JP5444833B2 - Photosensitive resin composition, rib pattern forming method and electronic component - Google Patents

Description

  The present invention relates to a photosensitive resin composition that is excellent in moist heat resistance and has a high elastic modulus at a high temperature and is capable of forming a thick film, a rib pattern forming method using the same, and an electronic component.

  In recent years, as semiconductor devices have been highly integrated and miniaturized, rapid increase in capacity and cost have been realized. A package of an element that exhibits a specific electrical function by forming an electrode pattern or a fine structure on the surface of a single crystal wafer, represented by a surface acoustic wave (SAW) filter, has characteristics when the functional part surface is covered with a resin or the like. In order to change, a hollow structure is required so that other objects do not touch particularly functionally important parts of the device surface. In addition, image sensors represented by CMOS and CCD sensors have a hollow structure in which the light receiving unit is covered with a glass lid in order to protect the element from moisture and dust that hinder imaging and not to block light from the outside. It has become. Also in MEMS, a hollow structure is used to protect the movable part.

These elements that require a hollow structure conventionally form a hollow structure by processing and joining inorganic materials (see Patent Document 1 below).
However, the processing of these inorganic materials is problematic in that the cost is increased due to an increase in the number of parts and the number of processes, and it is difficult to reduce the size and height due to structural limitations (Patent Document 2 below). 3).

In order to solve this problem, a hollow structure forming method using a non-photosensitive resin film has been proposed as an alternative to inorganic materials (ceramics) (see Patent Document 4 below).
However, even with this method, there are problems with reliability such as heat and humidity resistance and retention of hollow parts, and the need for drilling electrode parts with a laser for miniaturization is a problem, which is satisfactory in terms of quality and cost. It is not something that can be done.

  Therefore, it is desired to develop a photosensitive resin material that can be easily drilled by photolithography and that has moisture and heat resistance and hollow portion retention properties (see Patent Documents 5 and 6 above).

JP-A-8-191181 JP 2001-244785 A JP-A-8-204482 JP-A-6-164292 JP 2008-227748 A JP 2004-64732 A

  By the way, as a photosensitive resin having high heat resistance and high reliability, a photosensitive polyimide resin can be considered. However, it is difficult to form a film having a thickness of 10 μm or more with a conventional photosensitive polyimide resin. is there. For this reason, it is difficult to form a sufficient height required for forming the hollow structure.

On the other hand, as a photosensitive resin necessary for forming a hollow structure and capable of forming a thick film with a thickness of about 30 μm, a photosensitive epoxy resin can be cited. However, a photosensitive epoxy resin generally has a high water absorption rate and does not provide sufficient moisture and heat resistance as compared with a polyimide resin. Therefore, it is considered that moisture permeation at a high temperature adversely affects the element in the hollow portion.
In general, an epoxy resin has a low elastic modulus at a high temperature as compared with a polyimide resin, and the hollow may be crushed when pressure is applied to the hollow structure under a high temperature and high pressure condition. Further, when the resolution is low, there is a problem because a fine pattern cannot be formed or a development residue is generated.

  Therefore, the present invention was made to solve the conventional problems as described above, and has excellent moisture and heat resistance, a cured product having a high elastic modulus at a high temperature, and excellent hollow structure retention. It aims at providing the resin composition, the formation method of the rib pattern using the same, and an electronic component.

  In order to achieve the above object, the present invention provides (A) a polyamic acid, (B) a photopolymerizable compound having an ethylenically unsaturated group, and (C) a heat having at least one methylol group or alkoxyalkyl group. A photosensitive resin composition containing a polymerizable compound and (D) a photopolymerization initiator is provided.

According to such a photosensitive resin composition, the heat and moisture resistance is excellent, the cured product has a high elastic modulus at a high temperature, and the hollow structure retainability is also excellent.
By having the said structure containing the (A) polyamic acid which is a polyimide precursor, the said resin cured material exhibits the outstanding heat-and-moisture resistance. In addition, by using the above (A) polyamic acid, the cured resin exhibits excellent heat resistance and rigidity. Furthermore, the photosensitive resin composition can form a thick film with good resolution by using (B) a photopolymerizable compound having an ethylenically unsaturated group. Moreover, the photosensitive resin composition has a high elastic modulus at a high temperature by containing the (A) polyamic acid and (C) a thermopolymerizable compound having at least one methylol group or alkoxyalkyl group, For example, it is possible to obtain a hollow portion retainability that can withstand a sealing resin mold pressure at a high temperature.

The (C) thermopolymerizable compound is preferably a compound represented by the following general formula (1), and more preferably a compound represented by the following general formula (2).

[In formula (1), X represents a single bond or an n-valent organic group, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4. P represents an integer of 1 to 4, q represents an integer of 0 to 3, and the sum of p and q is 4. When q and / or n is 2 or more, a plurality of R ¹ may be the same or different, and when p and / or n is 2 or more, a plurality of R ² are the same or different. May be. ]

[In formula (2), two Y each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ^{3 to} R ⁶ each independently represents a monovalent organic group, and p1 and p2 Are each independently an integer of 1 to 4, and q1 and q2 are each independently an integer of 0 to 3. However, some carbon atoms of the alkyl group in Y may be substituted with oxygen atoms, and some or all of the hydrogen atoms in Y may be substituted with fluorine atoms. ]

The (A) polyamic acid preferably includes a polyamic acid having a structure represented by the following general formula (3).

