a divalent organic group represented by General Formula (3), and W is a divalent organic group represented by General Formula (4-1). / Or a monovalent organic group represented by general formula (4-2).

(26)

(Wherein Z is

(27)

It is a divalent organic group chosen from either, n is 0 or 1. R <^5> and R <^6> is a C1-C4 alkyl group or alkoxy group, respectively, and may mutually differ or may be the same. k is any one of 0, 1, 2)

Specific examples of R ⁵ and R ⁶ include a methyl group, ethyl group, isopropyl group, tert-butyl group, methoxy group, ethoxy group, isopropyloxy group and the like.

(28)

Where V is

[Formula 29]

It is a divalent organic group chosen from either, and p is 0 or 1. R <^7> and R <^8> is a C1-C4 alkyl group or alkoxy group, respectively, and may mutually differ or may be the same. h is any one of 0, 1, 2)

As a specific example of R <^7> and R <^8>, the same thing as R <^5> or R <^{6> is} mentioned.

(30)

(Wherein T ¹ and T ² may be the same or different,

(31)

Of a monovalent group selected from any one, R ⁹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ¹⁰ is an alkyl group or an alkoxy group of a hydrogen atom, a group having 1 to 4 carbon atoms, or - (CH _{2) s} OH ( Where s is 0, 1, 2 or 3)

Specific examples of R ^9, R ⁵ or R ⁶ may be the same with that, there may be mentioned Specific examples of R ¹⁰ being the same as R ⁵ or R ^6, a hydroxyl group, methylol group, hydroxyl group and the like.

T ^1, T ² is preferably a substituent group to one among the foregoing.

(32)

The weight average molecular weight of the silicone skeleton-containing polymer compound of the present invention is from 3,000 to 500,000, preferably from the viewpoint of the compatibility and photocurability of the photocurable resin composition using the same, and the mechanical properties of the cured product obtained from the photocurable resin composition. 5,000 to 300,000. In addition, in this invention, a weight average molecular weight is the polystyrene conversion value by gel permeation chromatography (GPC).

Hydrogensilphenylene (1,4-bis (dimethylsilyl) benzene) of the following general formula (5) which is a raw material so that the silicone skeleton containing polymer compound of this invention may become a composition of general formula (1).

(33)

Hydrogensilphenylene represented by the following, and dihydroorganosiloxane represented by the following general formula (6)

[Formula 34]

(In formula, R <^3> , R <^4> and m are the same as the above.)

And the specific epoxy group containing compound which has a diallyl group represented by following General formula (7)

(35)

(V, R ⁷ , R ⁸ , p, h are the same as above.)

And / or a specific phenolic compound having a diallyl group represented by the following general formula (8),

(36)

(Wherein Z, R ⁵ , R ⁶ , n, k are the same as above)

Moreover, the isocyanuric acid skeleton containing compound which has the diallyl group represented by following General formula (9), and / or the monoallyl group represented by following General formula (10)

[Formula 37]

(In formula, T <^1> , T <^2> is the same as the above.)

And by adding 0.1-10.0 mass% of isocyanuric acid frame | skeleton containing compound with respect to the silicon polymer compound raw material total amount, it can manufacture by performing what is called a "hydrosilylation" polymerization reaction in presence of a catalyst. And it is preferable to use the epoxy group containing compound of General formula (7), and the phenol compound of General formula (8) in combination. In addition, when using the monoallyl substituted isocyanuric acid skeleton containing compound (10) in the said General Formula (4-1), (4-2) as an isocyanuric acid skeleton containing compound, It is preferable to perform a polymerization reaction.

And the weight average molecular weight of the silicone skeleton containing high molecular compound of this invention is a specific epoxy group containing compound which has a diallyl group represented by the said General formula (7), and the specific phenolic compound which has a diallyl group represented by the said General formula (8). And the total number of allyl groups of the specific isocyanuric acid skeleton-containing compound having a diallyl group represented by the general formula (9) or a monoallyl group represented by the general formula (10), and the general formula (5) It can be controlled easily by adjusting the ratio (total number of allyl groups / total number of hydrosilyl groups) of the hydrogensilyl phenylene and the total number of the hydrosilyl groups of the dihydroorganosiloxane represented by the said General formula (6). . Or at the time of superposition | polymerization of the specific epoxy group containing compound which has the said diallyl group, the specific phenolic compound which has a diallyl group, and the specific isocyanuric acid skeleton containing compound which has (di) allyl group, and hydrogensylphenylene and dihydroorganosiloxane, For example, the weight average molecular weight can be easily controlled by using a monoallyl compound such as o-allylphenol, or monohydrosilane or monohydrosiloxane such as triethylhydrosilane as the molecular weight modifier.

In the polymerization reaction, examples of the catalyst include platinum group metals such as platinum (including platinum black), rhodium and palladium;

_{H 2 PtCl 4 · xH 2 O} , H 2 PtCl 6 · xH 2 O, NaHPtCl 6 · xH 2 O, KHPtCl 6 · xH 2 O, Na 2 PtCl 6 · xH 2 O, K 2 PtCl 4 · xH 2 O, Platinum chloride, chloroplatinic acid, such as PtCl ₄ xH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ xH ₂ O (wherein x is preferably an integer of 0 to 6, and particularly preferably 0 or 6); Chlorinated platinum salts; alcohol-modified chloroplatinic acid (US Pat. No. 3,220,972); complexes of chloroplatinic acid with olefins (US Pat. No. 3,159,601, US Pat. No. 3,159,662, US Pat. No. 3,775,452); Platinum group metals such as palladium supported on carriers such as alumina, silica and carbon; rhodium-olefin complexes; chlorotris (triphenylphosphine) rhodium (so-called Wilkinson's catalyst); platinum chloride, chloroplatinic acid or chloroplatinic acid salt and vinyl chloride And complexes with group-containing siloxanes (in particular, vinyl group-containing cyclic siloxanes).

The amount used is catalytic amount, and it is preferable that it is 0.001 to 0.1 mass% normally with respect to the gross mass of a reaction polymer as a platinum group metal.

In the said polymerization reaction, you may use a solvent as needed. As a solvent, hydrocarbon type solvents, such as toluene and xylene, are preferable, for example.

As said polymerization conditions, from a viewpoint that a catalyst does not deactivate and completion of superposition | polymerization can be completed in a short time, as for superposition | polymerization temperature, 40-150 degreeC is especially preferable 60-120 degreeC. Although superposition | polymerization time changes with kinds and quantity of polymers, it is preferable to complete in about 0.5 to 100 hours, especially 0.5 to 30 hours, in order to prevent the intervention of moisture in a polymerization system. Thus, after completion | finish of a polymerization reaction, when a solvent is used, this is distilled off and the silicone skeleton containing high molecular compound represented by General formula (1) of this invention which has an isocyanuric acid skeleton in a molecule or a terminal group is obtained. Can be.

And when the weight average molecular weight of a silicone skeleton containing high molecular compound falls, the viscosity of the said silicone skeleton containing high molecular compound will fall. Therefore, the viscosity rate of the resin layer formed using the chemically amplified negative resist material using the said silicone skeleton containing high molecular compound also falls. Moreover, in the molecule | numerator of a silicone skeleton containing high molecular compound, when the ratio (b, d, and f of General formula (1)) of the molecular unit containing linear polysiloxane increases, it contains relatively aromatic compounds, such as silphenylene, relatively. The ratio of the molecular units to be reduced (a, c and e in the general formula (1)) decreases, and the viscosity of the silicone skeleton-containing polymer compound decreases. Therefore, the viscosity rate of the resin layer formed using the chemically amplified negative resist material using the said silicone skeleton containing high molecular compound also falls. In addition, in the molecule | numerator of a silicone skeleton containing high molecular compound, when the length of the molecular chain of linear polysiloxane increases, ie, the value of m of General formula (1) increases, the viscosity of the said silicone skeleton containing high molecular compound will fall. Therefore, the viscosity rate of the resin layer formed using the chemically amplified negative resist material using the said silicone skeleton containing high molecular compound also falls.

[Resin composition and chemically amplified negative resist material]

In the resin composition of the present invention,

(A) said silicone skeleton containing high molecular compound,

(B) an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, or a compound in which a hydroxyl group of a polyhydric phenol is substituted with a glycidoxy group One or two or more crosslinking agents selected from

(C) a photoacid generator which is decomposed by light having a wavelength of 190 to 500 nm and generates an acid,

(D) solvent

It is made to contain.

Moreover, the chemically amplified negative resist material of this invention consists of this resin composition.

Here, as the (B) crosslinking agent, an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having two or more methylol groups or alkoxymethylol groups on average in one molecule, and a hydroxyl group of polyhydric phenol are glycidoxy groups. 1 type, or 2 or more types chosen from the compound substituted by the can be used.

The amino condensate modified with formaldehyde or formaldehyde-alcohol may include, for example, melamine condensate modified with formaldehyde or formaldehyde-alcohol, or urea condensation modified with formaldehyde or formaldehyde-alcohol. There is water.

The preparation of the melamine condensate modified with formaldehyde or formaldehyde-alcohol, for example, first denatures the melamine monomer by formaldehyde methylol according to a known method, or further denatures it by alkoxylation with alcohol. And modified melamine represented by the following general formula (11). And as said alcohol, a lower alcohol, for example, a C1-C4 alcohol is preferable.

(38)

(In formula, R <^11> may be the same or different and is an alkoxymethyl group or a hydrogen atom containing a methylol group, the C1-C4 alkoxy group, but at least 1 is a methylol group or the said alkoxymethyl group.)

As said R <^11> , there exists an alkoxy methyl group, such as a methylol group, a methoxymethyl group, an ethoxymethyl group, a hydrogen atom, etc., for example.