[In the formula (3), Ar ¹ represents a tetravalent organic group represented by the following general formula (4) or the following general formula (5), and Ar ² represents the following general formula (6) or the following general formula (7 ), A divalent organic group represented by the following general formula (8) or the following general formula (9), and k represents an integer of 1 or more. When k is 2 or more, a plurality of Ar ¹ and Ar ² may be the same or different. ]

[In the formula (4), X ² represents a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,

(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. M2 and n2 each independently represent an integer of 0 to 3. In addition, when m2 is 2 or more, a plurality of R ¹¹ may be the same or different, and when n2 is 2 or more, a plurality of R ¹² may be the same or different. ]

Wherein (5), ^{X 3} represents an alkylene group having 5 to 20 carbon ^{atoms, R 14} and ^{R 15} each independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, m3 and n3 each independently represents an integer of 0 to 3. In addition, when m3 is 2 or more, a plurality of R ¹⁴ may be the same or different, and when n3 is 2 or more, a plurality of R ¹⁵ may be the same or different. ]

[In Formula (6), Y ¹ is a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,

(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹⁶ and R ¹⁷ each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. , P and q each independently represent an integer of 0 to 4. In addition, when p is 2 or more, a plurality of R ¹⁶ may be the same or different, and when q is 2 or more, a plurality of R ¹⁷ may be the same or different. ]

[In the formula (7), Z ¹ represents a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,

(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group having 1 to 6 carbon atoms or 1 to 1 carbon atoms. 3 represents an alkoxy group, and r, s, t and u each independently represents an integer of 0 to 4. When r is 2 or more, a plurality of R ¹⁸ may be the same or different. When s is 2 or more, a plurality of R ¹⁹ may be the same or different, and when t is 2 or more. The plurality of R ²⁰ may be the same or different, and when u is 2 or more, the plurality of R ²¹ may be the same or different. ]

Wherein ^{(8), R 22} represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, v is an integer of 0 to 3. When v is 2 or more, a plurality of R ²² may be the same or different. ]

Wherein (9), ^{Z 2} represents a single bond or a divalent organic group, ^{Y 2} and ^{Y 3} represents an alkylene group having 5 to 20 carbon atoms independently. ]

Here, Z ² in the general formula (9) is preferably a divalent organic group represented by the following general formula (10), (11) or (12). Thereby, the heat-and-moisture resistance of the resin cured material obtained by hardening | curing the photosensitive resin composition can be improved more.

Wherein ^{(10), R 23} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 10 carbon atoms having 1 to 10 carbon atoms, w1 is an integer of 0-4. In addition, when w1 is 2 or more, a plurality of R ²³ may be the same or different. ]

[In the formula (11), R ²⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w2 represents an integer of 0 to 4. When w2 is 2 or more, a plurality of R ²⁴ may be the same or different. ]

[In Formula (12), R ²⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w3 represents an integer of 0 to 4. In addition, when w3 is 2 or more, a plurality of R ²⁵ may be the same or different. ]

The present invention also includes a step of laminating a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention on a substrate, and exposure by irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays. A photocuring part of the photosensitive resin composition layer, a removal process of removing a part other than the exposed part of the photosensitive resin composition layer using a developer, and a cured resin product obtained by thermally curing the exposed part of the photosensitive resin composition layer. And a method of forming a rib pattern having a thermosetting process.
According to such a forming method, since the photosensitive resin composition of the present invention is used, solvent development using an organic solvent is possible, an image can be formed with good resolution with a thick film, and high at a high temperature. Has elastic modulus. Therefore, hollow crushing at the time of resin sealing can be sufficiently suppressed.

  The present invention further has a hollow structure in which a cured product formed by curing the photosensitive resin composition of the present invention in the form of a film is formed on the rib pattern formed by the rib pattern forming method of the present invention. Provide electronic components.

  According to the present invention, a photosensitive resin composition that can be applied to solvent development, has excellent heat and humidity resistance, has a high high temperature elastic modulus, and can form an image with a high resolution with a thick film, and a hollow structure forming method using the same. Can be provided.

1 is a schematic cross-sectional view showing a preferred embodiment of a SAW filter that is one of the electronic components of the present invention. It is process drawing which shows suitable one Embodiment of the manufacturing method of a SAW filter.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the following description, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

(Photosensitive resin composition)
The photosensitive resin composition of the present invention comprises (A) polyamic acid (hereinafter sometimes referred to as “component (A)”) and (B) a photopolymerizable compound (hereinafter sometimes referred to as “component (B)”). And (C) a thermally polymerizable compound (hereinafter sometimes referred to as “(C) component”) and (D) a photopolymerization initiator (hereinafter sometimes referred to as “(D) component”), The component (B) is a polymerizable compound having an ethylenically unsaturated group, and the (C) thermopolymerizable compound is a compound having at least one methylol group or alkoxyalkyl group. Hereinafter, each component will be described in detail.

  (A) The polyamic acid can be obtained, for example, by reacting (a1) a tetracarboxylic dianhydride component with (a2) a diamine component.

  Examples of the (a1) tetracarboxylic dianhydride component include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic acid. Anhydride, 1,2,4,5-cyclopentanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3, 3 ', 4,4'-bicyclohexyltetracarboxylic anhydride, 3,3', 4,4'-biphenyltetracarboxylic anhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenone tet Carboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic anhydride (4,4′-oxydiphthalic dianhydride), 2,3 ′, 4,4′-diphenyl ether tetracarboxylic acid Dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic anhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic Acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis [4- (3 4-dicarbo Cibenzoyloxy) phenyl] nonane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [4- (3,4-di Carboxybenzoyloxy) phenyl] tridecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] tetradecane dianhydride, 2,2-bis [4- (3,4-di Carboxybenzoyloxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-methyldecane dianhydride, 1,1-bis [4- (3 4-Dicarboxybenzoyloxy) phenyl] -2-methyloctane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2- Ethylpentadecane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] dodecane dianhydride, 2,2-bis [3,5-dimethyl-4 -(3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] tridecane dianhydride, 2 , 2-bis [3,5-diethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] Cyclohexane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] propylcyclohexane dianhydride, 1,1-bis [4- (3,4 Dicarboxybenzoyloxy) phenyl] heptylcyclohexane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 4,4-bis (2,3-dicarboxyphenoxy) diphenylmethane An anhydride etc. are mentioned. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the (a2) diamine component include 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4. '-Diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4 '-Methylenebis (cyclohexylamine), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'-diethoxy-4,4' -Diaminodiphenylmethane, bis (3-aminophenyl) ether, bis (4-aminophenyl) ether, 3,4'-diamino Phenyl ether, 3,3′-diethyl-4,4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 3,3 '-Dimethyl-4,4'-diaminodiphenylsulfone, 3,3'-diethyl-4,4'-diaminodiphenylsulfone, 3,3'-dimethoxy-4,4'-diaminodiphenylsulfone, 3,3'- Diethoxy-4,4′-diaminodiphenylsulfone, 3,3′-dimethyl-4,4′-diaminodiphenylpropane, 3,3′-diethyl-4,4′-diaminodiphenylpropane, 3,3′-dimethoxy- 4,4′-diaminodiphenylpropane, 3,3′-diethoxy-4,4′-diaminodiphenylpropane, 2 2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfide 3,3′-dimethyl-4,4′-diaminodiphenyl sulfide, 3,3′-diethyl-4,4′-diaminodiphenyl sulfide, 3,3′-dimethoxy-4,4′-diaminodiphenyl sulfide, 3, , 3′-diethoxy-4,4′-diaminodiphenyl sulfide, 2,2′-diaminodiethyl sulfide, 2,4′-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,3-bis (4 -Aminophenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (4-amino) Nophenyl) ethane, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, o-toluidinesulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, 4,4′-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, bis (4- Aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) -N-phenylamine, bis (4-aminophenyl) -N-methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5 -Diaminonaphthalene, 1,6-diaminonaphthalene, 1 7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene, 1,5-diamino-2-methylnaphthalene, 1, 3-diamino-2-phenylnaphthalene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 3,3′-dihydroxy-4,4′- Diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,4′-dimethyl-4,4′-diaminobiphenyl, 3, 3′-dimethoxy-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 2,4-diaminotoluene 2,5-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino-4,6-dimethylbenzene, 1,4- Diamino-2,5-dimethylbenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,4-bis (2- Methoxy-4-aminopentyl) benzene, 1,4-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,4-bis (4-aminophenoxy) benzene, o-xylenediamine, m-xylenediamine P-xylenediamine, 9,10-bis (4-aminophenyl) anthracene, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4-aminophenyl-3-aminobenzoate, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2- (3-aminophenyl) -2 -(4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, , 1-bis (4-aminophenyl) -1-phenyl-2,2,2-trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2, 2-trifluoroethane, 1,3-bis (3-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenyl) decafluoropro 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-) 4-methylphenyl) hexafluoropropane, 1,4-bis (3-aminophenyl) but-1-ene-3-yne and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Here, when either or both of (a1) tetracarboxylic dianhydride component and (a2) diamine component are used, those having an alkylene group of 5 to 20 carbon atoms in the main chain are used. , Low water absorption, low warpage, and resist wettability during thermocompression bonding are preferable.

  Moreover, if an alicyclic hydrocarbon group and / or an aromatic group is contained in the main chain of either or both of the (a1) tetracarboxylic dianhydride component and the (a2) diamine component, the heat resistance is further improved. Can be improved.

Moreover, it is preferable that (A) polyamic acid does not contain ether bonds, such as a polyalkyleneoxy group. The ether bond is fragile at high temperatures and therefore tends to cause a decrease in the heat resistance (5% mass reduction temperature) of the resin. Furthermore, when it has an ether bond, it tends to absorb water and tends to be a factor that adversely affects insulation properties (HAST) and the like. Examples of the polyamic acid having an alkylene group having 5 to 20 carbon atoms that does not contain an ether bond include compounds having a structure represented by the following general formula (3).

In General Formula (3), Ar ¹ represents a tetravalent organic group represented by the following General Formula (4) or the following General Formula (5), and Ar ² represents the following General Formula (6) or the following General Formula (7) ), A divalent organic group represented by the following general formula (8) or the following general formula (9), and k represents an integer of 1 or more. When k is 2 or more, a plurality of Ar ¹ and Ar ² may be the same or different.

In the general formula (4), X ² represents a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,

(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. M2 and n2 each independently represent an integer of 0 to 3. In addition, when m2 is 2 or more, a plurality of R ¹¹ may be the same or different, and when n2 is 2 or more, a plurality of R ¹² may be the same or different.

In the general formula (5), X ³ represents an alkylene group having 5 to 20 carbon atoms, preferably an alkylene group having 6 to 12 carbon atoms. R ¹⁴ and R ¹⁵ each independently represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. Further, m3 and n3 each independently represents an integer of 0 to 3. In addition, when m3 is 2 or more, a plurality of R ¹⁴ may be the same or different, and when n3 is 2 or more, a plurality of R ¹⁵ may be the same or different.