Specific examples of the modified melamine of the general formula (11) include trimethoxymethyl monomethylolmelamine, dimethoxymethylmonomethylolmelamine, trimethylolmelamine, hexamethylolmelamine, hexamethoxymethylolmelamine, and the like. Can be. Next, the modified melamine of the general formula (11) or a multimer thereof (for example, oligomers such as dimers and trimers) is subjected to addition condensation polymerization to formaldehyde and the desired molecular weight according to a conventional method, Melamine condensates modified with formaldehyde or formaldehyde-alcohol can be obtained.

In addition, the preparation of the urea condensate modified with formaldehyde or formaldehyde-alcohol can be modified by, for example, formaldehyde methylolation of the urea condensate of a desired molecular weight according to a known method, or by alkoxy To denature more.

Specific examples of the urea condensate modified with formaldehyde or formaldehyde-alcohol include methoxymethylated urea condensates, ethoxymethylated urea condensates, propoxymethylated urea condensates and the like.

In addition, one or two or more of these modified melamine condensates and modified urea condensates may be mixed and used.

Subsequently, as a phenolic compound which has an average of 2 or more methylol groups or an alkoxy methylol group in 1 molecule, it is (2-hydroxy-5-methyl) -1,3-benzenedimethanol, 2,2 ', 6, for example. , 6'-tetramethoxymethylbisphenol A and the like. 1 type, or 2 or more types of these phenolic compounds can be used as a crosslinking agent.

And the said crosslinking agent can be used 1 type or in combination of 2 or more types.

In addition, as a compound which substituted the hydroxyl group of polyhydric phenol with glycidoxy group, the hydroxyl group of bisphenol A, tris (4-hydroxyphenyl) methane, and 1,1, 1- tris (4-hydroxyphenyl) ethane in presence of a base is mentioned. , 1,1'-diglycidoxy bisphenol A, tris (4-glycidoxyphenyl) methane, 1,1,1-tris (4-glycidoxyphenyl) ethane obtained by reacting with epichlorohydrin, etc. For example.

One or two types of compounds in which the hydroxyl group of these polyhydric phenols are substituted by glycidoxy group can be used as a crosslinking agent.

The said crosslinking agent is a component for making hardening reaction with the silicone skeleton containing high molecular compound mentioned above, and making formation of a pattern easy, and also a component which raises the intensity | strength of hardened | cured material further. It is preferable that the weight average molecular weight of such a crosslinking agent is 150-10,000, especially 200-3,000 from a viewpoint of photocurability and heat resistance.

The compounding quantity of the said crosslinking agent is 0.5-50 mass parts, especially 1-30 mass parts with respect to 100 mass parts of said silicone skeleton containing polymer compounds from a viewpoint of photocurability and the reliability as a protective film for electrical and electronic components which went through postcure. desirable.

As the (C) photoacid generator, an acid is generated by light irradiation with a wavelength of 190 to 500 nm, and this can be used as a curing catalyst. Since the photocurable resin composition of this invention is excellent in compatibility with a photo-acid generator, various types of photo-acid generator can be used. Examples of the photoacid generator include onium salts, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, nitrobenzylsulfonate derivatives, sulfonic acid ester derivatives and imide-yl-sulfonate derivatives. , Oxime sulfonate derivatives, iminosulfonate derivatives, triazine derivatives and the like.

As said onium salt, the compound represented by following General formula (12) is mentioned, for example.

_{^{(R 12) j M + K}} - (12)

(In formula, R <^12> represents the C1-C12 linear, branched or cyclic alkyl group which may have a substituent, the C6-C12 aryl group, or the C1-C12 aralkyl group, and M <^+> is Io Donium or sulfonium, K ⁻ represents a non-nucleophilic counter ion, j represents 2 or 3)

In said R <^12> , as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, 2-oxocyclohexyl group, a norbornyl group, an adamantyl group etc. are mentioned, for example. Examples of the aryl group include a phenyl group; alkoxyphenyl groups such as o-, m- or p-methoxyphenyl group, ethoxyphenyl group, m- or p-tert-butoxyphenyl group; 2-, 3- or 4-methylphenyl Alkylphenyl groups such as groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, and dimethylphenyl groups. As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example.

Examples of non-nucleophilic counter ions of K ⁻ include halide ions such as chloride ions and bromide ions; fluoroalkyl sulfonates such as triflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate; Arylsulfonates such as tosylate, benzenesulfonate, 4-fluorobenzenesulfonate, 1,2,3,4 and 5-pentafluoro benzenesulfonate; alkylsulfonates such as mesylate and butanesulfonate; For example.

As a diazomethane derivative, the compound represented by following General formula (13) is mentioned.

[Chemical Formula 39]

(In formula, R <^13> may be same or different, and is a C1-C12 linear, branched or cyclic alkyl group or a halogenated alkyl group, a C6-C12 aryl group or a halogenated aryl group, or C7-C12. 12 shows aralkyl groups)

In said R <^13> , an alkyl group includes a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, etc., for example. Examples of the halogenated alkyl group include trifluoromethyl group, 1,1,1-trifluoroethyl group, 1,1,1-trichloroethyl group, and nonafluorobutyl group. Examples of the aryl group include a phenyl group; alkoxyphenyl groups such as o-, m- or p-methoxyphenyl group, ethoxyphenyl group, m- or p-tert-butoxyphenyl group; 2-, 3- or 4-methylphenyl Alkylphenyl groups such as groups, ethylphenyl groups, 4-tert-butylphenyl groups, 4-butylphenyl groups, and dimethylphenyl groups. As a halogenated aryl group, a fluorophenyl group, a chlorophenyl group, 1,2,3,4,5-pentafluoro phenyl group etc. are mentioned, for example. As an aralkyl group, a benzyl group, a phenethyl group, etc. are mentioned, for example.

Specifically as a photo-acid generator, for example, trifluoromethanesulfonic acid diphenyl iodonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) phenyl iodonium, and p-toluenesulfonic acid diphenyl iodo P-toluenesulfonic acid (p-tert-butoxyphenyl) phenyl iodonium, trifluoromethanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, tri Fluoromethanesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, trifluoromethanesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, p-toluenesulfonic acid triphenylsulfonium, p-toluenesulfonic acid ( p-tert-butoxyphenyl) diphenylsulfonium, p-toluenesulfonic acid bis (p-tert-butoxyphenyl) phenylsulfonium, p-toluenesulfonic acid tris (p-tert-butoxyphenyl) sulfonium, nonafluor Robutanesulfonic acid triphenylsulfonium, butanesulfonic acid triphenylsulfonium, trifluoromethanesulfonic acid trimethylsulfonium, p-toluene Trimethylsulfonium phosphonic acid, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonic acid, cyclohexylmethyl (2-oxocyclohexyl) sulfonium p-toluenesulfonic acid, dimethylphenylsulfonium trifluoromethanesulfonate, p-toluenesulfonic acid dimethylphenylsulfonium, trifluoromethanesulfonic acid dicyclohexylphenylsulfonium, p-toluenesulfonic acid dicyclohexylphenylsulfonium, diphenyl (4-thiophenoxyphenyl) sulfoniumhexafluoroantimo Onium salts such as nate; bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (Cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propyl Sulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-part Sulfonyl) diazomethane, bis (n-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) Diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsul Diazomethane derivatives, such as ponyl-1- (tert-butylsulfonyl) diazomethane; bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime and bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2,3-pentanedioneglyoxime, bis -o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedioneglyoxime, bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, bis-o- (n-butane Sulfonyl) -α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanedionegly Oxime, bis-o- (n -Butanesulfonyl) -2-methyl-3,4-pentanedioneglyoxime, bis-o- (methanesulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α- Dimethylglyoxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o -(Perfluorooctanesulfonyl) -α-dimethylglyoxime, bis-o- (cyclohexanesulfonyl) -α-dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis -o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butyl benzene sulfonyl) -α-dimethylglyoxime, bis-o- (xylenesulfonyl)- glyoxime derivatives such as α-dimethylglyoxime and bis-o- (camphorsulfonyl) -α-dimethylglyoxime; oxime sulfonate derivatives such as α- (benzenesulfoniumoxyimino) -4-methylphenylacetonitrile 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane, 2-isopropylcarbonyl-2- (p-toluenesul Β-ketosulfone derivatives such as nil) propane; disulfone derivatives such as diphenyl disulfone and dicyclohexyl disulfone; p-toluenesulfonic acid 2,6-dinitrobenzyl, p-toluenesulfonic acid 2,4-dinitrobenzyl Nitrobenzylsulfonate derivatives such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p Sulfonic acid ester derivatives such as -toluenesulfonyloxy) benzene; phthalimide-yl-triplate, phthalimide-yl-tosylate, 5-norbornene 2,3-dicarboxyimide-yl-triplate, 5 Norbornene 2,3-dicarboxyimide-yl-tosylate, 5-norbornene 2,3-dicarboxyimide-yl-n-butylsulfonate, n-trifluoromethylsulfonyloxynaphthyl Imide-yl-sulfonate derivatives such as mead; (5- (4-methylphenyl) sulfonyloxyimino-5H-thiophen-2-iridene)-(2-methylphenyl) acetonitrile, (5- (4- (4-methylphenylsulphur Iminosulfonates, such as phenylyl) phenylsulfonyloxyimino) -5H-thiophene-2-iridene)-(2-methylphenyl) -acetonitrile, 2-methyl-2 [(4-methylphenyl) sulfonyl] -1-[(4-methylthio) phenyl] -1-propane and the like. Among these, imide-yl- sulfonates, imino sulfonates, oxime sulfonates, etc. are used preferably.

The said photo-acid generator can use 1 type (s) or 2 or more types.