In General Formula (6), Y ¹ is a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,

(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹⁶ and R ¹⁷ each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. P and q each independently represents an integer of 0 to 4. In addition, when p is 2 or more, a plurality of R ¹⁶ may be the same or different, and when q is 2 or more, a plurality of R ¹⁷ may be the same or different.

In General Formula (7), Z ¹ is a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,

(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group having 1 to 6 carbon atoms or 1 carbon atom. Represents an alkoxy group of ˜3, and r, s, t and u each independently represents an integer of 0 to 4. When r is 2 or more, a plurality of R ¹⁸ may be the same or different. When s is 2 or more, a plurality of R ¹⁹ may be the same or different, and when t is 2 or more. The plurality of R ²⁰ may be the same or different, and when u is 2 or more, the plurality of R ²¹ may be the same or different.

In General Formula (8), R ²² represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and v represents an integer of 0 to 3. When v is 2 or more, a plurality of R ²² may be the same or different.

In the general formula (9), Z ² represents a single bond or a divalent organic group, and preferably represents a divalent organic group represented by the following general formula (10), (11) or (12). Y ² and Y ³ each independently represent an alkylene group having 5 to 20 carbon atoms, preferably an alkylene group having 6 to 16 carbon atoms. By using a polyamic acid having a structure of the above general formula (9) in which Z ² is a group represented by the following general formula (10), (11) and / or (12), low temperature curability (for example, 200 ° C. ), Low warpage, heat resistance (5% mass reduction temperature), insulation and low water absorption can be further improved.

In General Formula (10), R ²³ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w1 represents an integer of 0 to 4. In addition, when w1 is 2 or more, a plurality of R ²³ may be the same or different.

In the general formula (11), R ²⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w2 represents an integer of 0 to 4. When w2 is 2 or more, a plurality of R ²⁴ may be the same or different.

In General Formula (12), R ²⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w3 represents an integer of 0 to 4. In addition, when w3 is 2 or more, a plurality of R ²⁵ may be the same or different.

  Moreover, the compound represented by the following general formula (13) is mentioned as (a1) tetracarboxylic dianhydride component which has a C5-C20 alkylene group in the main chain mentioned above.

Wherein (13), ^{X 3} represents an alkylene group having 5 to 20 carbon atoms. ]
Examples of the compound represented by the general formula (13) include pentamethylene bis trimellitate dianhydride, hexamethylene bis trimellitate dianhydride, heptamethylene bis trimellitate dianhydride, octamethylene bis trimellitate dianhydride. Products, nonamethylene bistrimellitic dianhydride, decamethylene bistrimellitate dianhydride, dodecamethylene bistrimellitate dianhydride, and the like. These can be used alone or in combination of two or more.

  Examples of the (a2) diamine component having an alkylene group having 5 to 20 carbon atoms in the main chain described above include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, and 2,11-diamino. Dodecane, 1,12-diaminooctadecane, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, Examples thereof include aliphatic diamines such as 3-methoxyhexamethylenediamine and compounds represented by the following general formula (14), (15) or (16).

[In Formula (14), Y ² and Y ³ each independently represent an alkylene group having 5 to 20 carbon atoms, and R ²³ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms or a carbon number. 1-3 represents an alkoxy group, and w1 represents an integer of 0-4. In addition, when w1 is 2 or more, a plurality of R ²³ may be the same or different. ]

[In Formula (15), Y ² and Y ³ each independently represent an alkylene group having 5 to 20 carbon atoms, and R ²⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or a carbon number. 1-3 represents an alkoxy group, and w2 represents an integer of 0-4. When w2 is 2 or more, a plurality of R ²⁴ may be the same or different. ]

[In Formula (16), Y ² and Y ³ each independently represent an alkylene group having 5 to 20 carbon atoms, and R ²⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms or a carbon number. 1-3 represents an alkoxy group, and w3 represents an integer of 0-4. In addition, when w3 is 2 or more, a plurality of R ²⁵ may be the same or different. ]

  Examples of the compound represented by the general formula (15) include [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene (trade name “Versamine 551”, Cognis Japan ( (Made by Co., Ltd.) is available as a commercial product. These can be used alone or in combination of two or more.

  The (A) polyamic acid is composed of (a1) a tetracarboxylic dianhydride component and (a2) a diamine, as described above, from the viewpoints of low-temperature curability (for example, 200 ° C. or less), low water absorption, and moist heat resistance. It is preferably a compound having an alkylene group having 5 to 20 carbon atoms in the main chain, obtained by reaction with a component, more preferably a compound having an alkylene group having 6 to 16 carbon atoms. A compound having 7 to 14 alkylene groups is particularly preferable. In the case of having an alkylene group having less than 5 carbon atoms, the water absorption and elastic modulus of the resulting cured resin product tend to increase. In the case of having an alkylene group having more than 20 carbon atoms, There exists a tendency for heat resistance etc. to fall.

  The (A) polyamic acid used in the present invention is, for example, a reaction of approximately equimolar (a1) tetracarboxylic dianhydride component and (a2) diamine component in an organic solvent at 80 ° C. or lower, preferably 60 ° C. or lower. It can be obtained by an addition polymerization reaction at a temperature for 1 to 12 hours.

  Examples of the solvent for reacting the (a1) tetracarboxylic dianhydride component with the (a2) diamine component include nitrogen-containing solvents (N, N′-dimethylsulfoxide, N, N′— Dimethylformamide, N, N′-diethylformamide, N, N′-dimethylacetamide, N, N′-diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide N-methylpyrrolidone, etc.), lactones (γ -Butyrolactone, γ-valerolactone, γ-caprolactone, ε-caprolactone, α-acetyl-γ-butyrolactone, etc.), alicyclic ketones (cyclohexanone, 4-methylcyclohexanone, etc.), ethers (3-methyl-3- Methoxybutyl acetate, diethylene glycol dimethyl ether acetate, etc.) It is below. Among these, from the viewpoints of solubility and reactivity, cyclic ester solvents or nitrogen-containing solvents are preferable, and N-methyl-2-pyrrolidone is particularly preferable. These can be used alone or in combination of two or more.

  The combination of the (a1) tetracarboxylic dianhydride component and the (a2) diamine component is selected in consideration of the heat resistance, mechanical properties, and electrical properties of the polyimide resin film (resin cured product) after final curing. It is preferable to do.

  Moreover, in order to improve the adhesiveness of (A) polyamic acid, it is preferable to introduce aminophenol or a derivative thereof into (A) polyamic acid. Examples of aminophenol and derivatives thereof include o-aminophenol, m-aminophenol, and p-aminophenol. Among these, m-aminophenol is preferable from the viewpoint of adhesiveness.

  The amount introduced when aminophenol or a derivative thereof is introduced is preferably 0.1 to 10 mol, more preferably 1 to 5 mol, based on 100 mol of (A) polyamic acid, and 2 to 3 It is particularly preferred that it be a mole. If the amount of aminophenol or its derivative introduced is less than 0.1 mol, the effect of improving adhesiveness tends to be insufficient, and if it exceeds 10 mol, the developability and storage stability tend to be lowered.

  The weight average molecular weight of the polyamic acid as the component (A) is preferably 10,000 to 60,000, and more preferably 20,000 to 50,000. If the weight average molecular weight is less than 10,000, the cured film tends to be brittle, and if it exceeds 60,000, the developability tends to decrease.

  The content of the (A) polyamic acid is preferably 20 to 80 parts by mass and preferably 30 to 60 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). More preferred. When this content is less than 20 parts by mass, the developability tends to be lower than when the content is within the above range. When the content exceeds 80 parts by mass, the content is within the above range. Compared with the case where it exists in the inside, it exists in the tendency for the resolution to fall or the imidation rate at low temperature to fall.

  The component (B) may be a photopolymerizable compound having at least one ethylenically unsaturated group.

  Examples of the polymerizable compound having at least one ethylenically unsaturated group include a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, an amide bond, and two or more ethylenically unsaturated groups. Urethane monomer or urethane such as a polymerizable compound, a bisphenol A-based (meth) acrylate compound, a compound obtained by reacting a glycidyl group-containing compound with an α, β-unsaturated carboxylic acid, a (meth) acrylate compound having a urethane bond Examples include oligomers, nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, and (meth) acrylic acid alkyl esters. These are used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. These are used alone or in combination of two or more.

The polymerizable compound having the amide bond and two or more ethylenically unsaturated groups is preferably a compound represented by the following general formula (31).

[In the formula (31), R ³¹ , R ³² and R ³³ each independently represents a divalent organic group, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ and R ³⁶ each independently represent hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group is shown. ]

  The polymerizable compound represented by the general formula (31) is a di (meth) acrylate having an amide bond, obtained by reacting an oxazoline group-containing compound with a carboxyl group-containing compound and / or a phenolic hydroxyl group-containing compound. Preferably there is. The polymerizable compound represented by the general formula (1) includes, for example, a bisoxazoline represented by the following general formula (17), a compound having two phenolic hydroxyl groups in one molecule, and (meth) acrylic. It can be obtained by reacting with an acid.

In General Formula (17), Y ⁴ represents a divalent organic group, and may have a phenylene group that may have a substituent, a pyridylene group that may have a substituent, or C 1-10. An alkylene group which may be branched is preferred. R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

  Examples of the bisoxazoline represented by the general formula (17) include 2,2 ′-(1,3-phenylene) bis-2-oxazoline and 2,6-bis (4-isopropyl-2-oxazoline-2). -Yl) pyridine, 2-2'-isopropylidenebis (4-phenyl-2-oxazoline), 2-2'-isopropylidenebis (4-tertiarybutyl-2-oxazoline) and the like. These can be used alone or in combination of two or more.

Examples of the compound having two phenolic hydroxyl groups in one molecule include biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy) -3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) Xafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxy) Phenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxy) Phenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9- Bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9 , 9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-) 3,5-dibromophenyl) fluorene and the like. Among these, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane is particularly preferable. These can be used alone or in combination of two or more.
The above-mentioned polymerizable compound having an amide bond and two or more ethylenically unsaturated groups in the molecule can be used alone or in combination of two or more.

  The reaction between the phenolic hydroxyl group-containing compound and / or the carboxyl group-containing compound and the oxazoline group-containing compound is preferably performed at a reaction temperature of 50 to 200 ° C. When the reaction temperature is less than 50 ° C., the reaction is slow, and when the reaction temperature is 200 ° C., many side reactions tend to occur. In some cases, the reaction may be carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethylsulfoxide.