The compounding quantity of the said photo-acid generator is 0.05-20 mass parts, especially 0.2-5 mass with respect to 100 mass parts of silicone skeleton containing high molecular compounds from the light absorption of photo-acid generator itself and photocurability in a thick film. Addition is preferred.

As the solvent (D), those which can dissolve the aforementioned silicone skeleton-containing polymer compound, a crosslinking agent and a photoacid generator can be used.

For example, ketones, such as cyclohexanone, cyclopentanone, and methyl-2-n-amyl ketone; 3-methoxy butanol, 3-methyl-3- methoxy butanol, 1-methoxy-2-propanol, 1 Alcohols such as ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-methoxypropionate methyl, 3-ethoxypropionate ethyl tert-butyl, tert-butyl propionate, propylene glycol Esters such as mono-tert-butyl ether acetate and γ-butyrolactone, and the like, and one or two or more of them can be used. In particular, ethyl lactate, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, γ-butyrolactone or a mixed solvent having the highest solubility of the photoacid generator is preferable.

The compounding quantity of the said solvent is 50-2,000 mass parts especially with respect to a total of 100 mass parts of compounding quantities of the silicone skeleton containing polymer compound, crosslinking agent, and photo-acid generator mentioned above from the viewpoint of the compatibility, viscosity, and applicability | paintability of a photocurable resin composition. 100-1,000 mass parts is preferable.

In addition, in this invention, a basic compound can be added as (E) component as needed. As said basic compound, the compound which can suppress the diffusion rate at the time when the acid which arises from a photo-acid generator diffuses a photocurable resin layer is suitable. And by mix | blending the said basic compound, resolution improves, the sensitivity change after exposure can be suppressed, dependency on a board | substrate and the environment can be reduced, and exposure margin, pattern shape, etc. can be improved.

Examples of the basic compound include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, and nitrogen having a hydroxy group. And a compound represented by the following general formula (14), including a containing compound, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, an imide derivative, and the like.

N (α) _q (β) _3-q (14)

In the formula, q = 1, 2 or 3. Side chain (alpha) may be same or different, and is any substituent represented by following General formula (15)-(17). The side chain β may be the same or different and may represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may include an ether bond or a hydroxyl group. In addition, the side chains α may be bonded to each other to form a ring.

[Formula 40]

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms or linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms. One or more, hydroxyl group, ether bond, ester bond, or lactone ring may be included. R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and is a hydroxy group, ether bond, ester bond, or One or more lactone rings may be included.

Specifically, as the primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like are exemplified.

As secondary aliphatic amines, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, and dish Clopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethyl Ethylenediamine, N, N- dimethyl tetraethylene pentamine, etc. are illustrated.

As tertiary aliphatic amines, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tri Cyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethyl Methylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine, etc. are illustrated.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, benzyldimethylamine, and the like.

As aromatic amines and heterocyclic amines, aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4 -Methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitro Aniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole and the like), oxazole derivatives (e.g., oxazole, isoxazole, etc.), thiazole derivatives (E.g., thiazole, isothiazole, etc.), imidazole derivatives (e.g., imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, etc.), pyrazole Conductors, furazane derivatives, pyrroline derivatives (e.g., pyrroline, 2-methyl-1-pyrroline, etc.), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrroli Dinon, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives [e.g. pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) Pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine , 1-methyl-2-pyridine, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine and the like], pyridazine derivatives, pyrimidine Derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, mor Lean derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indolin derivatives, quinoline derivatives (e.g. quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxine derivatives Saline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthrizine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine Derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Examples of the nitrogen-containing compound having a carboxyl group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (e.g., nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycyleucine, leucine, methionine, phenylalanine, and the like. , Threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine and the like).

As a nitrogen containing compound which has a sulfonyl group, 3-pyridine sulfonic acid, p-toluene sulfonic acid pyridinium, etc. are illustrated.

Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolmethanol hydrate, monoethanolamine, di Ethanolamine, triethanolamine, N-ethyl diethanolamine, N, N-diethylethanolamine, triisopropanoamine, 2,2'-imino diethanol, 2-aminoethanol, 3-amino-1-propanol , 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- ( 2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperi Dino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinocridinol, 3-tropanol, 1-methyl-2-pyrrolidine ethanol, 1-azilidine ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. are illustrated.

Examples of the amide derivatives include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide and the like. Phthalimide, succinimide, maleimide, etc. are illustrated as an imide derivative.

Examples of the compound represented by the general formula (14) include tris [2- (methoxymethoxy) ethyl] amine, tris [2- (2-methoxyethoxy) ethyl] amine, and tris [2- (2-methoxy Methoxyethoxymethoxy) ethyl] amine, tris [2- (1-methoxyethoxy) ethyl] amine, tris [2- (1-ethoxyethoxy) ethyl] amine, tris [2- (1-e Oxypropoxy) ethyl] amine, tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-dia Xavicyclo [8.8.8] hexacoic acid, 4,7,13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eichoic acid, 1,4,10,13-tetraoxa-7,16 Diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris ( 2-acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2- valeryloxyethyl Amine, Tris Iloxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxy Carbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyl Oxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis ( 2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxy Ethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonbo Nyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetyl Methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- [methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2 -[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2- Acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( 2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl ] Ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-ha Hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2 -Hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (3-hydroxy- 1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxy Methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl ) Ethyl] amine, N-methylbis (2-acetoxyethyl) Min, N-ethylbis (2-acetoxyethyl) amine, N-methylbis (2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N- Ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine , N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) -δ-valerolactone can be exemplified, but is not limited thereto.

The said basic compound can use 1 type (s) or 2 or more types.

As for the compounding quantity of the said basic compound, 0-3 mass parts, especially 0.01-1 mass part are preferable with respect to 100 mass parts of said silicone skeleton containing polymer compounds from a viewpoint of a sensitivity.

In addition, in this invention, in addition to each component mentioned above, the addition component can also be mix | blended with the photocurable resin composition used when forming a photocurable resin layer. As said addition component, the light absorbing agent conventionally used for improving the light absorption efficiency, such as surfactant and the photo-acid generator which are conventionally used for improving applicability | paintability, is mentioned.

As said surfactant, it is preferable that it is nonionic, For example, a fluorochemical surfactant, Specifically, a perfluoroalkyl polyoxyethylene ethanol, a fluorinated alkyl ester, a perfluoroalkylamine oxide, a fluorine-containing organosiloxane type compound Etc.

These can use a commercially available thing, For example, Fluorad "FC-4430" (made by Sumitomo 3M), Suflon "S-141", and "S-145" ( All Asahi Glass Co., Ltd.), Unidyne "DS-401", "DS-4031" and "DS-451" (all Daikin Industries Co., Ltd. product), mega pack "F-8151" (DIC Corporation) Manufacture) and "X-70-093" (made by Shin-Etsu Chemical Co., Ltd.). Among these, fluoride "FC-4430" (made by Sumitomo 3M Co., Ltd.) and "X-70-093" (made by Shin-Etsu Chemical Co., Ltd.) are preferable.

As said light absorber, a diaryl sulfoxide, a diaryl sulfone, 9, 10- dimethyl anthracene, 9-fluorenone, etc. are mentioned, for example.

In the chemically amplified resist material of the present invention, the preparation is performed by a conventional method. The said chemically amplified negative resist material can be prepared by stirring-mixing each component mentioned above and filtering by a filter etc. after that.

[Photocurable Dry Film]

The photocurable dry film of this invention has a structure where the photocurable resin layer was sandwiched between a support film and a protective film, and the said photocurable resin layer was formed from the said resin composition (photocurable resin composition).

Moreover, if the structure which the photocurable dry film of this invention has is demonstrated, a photocurable dry film has a structure which the photocurable resin layer was sandwiched between a support film and a protective film. The photocurable resin layer is formed of the resin composition suitable for forming an electrical / electronic component protective film, and enables fine pattern formation in a wide film thickness and a wavelength region, and enables low temperature postcure. It is excellent in flexibility, heat resistance, electrical properties, adhesion, reliability, and chemical resistance.

In the present invention, the photocurable dry film is a solid, and in the photocurable resin layer, there is no fear that bubbles due to volatilization remain between the inside of the photocurable resin layer and the uneven substrate. Further, miniaturization, thinning, and multilayering of semiconductor devices are progressing, and the interlayer insulating layer, in which the present invention is one of the application ranges, tends to be thin, but considering the flatness and step coverage on the uneven substrate, an appropriate film thickness Range exists. Therefore, the film thickness of the said photocurable resin layer is 10-100 micrometers from a viewpoint of the flatness and a step coverage, Preferably it is 10-70 micrometers, Especially preferably, it is 10-50 micrometers.

Moreover, the said photocurable resin layer can exhibit favorable fluidity | liquidity, and can enter to the inside of a narrow gap.

Therefore, when the photocurable dry film of this invention adheres to the board | substrate which has an unevenness | corrugation, a photocurable resin layer can follow and coat | cover the said unevenness | corrugation, and can achieve high flatness. In particular, since the main component of the photocurable resin layer is the silicone skeleton-containing polymer compound and has a low surface tension, higher flatness can be achieved. In addition, when the photocurable resin layer is brought into close contact with the substrate in a vacuum environment, generation of these gaps can be prevented more effectively.

Here, in the photocurable dry film of this invention, preparation of the photocurable resin composition used when forming a photocurable resin layer is carried out stirring-mixing each component similarly to preparation of the chemically amplified negative resist material mentioned above, Thereafter, the photocurable resin composition can be prepared by filtration with a filter or the like.