Examples of the compound obtained by reacting the glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include epoxy resins such as novolak type epoxy resins, bisphenol type epoxy resins, salicylaldehyde type epoxy resins, and (meth) Examples thereof include an epoxy acrylate compound obtained by reacting acrylic acid. An acid-modified epoxy acrylate compound obtained by reacting an acid anhydride such as tetrahydrophthalic anhydride with the OH group of the epoxy acrylate compound can also be used. As such an acid-modified epoxy acrylate compound, for example, EA-6340 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) having a structural unit represented by the following general formula (18) is commercially available.

[Wherein, the ratio of m to n is 100/0 to 0/100. ]

As the (meth) acrylate compound having a urethane bond, a (meth) acrylic monomer having an OH group at the β-position, isophorone diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene Addition reaction products with diisocyanate compounds such as diisocyanate; EO-modified urethane di (meth) acrylate; EO or PO-modified urethane di (meth) acrylate; carboxyl group-containing urethane (meth) acrylate; diol compound and the like.
The photopolymerizable compound having an ethylenically unsaturated group described above is used singly or in combination of two or more.
Among these photopolymerizable compounds, (A) a photopolymerizable compound having an amide bond and two or more ethylenically unsaturated groups is preferable from the viewpoint of compatibility with the polyamic acid and the heat resistance of the cured film.

  Examples of the compound having at least one methylol group or alkoxyalkyl group as component (C) include two or more methylol groups and alkoxymethyl groups in the molecule, and these groups are bonded to the benzene ring. Or a melamine resin substituted with a methylol group and / or an alkoxymethyl group at the N-position, a urea resin, or the like. Among these, a compound having at least one methylol group in the molecule is more preferable from the viewpoints of solubility, varnish stability, and elastic modulus at high temperature of the cured film.

Examples of the compound having at least one methylol group or alkoxyalkyl group as component (C) include compounds having the following structures, and these are commercially available.

Although there is no restriction | limiting in particular in these compounds which can be used for this invention, The compound represented by following General formula (1) from the point of stability and the elasticity modulus in the high temperature of a cured film is preferable, and following General formula (2) ) Is more preferable.

[In formula (1), X represents a single bond or an n-valent organic group, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 4. P represents an integer of 1 to 4, q represents an integer of 0 to 3, and the sum of p and q is 4. When q and / or n is 2 or more, a plurality of R ¹ may be the same or different, and when p and / or n is 2 or more, a plurality of R ² are the same or different. May be. ]

[In formula (2), two Y each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ^{3 to} R ⁶ each independently represents a monovalent organic group, and p1 and p2 Are each independently an integer of 1 to 4, and q1 and q2 are each independently an integer of 0 to 3. However, some carbon atoms of the alkyl group in Y may be substituted with oxygen atoms, and some or all of the hydrogen atoms in Y may be substituted with fluorine atoms. ]

Specifically, an alkoxy group or the like in which some carbon atoms of the alkyl group in Y are substituted with oxygen atoms, and some or all of the hydrogen atoms in Y are substituted with fluorine atoms As a perfluoroalkyl group. Moreover, as monovalent organic groups of R ^{3 to} R ⁶ , specifically, hydrocarbons such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, and amyl group Groups are illustrated as typical examples, but are not limited thereto.

In the general formula (1), as the organic group represented by X, an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group or a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, Arylene groups having 6 to 30 carbon atoms such as phenylene groups, groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms, sulfone groups, carbonyl groups, ether bonds, thioether bonds, An amide bond etc. are mentioned, The divalent organic group shown by following General formula (19) is mentioned as a preferable thing.

[In formula (19), each X ′ is independently a divalent organic group, an alkylene group (for example, one having 1 to 10 carbon atoms), an alkylidene group (for example, having 2 to 10 carbon atoms). And a group in which part or all of these hydrogen atoms are substituted with a halogen atom, a sulfone group, a carbonyl group, an ether bond, a thioether bond, an amide bond, etc., and R ⁹ is a hydrogen atom, a hydroxy group A group, an alkyl group or a haloalkyl group, and when there are plural groups, R ⁹ and X ′ may be the same as or different from each other, and m4 is 1 to 10. ]

Specific examples of monovalent organic groups for R ¹ and R ² include hydrocarbons such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, and amyl groups. Groups are illustrated as typical examples, but are not limited thereto.

  Among the above components (C), from the viewpoint of improving the high-temperature elastic modulus of the cured film, in general formula (2), each Y is independently a methyl group, or some or all of the hydrogen atoms are substituted with fluorine atoms. Particularly preferred are compounds in which p1 and p2 are 2, and q1 and q2 are 0.

  The content of the component (C) is preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, with respect to 100 parts by weight of the component (A). 20 parts by weight is particularly preferable. When this content is less than 0.1 parts by mass, the elastic modulus at high temperature tends to be lower than when the content is in the above range, and when the content exceeds 50 parts by mass, Compared with the case where the amount is within the above range, the resolution tends to be lowered.

  The photopolymerization initiator as the component (D) is not particularly limited as long as it generates free radicals by actinic rays. For example, aromatic ketone, acylphosphine oxide, oxime esters, quinones, benzoin ether Examples thereof include compounds, benzyl derivatives, 2,4,5-triarylimidazole dimers, acridine derivatives, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds.

  Examples of the aromatic ketone include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (that is, Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4. '-Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Propan-1-one is mentioned.

  Examples of the acylphosphine oxide include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  Examples of oxime esters include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)].

  Examples of quinones include 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenyl. Examples include anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether.

  Examples of the benzyl derivative include benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, and benzyldimethyl ketal.

Examples of the 2,4,5-triarylimidazole dimer include 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2- Yl] -4,5-diphenylimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer is mentioned.