The support film used in the photocurable dry film of this invention may be single, and the multilayer film which laminated | stacked several polymer films may be sufficient. Examples of the material include synthetic resin films such as polyethylene, polypropylene, polycarbonate, and polyethylene terephthalate, but polyethylene terephthalate having appropriate flexibility, mechanical strength, and heat resistance is preferable. Moreover, about these films, various processes, such as corona treatment and peeling agent application, may be performed. These can use a commercial item, for example, Cerafil WZ (RX), Cerafil BX8 (R) (above, manufactured by Toray Film Processing Co., Ltd.), E7302, E7304 (above, manufactured by Toyo Spinning Co., Ltd.), PUREX G31, PUREX G71T1 (above, made by Teijin Dupont Film Co., Ltd.), PET38x1-A3, PET38x1-V8, PET38x1-X08 (above, Nippa Corporation make), etc. are mentioned.

Although the protective film used in the photocurable dry film of this invention can use the same thing as the above-mentioned support film, The polyethylene terephthalate and polyethylene which have appropriate flexibility are preferable. These can use a commercial item, As what is already illustrated as polyethylene terephthalate, As polyethylene, For example, GF-8 (made by Damapoly) and PE film 0 type (made by Nippa Corporation) There is this.

The thickness of the support film and the protective film is preferably from 10 to 100 µm, particularly preferably from 25 to 100, from the viewpoint of preventing the curling of the stability and winding of the photocurable dry film production and the so-called curl. 50 μm.

Next, the manufacturing method of the photocurable dry film in this invention is demonstrated. As a manufacturing apparatus of the said photocurable dry film, the film coater for manufacturing an adhesive product can be used generally. Examples of the film coater include a comma coater, a comma reverse coater, a multi coater, a die coater, a lip coater, a lip reverse coater, a direct gravure coater, an offset gravure coater, a three bottom reverse coater, and a four bottom reverse coater.

When the support film is released from the unwinding axis of the film coater and passed through the coater head of the film coater, the photocurable resin composition is applied to the support film to a predetermined thickness, and then hot air circulation oven at a predetermined temperature and a predetermined time. Passed through a laminate roll at a predetermined pressure together with a protective film released from the other unwinding axis of the film coater, and the photocurable resin layer dried on the support film was bonded to the photocurable resin layer on the support film. Then, it is manufactured by winding up to the winding axis | shaft of the said film coater. In this case, as said temperature, 25-150 degreeC is preferable, 1-100 minutes are preferable for the said time, and the said pressure has preferable 0.01-5 MPa.

[Pattern formation method]

First, the pattern formation method at the time of using the chemically amplified negative resist material mentioned above is demonstrated.

In order to form a pattern by using the negative resist composition of the invention, can be carried out by employing a lithographic technique known, for example, a substrate, or a copper wiring on the substrates such as a silicon wafer or SiO ₂ substrate, SiN substrate It is applied to a substrate having a pattern such as a spin coating by a known method such as spin coating, and prebaked under the conditions of about 80 to 130 ° C. for about 50 to 600 seconds to have a thickness of 1 to 50 μm, preferably 1 to 30 μm. More preferably, a resist film of 5 to 20 mu m is formed. Subsequently, a mask for forming a desired pattern is applied on the resist film, and high energy rays having a wavelength of 190 to 500 nm such as i-ray and g-ray are exposed at an exposure dose of about ¹ to 5,000 mJ / cm ² , preferably 100 to Irradiate to 2,000 mJ / cm ² . Next, if necessary, post-exposure heat treatment (post exposure bake, PEB) may be performed on the hot plate at 60 to 150 ° C. for 1 to 10 minutes, preferably at 80 to 120 ° C. for 1 to 5 minutes. By exposing in this way, an insoluble pattern which does not melt | dissolve in the following solvent which is an exposure part bridge | crosslinks and is a developing solution is formed.

Thereafter, development is carried out with a developer. The said solvent can use the above-mentioned solvent used when the chemically amplified negative resist material of this invention was prepared. For example, alcohols, such as isopropyl alcohol (IPA), ketones, such as cyclohexanone, glycol, such as propylene glycol monomethyl ether, etc. are preferable. The development can be performed by a conventional method, for example, immersing the substrate on which the pattern is formed in the developer. Then, washing | cleaning, rinsing, drying, etc. are performed as needed, and the film of the photocurable resin layer which has a desired pattern can be obtained. And when it is not necessary to form a pattern, for example, when only a uniform film is to be formed, it is good to carry out by the method similar to the content described in the said pattern formation method except the said photomask not being used.

In addition, the obtained pattern can be post-cured using an oven or a hot plate at a temperature of 100 to 250 ° C, preferably 150 to 220 ° C, more preferably 170 to 190 ° C. If the post-curing temperature is 100 to 250 ° C, the crosslinking density of the film of the photocurable resin composition can be increased, and the remaining volatile components can be removed, which is preferable in view of adhesion to the substrate, heat resistance and strength, and furthermore, electrical properties. . The post curing time can be 10 minutes to 10 hours.

The cured film thus obtained is excellent in flexibility, adhesion to substrates, heat resistance, electrical properties, mechanical strength, and chemical resistance to solder flux solution, and is excellent in reliability of semiconductor devices having this as a protective film. Crack generation at the time of the temperature cycle test can be prevented, and it is preferably used as a protective film for electrical / electronic parts, semiconductor elements and the like.

Moreover, the pattern formation method of the photocurable dry film in this invention is demonstrated. The protective film is peeled from the photocurable dry film of the present invention, the photocurable resin layer is brought into close contact with the substrate, exposed, and post-exposure heat treatment (post exposure bake, PEB) is carried out and developed, and after curing as necessary. By forming a pattern to obtain an electrical / electronic component protective film for the final purpose.

First, a photocurable dry film is made to adhere to a board | substrate using a film sticking apparatus. Examples of the substrate include silicon wafers, TSV silicon wafers, plastics, ceramics, various metal circuit boards, and the like, and particularly have grooves and holes having an opening width of 10 to 100 µm and a depth of 10 to 120 µm. There is a substrate. As the film attachment device, a vacuum laminator is preferable. The said photocurable dry film is attached to the said film attachment apparatus, the protective film of the said photocurable dry film is peeled off, and the exposed said photocurable resin layer is used the attachment roll of predetermined pressure in the vacuum chamber of predetermined vacuum degree. It adhere | attaches on the said board | substrate on the table of a predetermined temperature. And as said temperature, 60-120 degreeC is preferable, As said pressure, 0-5.0 Mpa is preferable, As said vacuum degree, 50-500 Pa is preferable. After the adhesion, a pattern can be formed using a known lithography technique. Here, in order to perform the photocuring reaction of the said photocurable resin layer efficiently, or to improve the adhesiveness of a photocurable resin layer and a board | substrate, preheating (prebaking) may be performed as needed. Prebaking can be performed, for example at 40-140 degreeC for 1 minute-about 1 hour. Subsequently, it exposes and hardens | cures with the light of wavelength 190-500nm through a photomask or the state which peeled the said support film through a photomask. The photomask may be a pattern obtained by cutting out a desired pattern, for example. The material of the photomask preferably shields light having the wavelength of 190 to 500 nm. For example, chromium or the like is preferably used, but is not limited thereto. Examples of the light having a wavelength of 190 to 500 nm include light having various wavelengths generated by the radiation generating device, for example, ultraviolet light such as g-ray and i-ray and ultraviolet light (248 nm, 193 nm). Etc. And, the wavelength is preferably 248 to 436 nm. As for an exposure amount, 10-3,000 mJ / cm <^2> is preferable, for example. By exposing in this way, an insoluble pattern which does not melt | dissolve in the following solvent which is an exposure part bridge | crosslinks and is a developing solution is formed.

Moreover, in order to raise image development sensitivity, post-exposure heat processing (PEB) is performed. The post-exposure heat treatment can be performed at 40 to 140 ° C. for 0.5 to 10 minutes, for example.

Thereafter, development is carried out with a developer. The photocurable resin composition solvent used for formation of a photocurable resin layer in the photocurable dry film of this invention can be used for the said developing solution. For example, alcohols, such as isopropyl alcohol (IPA), ketones, such as cyclohexanone, glycol, such as propylene glycol monomethyl ether, etc. are preferable. The development can be performed by a conventional method, for example, immersing the substrate on which the pattern is formed in the developer. Then, washing | cleaning, rinsing, drying, etc. are performed as needed, and the film of the photocurable resin layer which has a desired pattern can be obtained. And when it is not necessary to form a pattern, for example, when only a uniform film is to be formed, it is good to carry out by the method similar to the content described in the said pattern formation method except the point which does not use the said photomask.

In addition, the obtained pattern can be post-cured using an oven or a hot plate at a temperature of 100 to 250 ° C, preferably 150 to 220 ° C, more preferably 170 to 190 ° C. If the post-curing temperature is 100 to 250 ° C, the crosslinking density of the film of the photocurable resin composition can be increased, and the remaining volatile components can be removed, which is preferable in view of adhesion to the substrate, heat resistance and strength, and furthermore, electrical properties. . The post curing time can be 10 minutes to 10 hours.

The cured film thus obtained is excellent in flexibility, adhesion to substrates, heat resistance, electrical properties, mechanical strength, and chemical resistance to solder flux solution, and is excellent in reliability of semiconductor elements having this protective film as a protective film. Crack generation at the time of a cycle test can be prevented, and it is used suitably as a protective film of electrical / electronic components, a semiconductor element, etc.

And in this invention, the sight formed by the said photocurable dry film in the board | substrate which has the groove | channel and / or hole whose opening width is 10-100 micrometers and the depth is 10-120 micrometers obtained by forming as mentioned above. The film for electrical / electronic component protection which consists of a laminated body by which the hardened | cured material layer of a chemical composition is laminated | stacked, and the cured film obtained by the said pattern formation method is also provided.

[Example]

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following example.

In addition, in the following example, "part" represents a "mass part."

I. Preparation of Photocurable Resin Composition

The chemical structural formulas of the compounds (M-1) to (M-11) used in the following synthesis examples are shown.

(41)

(Me represents a methyl group)

Synthesis Example 1

After dissolving 118 g of compound (M-1) in 700 g of toluene in a 2 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, 50.3 g of a compound (M-2) and a compound (M-3) 353.2 g, the compound (M-4) 2.3g, and the compound (M-6) 1.1g were added, and it heated at 60 degreeC. Thereafter, 0.8 g of a carbon-supported platinum catalyst (5% by mass) was added thereto, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C, it was further warmed up to 90 ° C for 3 hours, and further cooled to 60 ° C, 0.8 g of carbon supported platinum catalyst (5% by mass) was added, and 40.4 g of compound (M-5) was added dropwise into the flask over 25 minutes. At this time, the flask internal temperature rose to 65-67 degreeC. After completion of dropping, the mixture was further aged at 90 ° C for 3 hours, cooled to room temperature, 637.5 g of methyl isobutyl ketone was added, and the reaction solution was filtered under pressure with a filter to remove the platinum catalyst. Furthermore, 285 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, followed by stirring and still liquid separation to remove the lower aqueous layer. This liquid washing and washing operation was repeated six times to remove trace acid components in the silicone skeleton-containing polymer compound solution. After distilling off the solvent in the silicone skeleton-containing polymer compound solution under reduced pressure, and further adding 975 g of cyclopentanone, the solvent was concentrated under reduced pressure to obtain a cyclopentanone solution having a solid content concentration of 65 to 70 mass%, and cyclopentanone was the main solvent. The silicone skeleton containing high molecular compound solution (A-1) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene. Similarly, the peak of Compound (M-6) was lost using GPC. It was confirmed that compound (M-6) was contained in the polymer. Moreover, as a result of converting a raw material into molar ratio in General formula (1), it was a = 0.395, b = 0.263, c = 0.198, d = 0.132, e = 0.007, f = 0.005.

[Synthesis Example 2]

After dissolving 100 g of compound (M-1) in 700 g of toluene in a 2 L flask equipped with a stirrer, a thermometer, a nitrogen substituent, and a reflux condenser, 82.9 g of a compound (M-2), a compound (M-3) 321.8 g, 2.6 g of compounds (M-4) and 1.1 g of compounds (M-6) were added and heated to 60 ° C. Thereafter, 0.7 g of a carbon supported platinum catalyst (5% by mass) was added thereto, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C, the mixture was further heated to 90 ° C for 3 hours, cooled to 60 ° C, 0.7 g of carbon supported platinum catalyst (5 mass%) was thrown in, and 53.0 g of compound (M-5) was dripped in the flask over 25 minutes. At this time, the flask internal temperature rose to 65-67 degreeC. After completion of dropping, the mixture was further aged at 90 ° C for 3 hours, cooled to room temperature, 650 g of methyl isobutyl ketone was added, and the reaction solution was filtered under pressure with a filter to remove the platinum catalyst. Furthermore, 285 g of pure water was added to the obtained silicon skeleton containing polymer compound solution, stirring and standing liquid separation were performed, and the water layer of the lower layer was removed. This liquid washing and washing operation was repeated six times to remove trace acid components in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and 875 g of cyclopentanone was added thereto, followed by concentration under reduced pressure to yield a cyclopentanone solution having a solid content concentration of 65 to 70 mass%, and cyclopentanone was the main solvent. A silicone skeleton-containing polymer compound solution (A-2) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the solution of the silicone skeleton-containing polymer compound was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene, and the compound (M-6) was lost by the disappearance of the peak of the compound (M-6). ) Was included in the polymer. Moreover, in General formula (1), it was a = 0.341, b = 0.161, c = 0.332, d = 0.156, e = 0.007, f = 0.003.

[Synthesis Example 3]

After dissolving 400 g of compound (M-1) in 2,900 g of toluene in a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substituent, and a reflux condenser, 340.1 g of a compound (M-2) and a compound (M-3) 943.5 g, the compound (M-4) 10.9g, and the compound (M-6) 3.9g were added, and it heated at 60 degreeC. Thereafter, 3.8 g of a carbon supported platinum catalyst (5% by mass) was added thereto, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C, the mixture was further warmed to 90 ° C for 3 hours, cooled to 60 ° C again, 3.8 g of carbon-supported platinum catalyst (5 mass%) were added, and 232.7 g of compound (M-5) was added dropwise into the flask over 1 hour. At this time, the flask internal temperature rose to 67-70 degreeC. After completion of dropping, the mixture was further aged at 90 ° C for 3 hours, cooled to room temperature, 2,940 g of methyl isobutyl ketone was added, and the reaction solution was filtered under pressure with a filter to remove the platinum catalyst. Further, 1,315 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, followed by stirring and still liquid separation to remove the lower aqueous layer. This liquid washing and washing operation was repeated six times to remove trace acid components in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and 3,500 g of cyclopentanone was added thereto, followed by concentration under reduced pressure to obtain a cyclopentanone solution having a solid content concentration of 65 to 70 mass%, and cyclopentanone was the main solvent. A silicone skeleton-containing polymer compound solution (A-3) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 50,000 in terms of polystyrene, and the compound (M-6) was lost by the disappearance of the peak of the compound (M-6). It confirmed that it contained in this polymer. Moreover, in General formula (1), it was a = 0.371, b = 0.131, c = 0.361, d = 0.127, e = 0.007, f = 0.003.

[Synthesis Example 4]

In Synthesis Example 1, compound (M-6) was changed to 1.1 g of compound (M-7), and synthesized in the same manner, a silicone skeleton-containing polymer compound having a solid content of 65 to 70% by mass of cyclopentanone as a main solvent A solution (A-4) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene, and the compound (M-7) was lost by the disappearance of the peak of the compound (M-7). ) Was included in the polymer. Moreover, in General formula (1), it was a = 0.395, b = 0.263, c = 0.198, d = 0.132, e = 0.007, f = 0.005.

Synthesis Example 5

In the synthesis example 1, the compound (M-6) was changed to 1.1 g of the compound (M-8), and it synthesize | combined by the same method, and the silicone skeleton containing polymer compound which uses cyclopentanone of 65-70 mass% of solid content concentration as a main solvent. A solution (A-5) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene, and the compound (M-8) was lost by the disappearance of the peak of the compound (M-8). ) Was included in the polymer. Moreover, in General formula (1), it was a = 0.395, b = 0.263, c = 0.198, d = 0.132, e = 0.007, f = 0.005.

[Synthesis Example 6]

In Synthesis Example 1, compound (M-6) was changed to 1.1 g of compound (M-9), and synthesized in the same manner, a silicone skeleton-containing polymer compound having a solid content of 65 to 70% by mass of cyclopentanone as a main solvent A solution (A-6) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene, and the compound (M-9) was lost by the peak of compound (M-9). ) Was included in the polymer. Moreover, in General formula (1), it was a = 0.395, b = 0.263, c = 0.198, d = 0.132, e = 0.007, f = 0.005.

[Synthesis Example 7]

In Synthesis Example 1, Compound (M-6) was changed to 1.1 g of Compound (M-10) and synthesized in the same manner to obtain a silicone skeleton-containing polymer compound having a solid content of 65 to 70% by mass of cyclopentanone as a main solvent. A solution (A-7) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene, and the compound (M-10) was lost by the disappearance of the peak of the compound (M-10). ) Was included in the polymer. Moreover, in General formula (1), it was a = 0.395, b = 0.263, c = 0.198, d = 0.132, e = 0.007, f = 0.005.

[Synthesis Example 8]

After dissolving 118 g of compound (M-1) in 700 g of toluene in a 2 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, 50.3 g of a compound (M-2) and a compound (M-3) 353.2 g and 2.3 g of compounds (M-4) were added and heated to 60 ° C. Thereafter, 0.8 g of a carbon-supported platinum catalyst (5% by mass) was added thereto, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C, it was further warmed up to 90 ° C for 3 hours, and further cooled to 60 ° C, 0.8 g of carbon supported platinum catalyst (5% by mass) was added, and 40.4 g of compound (M-5) was added dropwise into the flask over 25 minutes. At this time, the flask internal temperature rose to 65-67 degreeC. After completion of the dropwise addition, 1.1 g of the compound (M-11) was added, aged at 90 ° C for 3 hours, cooled to room temperature, 637.5 g of methyl isobutyl ketone was added, and the reaction solution was filtered under pressure with a filter to form a platinum catalyst. Removed. Furthermore, 285 g of pure water was added to the obtained silicon skeleton containing polymer compound solution, stirring and standing liquid separation were performed, and the water layer of the lower layer was removed. This liquid washing and washing operation was repeated six times to remove trace acid components in the silicone skeleton-containing polymer compound solution. After distilling off the solvent in the silicone skeleton-containing polymer compound solution under reduced pressure, and further adding 975 g of cyclopentanone, the solvent was concentrated under reduced pressure to obtain a cyclopentanone solution having a solid content concentration of 65 to 70 mass%, and cyclopentanone was the main solvent. The silicone skeleton containing high molecular compound solution (A-8) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the solution of the silicone skeleton-containing polymer compound was measured by GPC. The weight average molecular weight was 45,000 in terms of polystyrene, and the compound (M-11) was lost by the disappearance of the peak of the compound (M-11). It confirmed that it contained in this polymer. Moreover, in General formula (1), it was a = 0.395, b = 0.263, c = 0.198, d = 0.132, e = 0.007, f = 0.005.