  Examples of the acridine derivative include 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.

  (D) A photoinitiator may be synthesize | combined by a conventional method and a commercially available thing may be obtained. Available (D) photopolymerization initiators include, for example, Irgacure-369, Irgacure-907, Irgacure-651, Irgacure-819 (all of which are manufactured by Ciba Specialty Chemicals Co., Ltd., trade name), oxime Examples thereof include compounds having an ester bond.

Among the photopolymerization initiators (D) described above, compounds having an oxime ester bond are particularly preferable from the viewpoint of improving photocurability and increasing sensitivity. More specifically, as a compound having an oxime ester bond, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) represented by the following formula (8) (trade name) : OXE-01, manufactured by Ciba Specialty Chemicals), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) (trade name: OXE-02, manufactured by Ciba Specialty Chemicals), 1-phenyl-1,2-propanedione-2- [O- (ethoxycarbonyl) oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.), etc. Can be mentioned.

  The said (D) photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  The content of the photopolymerization initiator (D) is preferably 0.1 to 20% by mass, and preferably 0.5 to 10% by mass based on the total solid content of the photosensitive resin composition. More preferably, it is 1-5 mass% especially preferable. (D) When the content of the photopolymerization initiator is out of the above range, the sensitivity of the photosensitive resin composition is reduced or the resist shape is deteriorated as compared with the case where the content is within the above range. There is a tendency.

Further, (E) a sensitizer can be further added to the above-mentioned photosensitive resin composition. Examples of the (E) sensitizer include pyrazolines, anthracenes, coumarins, xanthones, and oxazoles. Benzoxazoles, thiazoles, benzothiazoles, triazoles, stilbenes, triazines, thiophenes, naphthalimides and the like.
These (E) sensitizers are used individually by 1 type or in mixture of 2 or more types.

  It is preferable that content of the said (E) sensitizer is 0.1-1 mass% on the basis of the solid content whole quantity of the photosensitive resin composition. (E) When the content of the sensitizing dye is out of the above range, the sensitivity of the photosensitive resin composition is decreased or the compatibility with the solvent is decreased as compared with the case where the content is within the above range. Tend.

  The photosensitive resin composition of the present embodiment is used as described above (A) polyamic acid, (B) photopolymerizable compound, (C) thermopolymerizable compound, (D) photopolymerization initiator, and as necessary. (E) A sensitizer can be obtained by mixing with a solvent.

  Although it does not restrict | limit especially as a solvent used at this time, For example, the polar solvent which has N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, propylene glycol monomethyl ether acetate etc. as a main component And a solvent such as γ-butyrolactone. These solvents are used alone or as a mixture of two or more.

  Moreover, in order to improve the adhesiveness of the photosensitive resin composition and a board | substrate as needed, you may add an adhesion assistant to the photosensitive resin composition. Examples of the adhesion assistant include silane coupling agents such as γ-glycidoxysilane, aminosilane, and γ-ureidosilane.

(Rib pattern forming method)
Next, the rib pattern forming method of this embodiment will be described. In the rib pattern forming method of the present embodiment, there are a lamination step of laminating a photosensitive resin composition layer (photosensitive resin film) made of the above-described photosensitive resin composition, and a predetermined step of the photosensitive resin composition layer. An exposure step of irradiating a portion with actinic rays to photocure the exposed portion, a removing step of removing a portion other than the exposed portion of the photosensitive resin composition layer using a developer, and a photosensitive resin composition layer A desired pattern can be formed through a thermosetting process in which the exposed portion is thermally cured to form a cured resin. Hereinafter, each step will be described.

In the lamination step, a photosensitive resin film can be formed by applying and drying the above-described photosensitive resin composition on a support substrate. As the support substrate, for example, a glass substrate, a semiconductor, metal oxide insulator (for example _TiO 2, SiO _2, etc.), and silicon nitride. Examples of the method for applying the photosensitive resin composition include, but are not limited to, spin coating using a spinner, spray coating, dip coating, roll coating, and the like.

  The coating thickness varies depending on the coating means, the solid content concentration and the viscosity of the photosensitive resin composition, etc., but is usually applied so that the thickness of the dried film (photosensitive resin composition layer) is 1 to 300 μm. Is done. In order to make the film thickness after drying become 1 to 300 μm, it is preferable to dissolve the above-mentioned photosensitive resin composition with a solvent and adjust the viscosity to 0.5 to 20 Pa · s. It is more preferable to adjust to 10 Pa · s. Further, the solid content concentration of the photosensitive resin composition is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass. When the film thickness of the obtained film exceeds 300 μm, the resolution tends to decrease.

  Then, the photosensitive resin film which is a film of the photosensitive resin composition can be formed on a support substrate by drying for 1 minute to 1 hour in the range of 60-120 degreeC using a hotplate, oven, etc. .

  It is also possible to apply a photosensitive resin composition to an organic film such as polyethylene terephthalate and dry it to remove the solvent to form a dry film resist, which can be attached to a substrate.

  Next, in the exposure step, the photosensitive resin film formed as a film on the support substrate is irradiated with actinic rays on a predetermined portion through a negative mask having a desired pattern as necessary, and the exposed portion is photocured.

  Here, examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays and visible rays are particularly preferable.

  Next, after forming a pattern by removing a portion other than the exposed portion (unexposed portion) of the photosensitive resin composition layer using an organic solvent-based or alkaline aqueous solution-based developer, the photosensitive resin composition layer The exposed portion is thermally cured to form a pattern made of a cured resin.