[Synthesis Example 9]

In the synthesis example 1, the compound (M-6) was increased to 2.2 g, synthesize | combined by the same method, and the silicone skeleton containing polymer compound solution (A-9) of 65-70 mass% of solid content concentration which uses cyclopentanone as a main solvent. Got. The molecular weight of the silicone skeleton-containing polymer compound in the solution of the silicone skeleton-containing polymer compound was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene, and the compound (M-6) was lost by the disappearance of the peak of the compound (M-6). ) Was included in the polymer. Moreover, in General formula (1), it was a = 0.391, b = 0.260, c = 0.196, d = 0.130, e = 0.014, and f = 0.009.

[Synthesis Example 10]

After dissolving 118 g of compound (M-1) in 700 g of toluene in a 2 L flask equipped with a stirrer, a thermometer, a nitrogen substituent, and a reflux condenser, 50.3 g of a compound (M-2), a compound (M-3) 477.3 g, 3.1 g of compound (M-4) and 35 g of compound (M-6) were added and heated to 60 ° C. Thereafter, 0.8 g of a carbon-supported platinum catalyst (5% by mass) was added thereto, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C, it was further warmed up to 90 ° C for 3 hours, and further cooled to 60 ° C, 0.8 g of carbon supported platinum catalyst (5% by mass) was added, and 54.5 g of compound (M-5) was added dropwise into the flask over 30 minutes. At this time, the flask internal temperature rose to 65-67 degreeC. After completion of dropping, the mixture was further aged at 90 ° C for 3 hours, cooled to room temperature, 637.5 g of methyl isobutyl ketone was added, and the reaction solution was filtered under pressure with a filter to remove the platinum catalyst. Furthermore, 285 g of pure water was added to the obtained silicon skeleton containing polymer compound solution, stirring and standing liquid separation were performed, and the water layer of the lower layer was removed. This liquid washing and washing operation was repeated six times to remove trace acid components in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and 975 g of cyclopentanone was added thereto. The silicone skeleton containing high molecular compound solution (A-10) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene. Similarly, the peak of Compound (M-6) was lost using GPC. It was confirmed that compound (M-6) was contained in the polymer. Moreover, as a result of converting a raw material into molar ratio in General formula (1), it was a = 0.292, b = 0.195, c = 0.146, d = 0.098, e = 0.161, f = 0.108.

[Comparative Synthesis Example 1]

After dissolving 118 g of compound (M-1) in 700 g of toluene in a 2 L flask equipped with a stirrer, a thermometer, a nitrogen substitution device, and a reflux condenser, 50.3 g of a compound (M-2) and a compound (M-3) 353.2 g and 2.3 g of compound (M-4) were added and it heated to 60 degreeC. Thereafter, 0.8 g of a carbon-supported platinum catalyst (5% by mass) was added thereto, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C, it was further warmed up to 90 ° C for 3 hours, and further cooled to 60 ° C, 0.8 g of carbon supported platinum catalyst (5% by mass) was added, and 40.4 g of compound (M-5) was added dropwise into the flask over 25 minutes. At this time, the flask internal temperature rose to 65-67 degreeC. After completion of dropping, the mixture was further aged at 90 ° C for 3 hours, cooled to room temperature, 637.5 g of methyl isobutyl ketone was added, and the reaction solution was filtered under pressure with a filter to remove the platinum catalyst. Furthermore, 285 g of pure water was added to the obtained silicon skeleton containing polymer compound solution, stirring and standing liquid separation were performed, and the water layer of the lower layer was removed. This liquid washing and washing operation was repeated six times to remove trace acid components in the silicone skeleton-containing polymer compound solution. After distilling off the solvent in the silicone skeleton-containing polymer compound solution under reduced pressure, and further adding 975 g of cyclopentanone, the solvent was concentrated under reduced pressure to obtain a cyclopentanone solution having a solid content concentration of 65 to 70 mass%, and cyclopentanone was the main solvent. The silicone skeleton containing high molecular compound solution (A-11) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene, and a = 0.400, b = 0.266, and c = in General Formula (1). 0.200, d = 0.134.

[Comparative Synthesis Example 2]

After dissolving 100 g of compound (M-1) in 700 g of toluene in a 2 L flask equipped with a stirrer, a thermometer, a nitrogen substituent, and a reflux condenser, 82.9 g of a compound (M-2), a compound (M-3) 321.8 g and 2.6 g of compound (M-4) were added and it heated to 60 degreeC. Thereafter, 0.7 g of a carbon supported platinum catalyst (5% by mass) was added thereto, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C, the mixture was further heated to 90 ° C for 3 hours, cooled to 60 ° C, 0.7 g of carbon supported platinum catalyst (5 mass%) was thrown in, and 53.0 g of compound (M-5) was dripped in the flask over 25 minutes. At this time, the flask internal temperature rose to 65-67 degreeC. After completion of dropping, the mixture was further aged at 90 ° C for 3 hours, cooled to room temperature, 650 g of methyl isobutyl ketone was added, and the reaction solution was filtered under pressure with a filter to remove the platinum catalyst. Furthermore, 285 g of pure water was added to the obtained silicon skeleton containing polymer compound solution, stirring and standing liquid separation were performed, and the water layer of the lower layer was removed. This liquid washing and washing operation was repeated six times to remove trace acid components in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and 875 g of cyclopentanone was added thereto, followed by concentration under reduced pressure to yield a cyclopentanone solution having a solid content concentration of 65 to 70 mass%, and cyclopentanone was the main solvent. The silicone skeleton containing high molecular compound solution (A-12) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC. The weight average molecular weight was 52,000 in terms of polystyrene, and a = 0.345, b = 0.162, and c = in General Formula (1). 0.335, d = 0.158.

[Comparative Synthesis Example 3]

After dissolving 400 g of compound (M-1) in 2,900 g of toluene in a 10 L flask equipped with a stirrer, a thermometer, a nitrogen substituent, and a reflux condenser, 340.1 g of a compound (M-2) and a compound (M-3) 943.5 g and 10.9 g of compound (M-4) were added and heated to 60 ° C. Thereafter, 3.8 g of a carbon supported platinum catalyst (5% by mass) was added thereto, and after confirming that the internal reaction temperature was raised to 65 to 67 ° C, the mixture was further warmed to 90 ° C for 3 hours, cooled to 60 ° C again, 3.8 g of carbon-supported platinum catalyst (5 mass%) were added, and 232.7 g of compound (M-5) was added dropwise into the flask over 1 hour. At this time, the flask internal temperature rose to 67-70 degreeC. After completion of dropping, the mixture was further aged at 90 ° C for 3 hours, cooled to room temperature, 2,940 g of methyl isobutyl ketone was added, and the reaction solution was filtered under pressure with a filter to remove the platinum catalyst. Further, 1,315 g of pure water was added to the obtained silicone skeleton-containing polymer compound solution, followed by stirring and still liquid separation to remove the lower aqueous layer. This liquid washing and washing operation was repeated six times to remove trace acid components in the silicone skeleton-containing polymer compound solution. The solvent in the silicone skeleton-containing polymer compound solution was distilled off under reduced pressure, and 3,500 g of cyclopentanone was added thereto, followed by concentration under reduced pressure to obtain a cyclopentanone solution having a solid content concentration of 65 to 70 mass%, and cyclopentanone was the main solvent. The silicone skeleton containing high molecular compound solution (A-13) was obtained. The molecular weight of the silicone skeleton-containing polymer compound in the silicone skeleton-containing polymer compound solution was measured by GPC, and the polystyrene equivalent weight average molecular weight was 50,000 and a = 0.375, b = 0.132 and c = 0.365 in General Formula (1). , d = 0.128.

[Examples and Comparative Examples]

Using the solution of resin synthesize | combined in the said synthesis examples 1-10, the crosslinking agent, the photo-acid generator, and the amine compound are mix | blended with the composition shown in Table 1 (mass part in parentheses), and a cyclopentanone is mix | blended as a solvent to add. Thus, a resist material having a solid content concentration of 45% by mass was prepared. Thereafter, after stirring, mixing, and dissolving, microfiltration was performed with a 0.5 µm filter made of Teflon (registered trademark) to obtain a resist material of the compositions 1 to 12.

In addition, as a comparative example, the solution of the resin synthesize | combined in the said Comparative Synthesis Examples 1-3 and the acid generator were mix | blended in the same way, and it stirred, mixed, and made to melt | dissolve, and then filtered fine with a 0.5 micrometer filter made from Teflon (trademark). The resist material of the composition 13-15 was obtained. The composition of the comparative example is also shown in Table 1.

[Table 1]

In addition, the photoacid generator (PAG-1), crosslinking agents (XL-1, XL-2), and basic compound (AMINE-1) of Table 1 are as showing below.

(42)

II. Exposure, pattern formation

The resist material can be applied onto the substrate by rotating the substrate after administering 5 mL of the resist material onto the silicon substrate. That is, it is a spin coat method. By adjusting the rotation speed, the film thickness of the resist film on the substrate can be easily adjusted. The resist material was applied onto a silicon substrate so as to have a film thickness of 20 μm.

The resist material was dispensed onto the substrate, spin-coated, and then prebaked at 100 ° C. for 2 minutes on a hot plate. Next, using a mask aligner (product name: MA-8) manufactured by Zus Microtec Co., Ltd., a mask was formed in which 20 µm holes in a width: length = 1: 1 array could be formed. Broadband light was exposed. The substrate was then exposed to light at 110 ° C. for 2 minutes, then heated (PEB) and cooled. Thereafter, paddle development was performed three times for 1 minute using isopropyl alcohol (IPA), and patterning was performed. Subsequently, the obtained substrate pattern was post-cured while being purged with nitrogen at 180 ° C. for 2 hours using an oven. Instead of the silicon substrate, patterning was performed on the SiN substrate and the Cu substrate in the same manner.

Next, each board | substrate was cut out and the hole pattern shape was observed using the scanning electron microscope (SEM) so that the shape of the obtained hole pattern could be observed. Table 2 shows the optimum exposure amount (exposure amount in terms of 365 nm light) in which the aperture size of the hole pattern is completed in the same size as the mask dimension of 20 µm.

[Table 2]

As shown in Table 2, when the patterning of the composition which does not use the silicone skeleton containing high molecular compound of this invention was tried, remarkable pattern peeling was observed on a SiN substrate and a Cu substrate, and patterning was impossible. Therefore, the adhesiveness of the pattern or film using a resist material and a board | substrate is obviously improved by using the silicone skeleton containing high molecular compound of this invention.

III. Preparation of Photocurable Dry Film

Next, as a photocurable dry film, using the solution of resin synthesize | combined in the synthesis examples 1-10 by the method similar to the above, the crosslinking agent, a photo-acid generator, and an amine by the composition (mass part in brackets) shown in Table 1 The compound is blended (cyclopentanone is not blended as a solvent differently from the above), and then stirred, mixed, and dissolved, followed by precise filtration with a 1.0 µm filter made of Teflon (registered trademark) to obtain a photocurable resin composition. Got it. In addition, as a comparative example, the solution of the resin synthesize | combined in the said Comparative Synthesis Examples 1-3 and the acid generator were mix | blended in the same way, and it stirred, mixed, and melt | dissolved, and then filtered fine with a 1.0 micrometer filter made from Teflon (trademark). Was performed to obtain a photocurable resin composition.

The photocurable resin compositions 1-15 of Table 1 were apply | coated on the support film using the polyethylene terephthalate film (38 micrometers in thickness) as a die coater and a support film as a film coater. Next, the photocurable resin layer was formed on the support film by passing a hot air circulation oven (length 4m) set to 100 degreeC for 5 minutes. Moreover, from the said photocurable resin layer, the polyethylene film (50 micrometers in thickness) was bonded together as a protective film by the pressure of 1 MPa using the lamination roll, and the photocurable dry film was manufactured. And the film thickness of the said photocurable resin layer is 50 micrometers. An example of a film is shown in Table 3 together with an Example and a comparative example.

IV. Exposure, pattern formation

Next, as summarized in Table 3, each of the photocurable dry films using the photocurable resin composition exemplified in Examples and Comparative Examples was peeled off of the protective film, and was manufactured by Takatori Co., Ltd. Using the (product name: TEAM-100RF), the inside of the vacuum chamber was set at a vacuum degree of 100 Pa, and the photocurable resin layer on the support film was brought into close contact with the silicon substrate at a temperature condition of 100 ° C. After returning to normal pressure, the said board | substrate was cooled to 25 degreeC, it took out from the said vacuum laminator, and the support film was peeled off.

Next, after peeling a support film, prebaking was performed at 100 degreeC for 5 minutes on the hotplate. Next, using a mask aligner (product name: MA-8) manufactured by Zus Microtec Co., Ltd., a mask was formed in which a hole having a width of 40 μm in a vertical length = 1: 1 array was formed. Band light was exposed. Subsequently, the substrate was post-exposure heated (PEB) and cooled at 130 ° C. for 5 minutes. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA), and patterning was performed. Subsequently, it post-cured by nitrogen purging at 180 degreeC for 2 hours using oven.

Similarly, after laminating the photocurable dry film manufactured as mentioned above on a SiN substrate and a Cu substrate instead of a silicon substrate, patterning was performed.

Next, each board | substrate was cut out and the hole pattern shape was observed using the scanning electron microscope (SEM) so that the shape of the obtained hole pattern could be observed. Table 3 shows the optimal exposure amount (exposure amount in terms of 365 nm light) in which the aperture size of the hole pattern is completed in the same size as the mask dimension of 40 µm.

[Table 3]

As shown in Table 3, also in the photocurable dry film of the composition which does not use the silicone skeleton containing polymer compound of this invention, remarkable peeling was observed on the SiN board | substrate and Cu board | substrate, and patterning was impossible. . Therefore, by using the silicone skeleton containing high molecular compound of this invention, the adhesiveness of a photocurable dry film also a pattern or a film, and a board | substrate is improved obviously.

V. Landfill Performance

A 6-inch silicon wafer was prepared in which 200 circular holes each having an opening diameter of 10 to 100 mu m (10 mu m unit size) and a depth of 10 to 120 mu m (10 mu m unit size) were formed. About the photocurable dry films of Examples 13, 14, and 15 of the said Table 3, the protective film was peeled off and a vacuum chamber was used using the vacuum laminator (product name: TEAM-100RF) manufactured by Takatori Co., Ltd. The inside was set to the vacuum degree of 100 Pa, and the photocurable resin layer on the support film was stuck to the said board | substrate on temperature conditions 100 degreeC. After returning to normal pressure, the substrate was cooled to 25 ° C., taken out of the vacuum laminator, and the supporting film was peeled off.

Next, after peeling a support film, 100 degreeC and the prebaking for 5 minutes were performed on the hotplate. Next, broadband light was irradiated to the said board | substrate by the exposure amount (wavelength 365nm) of Table 3 using the mask aligner (product name: MA-8) manufactured by Zus Microtec Co., Ltd. Subsequently, the substrate was post-exposure heated (PEB) at 110 ° C. for 5 minutes and cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Subsequently, it post-cured using nitrogen oven, purging nitrogen at 180 degreeC for 2 hours. Then, the obtained substrate was diced to form a cross section of a circular hole, and the cross section of the circular hole was observed using a scanning electron microscope (SEM) to evaluate the presence or absence of defects. The results are shown in Table 4.

As shown in Table 4, all are filled without a defect and it can be judged that the embedding performance as a film for electrical / electronic component protection is favorable.

[Table 4]

VI. Electrical Characteristics (Insulation Breakdown Strength)

About the photocurable dry film of the film thickness of 50 micrometers of Examples 13, 14, and 15 of the said Table 3, the protective film is peeled off and the photocurable resin layer on a support film is JISK on temperature conditions of 100 degreeC. It adhered to the board | substrate of 6249 regulation. And the said board | substrate was cooled to room temperature and the support film was peeled off. Next, after peeling a support film, 100 degreeC and the prebaking for 5 minutes were performed on the hotplate. Further, using the mask aligner, broadband light with an exposure amount of 1,000 mJ / cm ² (wavelength of 365 nm) was irradiated to the substrate through a quartz photomask. Subsequently, PEB was performed for 5 minutes at 110 degreeC, and it cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Subsequently, postcure was carried out while purging with nitrogen at 180 ° C. for 2 hours using an oven to prepare a substrate for measuring dielectric breakdown strength. And dielectric breakdown strength was measured according to the measuring method prescribed | regulated to JISK6249. The results are shown in Table 5.

As shown in Table 5, all the electrical characteristics as a coating film for protecting electrical and electronic components were good.

VII. Adhesiveness

About the photocurable dry film with a film thickness of 50 micrometers of Examples 13, 14, and 15 of the said Table 3, this protective film was peeled off and the inside of a vacuum chamber was set to the vacuum degree 100 Pa using the said vacuum laminator, The photocurable resin layer on the support film was adhered to an untreated 6-inch silicon wafer at a temperature condition of 100 ° C. After returning to normal pressure, the substrate was cooled to 25 ° C., taken out of the vacuum laminator, and the supporting film was peeled off. Next, after peeling a support film, 100 degreeC and the prebaking for 5 minutes were performed on the hotplate. Further, using the mask aligner, broadband light with an exposure amount of 1,000 mJ / cm ² (wavelength of 365 nm) was irradiated to the substrate through a quartz photomask. Subsequently, PEB was performed for 5 minutes at 110 degreeC, and it cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Subsequently, postcure was carried out while purging with nitrogen at 180 ° C. for 2 hours using an oven to obtain a post pattern cured film having a diameter of 300 μm and a height of 50 μm. The initial adhesiveness was evaluated for the said post-pattern hardened film by the resistance applied at the time of peeling a pattern hardened film from a board | substrate using the bond tester (product name: Dage series 4000-PXY) manufactured by the British Dage company. Measurement conditions were 50.0 micrometer / sec and 3.0 micrometers in measurement height.

1 is an explanatory diagram showing a method for measuring adhesion. In the drawing, reference numeral 1 denotes a silicon (Si) substrate, reference numeral 2 denotes a post pattern hardened film, reference numeral 3 denotes a measurement jig of a bond tester, and reference numeral 4 denotes a direction of movement of the measurement jig. The obtained numerical value is the average value of 15-point measurement, and shows that adhesiveness with respect to the board | substrate of a post pattern hardened film is high, so that a numerical value is high.

In addition, the said bond tester was apply | coated to the post pattern hardened film which apply | coated the solder flux liquid to the post pattern hardened film on a board | substrate, heated at 220 degreeC for 30 second, cooled, it wash | cleaned with pure water, and dried at room temperature for 2 hours. Then, the adhesiveness after deterioration was evaluated in the same manner as the initial stage by the resistance applied when peeling the pattern from the substrate. The three types of photocurable dry films were evaluated for adhesiveness by comparing the initial values, and by comparing the behaviors in which the values decreased after deterioration from the initial stage, respectively, the chemicals against the solder flux liquid together with the adhesiveness. Tolerance was also evaluated. The results are shown in Table 5. As shown in Table 5, adhesiveness as a coating film for protecting electrical and electronic components was good.

VIII. Crack resistance

About the photocurable dry film with a film thickness of 50 micrometers of Examples 13, 14, and 15 of the said Table 3, this protective film was peeled off and the inside of a vacuum chamber was set to the vacuum degree 100 Pa using the said vacuum laminator, The photocurable resin layer on a support film was stuck to the board | substrate used for the said embedding performance on the temperature condition of 100 degreeC. After returning to normal pressure, the substrate was cooled to 25 ° C., taken out of the vacuum laminator, and the supporting film was peeled off.

Next, after peeling a support film, 100 degreeC and the prebaking for 5 minutes were performed on the hotplate. Next, using the said mask aligner, the broadband light of 1000 mJ / cm <^2> (365 nm of wavelengths) of exposures was irradiated to the said board | substrate through the photomask made from quartz. Subsequently, PEB was performed for 5 minutes at 110 degreeC, and it cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Subsequently, it post-cured using nitrogen oven, purging nitrogen at 180 degreeC for 2 hours.

The board | substrate with which this cured film was formed was thrown into the temperature cycle tester which sets -55- + 150 degreeC as 1 cycle, and it investigated to the presence or absence of the crack generation in the said cured film to 1,000 cycles. The results are shown in Table 5. As shown in Table 5, crack resistance as a coating for protecting electrical and electronic components was good.

IX. Stripper resistance

About the photocurable dry film with a film thickness of 50 micrometers of Examples 13, 14, and 15 of the said Table 3, this protective film was peeled off and the inside of a vacuum chamber was set to the vacuum degree 100 Pa using the said vacuum laminator, The photocurable resin layer on the support film was adhered to an untreated 6-inch silicon wafer at a temperature condition of 100 ° C. After returning to normal pressure, the substrate was cooled to 25 ° C., taken out of the vacuum laminator, and the supporting film was peeled off.

Next, after peeling a support film, 100 degreeC and the prebaking for 5 minutes were performed on the hotplate. Next, using the said mask aligner, the broadband light of 1000 mJ / cm <^2> (365 nm of wavelengths) of exposures was irradiated to the said board | substrate through the photomask made from quartz. Subsequently, PEB was performed for 5 minutes at 110 degreeC, and it cooled. Thereafter, spray development was performed for 5 minutes using propylene glycol monomethyl ether acetate (PGMEA). Subsequently, it post-cured by nitrogen purging at 180 degreeC for 2 hours using the oven, and the square pattern cured film of 15 mm x 15 mm was obtained.

And after immersing the said board | substrate in NMP (N-methylpyrrolidone) for 1 hour at room temperature, the film thickness change and the external appearance were investigated, and peeling liquid tolerance was evaluated. The results are shown in Table 5. As shown in Table 5, peeling liquid tolerance as a coating film for electrical / electronic component protection was all favorable.

[Table 5]

According to the present invention, a general negative resist in which a hole pattern or a space pattern formed by using a photocurable dry film is observed in a negative taper shape or an overhang shape in which an upper portion protrudes extremely long. It is possible to improve the characteristics of the material, to cope with a wide film thickness, and to form a fine pattern in a wide wavelength range, and to refine the pattern in the redistribution technology according to the high density and high integration of the chip. It is possible to provide a chemically amplified negative resist material and a photocurable dry film useful for a film for protecting electrical and electronic components.

1: Si substrate
2: Post-pattern hardened film of 300 micrometers in diameter X 50 micrometers in height
3: measuring jig of bond tester
4: Movement direction of the measuring jig

Claims (17)

A resin containing a silicone skeleton having a reaction point at which a crosslinking group or a crosslinking reaction occurs in a molecule, wherein the isocyanuric acid skeleton is bonded to a molecule or a terminal group, and has a weight average molecular weight of 3,000 to 500,000, a silicone skeleton-containing polymer compound . The method of claim 1,
Silicone skeleton containing high molecular compound whose isocyanuric acid skeleton is a divalent organic group represented by following General formula (4-1), and / or monovalent organic group represented by following General formula (4-2):
(43)

(In the general formula (4-1) and the general formula (4-2), T ¹ and T ² may be the same or different,
(44)

Of a monovalent group selected from any one, R ⁹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ¹⁰ is an alkyl group or an alkoxy group of a hydrogen atom, a group having 1 to 4 carbon atoms, or - (CH _{2) s} OH ( s = 0 to 3). The method according to claim 1 or 2,
Silicone skeleton-containing polymer compound having a repeating unit represented by the following general formula (1):
[Chemical Formula 45]

(In the above general formula ^(1), R 1 ~R ⁴ will be the same and is one of 1 to 8 carbon atoms which may be different from a hydrocarbon group, m is an integer from 1~100, a, b, c, d Is 0 or positive, e and f are positive, and a, b, c, and d are not 0 at the same time, except that a + b + c + d + e + f = 1 and X is 2 represented by the following general formula (2) Is a divalent organic group, Y is a divalent organic group represented by the following general formula (3), and W is a divalent organic group represented by the following general formula (4-1) and / or the following general formula (4-2) Monovalent organic group represented by
(46)

(In the general formula (2), Z is
(47)

A divalent organic group selected from any one of which n is 0 or 1, R <^5> and R <^6> is a C1-C4 alkyl group or an alkoxy group, respectively, may mutually differ or may be the same, and k is 0 , 1 or 2)
(48)

(In the general formula (3), V is
(49)

A divalent organic group selected from any one of which p is 0 or 1, R <^7> and R <^8> is a C1-C4 alkyl group or an alkoxy group, respectively, and may mutually differ or may be the same, and h is 0 , 1 or 2)
(50)

(In the general formula (4-1) and the general formula (4-2), T ¹ and T ² may be the same or different,
(51)

Of a monovalent group selected from any one, R ⁹ is an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ¹⁰ is an alkyl group or an alkoxy group of a hydrogen atom, a group having 1 to 4 carbon atoms, or - (CH _{2) s} OH ( s = 0 to 3). The method according to claim 2 or 3,
In the said general formula (4-1) and said general formula (4-2), T <^1> or T <^2> is represented by a following formula, A silicone skeleton containing high molecular compound:
(52)

. Hydrogensilphenylene represented by following General formula (5), and dihydroorganosiloxane represented by following General formula (6);
An epoxy group-containing compound having a diallyl group represented by the following general formula (7) and / or a phenol compound having a diallyl group represented by the following general formula (8); And
The silicone of Claim 3 which superposes | polymerizes the isocyanuric acid skeleton containing compound which has the diallyl group represented by following General formula (9) and / or the allyl group represented by following General formula (10) in presence of a catalyst. Process for preparing a skeleton-containing polymer compound:
(53)

(54)

(In said general formula (6), R <^3> , R <^4> and m are the same as the above.)
(55)

(V, R ⁷ , R ⁸ , p, h are the same as described above in General Formula (7).)
(56)

(In General Formula (8), Z, R ⁵ , R ⁶ , n, k are the same as above.)
(57)

(T <^1> , T <^2> is the same as the above in the said General formula (9) and the said General formula (10).). The method of claim 5,
A method for producing a silicone skeleton-containing polymer compound, wherein 0.1 to 10.0% by mass of the isocyanuric acid skeleton-containing compound is added to the total amount of the silicone polymer compound raw material. (A) The silicone skeleton-containing polymer compound according to any one of claims 1 to 4;
(B) an amino condensate modified with formaldehyde or formaldehyde-alcohol, a phenol compound having an average of two or more methylol groups or alkoxymethylol groups in one molecule, or a compound in which a hydroxyl group of a polyhydric phenol is substituted with a glycidoxy group One or two or more crosslinking agents selected from;
(C) a photo-acid generator which decomposes | disassembles with the light of wavelength 190-500 nm, and produces | generates an acid; And
(D) solvent
Resin composition containing the. The chemically amplified negative resist material which consists of a resin composition of Claim 7. The photocurable resin layer with a film thickness of 10-100 micrometers is a photocurable dry film which has a structure sandwiched between a support film and a protective film, The photocurable resin composition used for formation of a photocurable resin layer is resin of Claim 7 Photocurable dry film which consists of a composition. (1) applying the chemically amplified negative resist material according to claim 8 on a substrate;
(2) Next, after heat processing, exposing to high energy rays or an electron beam of wavelength 190-500 nm through a photomask; And
(3) The process of developing using a developing solution after heat processing
Pattern forming method comprising a. The method of claim 10,
After the image development, (4) the pattern formation method further including the process of postcure the film formed by pattern development at the temperature of 100-250 degreeC. The hardened | cured material layer of the photocurable resin composition formed with the photocurable dry film of Claim 9 is laminated | stacked on the board | substrate which has a groove | channel and / or hole whose opening width is 10-100 micrometers, and a depth is 10-120 micrometers. Laminate. (i) applying the resin composition according to claim 7 on a support film;
(ii) drying the resin composition to form a photocurable resin layer on the support film; And
(iii) Furthermore, the process of bonding a protective film on the said photocurable resin layer
Method for producing a photocurable dry film comprising a. (i) Process of contacting the photocurable resin layer exposed by peeling a protective film from the photocurable dry film of Claim 9 to a board | substrate, and forming a film;
(ii) exposing to light having a wavelength of 190 to 500 nm through a photomask through the support film or in a state where the support film is peeled off;
(iii) performing post exposure bake (PEB); And
(iv) Process of developing with developer
Pattern forming method comprising a. 15. The method of claim 14,
After the image development (v) The pattern formation method further includes the process of post-curing the film patterned by image development at the temperature of 100-250 degreeC. 16. The method according to claim 14 or 15,
The pattern formation method in which a board | substrate is a board | substrate which has the groove | channel and / or hole of 10-100 micrometers in opening width, and 10-120 micrometers in depth. The protective film for electric and electronic components which consists of a hardened film obtained by the pattern formation method of Claim 15.

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