  Here, as the developing solution, an organic solvent such as N-methylpyrrolidone, ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate can be used. Moreover, alkaline aqueous solution, such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, can be used. Among these, it is preferable to use cyclohexanone from the viewpoint of development speed.

  Further, after development, it is preferable to rinse with water, alcohol such as methanol, ethanol, isopropyl alcohol, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate or the like, if necessary.

  The thermosetting (curing) after development is preferably carried out for 1 to 2 hours while selecting the temperature and gradually increasing the temperature. It is preferable to perform thermosetting at 120-240 degreeC. When the heating temperature is raised stepwise, for example, it is preferable to perform heat treatment at 120 ° C. and 170 ° C. for 30 minutes and then heat treatment at 240 ° C. for 60 minutes.

(Hollow structure forming method)
The pattern made of the resin cured product described above has a sufficient film thickness, and a hollow structure can be formed by covering a ceramic substrate, Si substrate, glass substrate, metal substrate, or the like as a lid.

  Here, for example, a film formed by previously forming the photosensitive resin composition of the present invention into a film can be used as the lid. That is, this film-formed photosensitive resin composition can be applied to the upper part of the above pattern, and then exposed, developed, and thermally cured to form a hollow structure.

  Moreover, adhesion | attachment with a cover part and a pattern can be performed by adhesion | attachment by the thermocompression bonding which used the roll laminator, for example.

  As described above, according to the present invention, in the hollow structure forming step, a thick film pattern can be collectively formed by photolithography, and further, a cured product (or ceramic or the like) of the photosensitive resin composition formed into a film shape thereon. A hollow structure can be formed by sealing with a sealing substrate. In addition, since the inside of the hollow space is moisture-proof by the surrounding photosensitive resin composition and the hollow portion is maintained even at high temperatures, electronic components that require a hollow structure such as a SAW filter, CMOS / CCD sensor, MEMS, etc. It is useful for reducing the size, height and functionality of electronic components. The photosensitive resin composition of the present invention is particularly suitable for a SAW filter.

(SAW filter and manufacturing method thereof)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of a SAW filter that is one of the electronic components of the present invention. As shown in FIG. 1, the SAW filter 100 includes a substrate 10, a comb-shaped electrode 20 formed on the substrate 10, and a hollow space in a portion where the comb-shaped electrode 20 is formed on the substrate 10. The rib part 30 and the cover part 40, and the wiring 50 electrically connected to the comb-shaped electrode 20 are provided. And the rib part 30 and the cover part 40 are comprised by the resin cured material formed by hardening | curing the above-mentioned photosensitive resin composition.

  As the substrate 10, for example, a piezoelectric substrate such as a lithium tantalate substrate, a lithium niobate substrate, or a gallium arsenide substrate is used. As a material of the comb electrode 20, for example, aluminum or the like is used. As a material of the wiring 50, for example, lead-tin, solder or the like is used.

  Next, a method for manufacturing the SAW filter 100 will be described. 2A to 2C are process diagrams showing a preferred embodiment of a method for manufacturing the SAW filter 100 of the present invention.

First, as shown in FIG. 2A, a photosensitive resin composition layer 32 made of the photosensitive resin composition of the present invention is laminated on the substrate 10 on which the comb-shaped electrode 20 is formed.
Here, examples of the method for applying the photosensitive resin composition include, but are not limited to, spin coating using a spinner, spray coating, dip coating, roll coating, and the like.
It is also possible to apply the photosensitive resin composition to an organic film such as polyethylene terephthalate and dry it to remove the solvent to obtain a dry film resist, which can be attached to the substrate 10.

  The coating thickness varies depending on the coating means, the solid content concentration and the viscosity of the photosensitive resin composition, etc., but is usually applied so that the thickness of the dried film (photosensitive resin composition layer) is 1 to 300 μm. Is done. In order to make the film thickness after drying become 1 to 300 μm, it is preferable to dissolve the photosensitive resin composition of the present invention with a solvent and adjust the viscosity to 1 to 50 Pa · s, preferably 20 to 20 μm. It is more preferable to adjust to 40 Pa · s. Further, the solid content concentration of the photosensitive resin composition is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass. When the film thickness of the obtained film exceeds 300 μm, the resolution tends to decrease.

  After coating the photosensitive resin composition on the substrate 10, the coating film is dried to obtain the photosensitive resin composition layer 32. Drying is preferably performed in the range of 60 to 120 ° C. for 1 minute to 1 hour using an oven, a hot plate, or the like.

Next, as shown in FIG. 2 (a), a predetermined portion of the photosensitive resin composition layer 32 is irradiated with actinic rays through a negative mask 60 having a desired pattern as required, and the exposed portion is photocured. .
Here, examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays and visible rays are particularly preferable.

Next, as shown in FIG. 2B, after forming a pattern by removing a portion other than the exposed portion (unexposed portion) of the photosensitive resin composition layer 32 using an organic solvent-based developer. Then, the exposed portion of the photosensitive resin composition layer 32 is thermally cured to form a rib portion 30 made of a cured resin.
Here, as the developing solution, an organic solvent such as N-methylpyrrolidone, ethanol, cyclohexanone, cyclopentanone, propylene glycol methyl ether acetate can be used. Among these, it is preferable to use cyclohexanone for development of the photosensitive resin composition layer 32 in order to more reliably prevent corrosion of the aluminum wiring.
Further, after development, it is preferable to rinse with an alcohol such as methanol, ethanol or isopropyl alcohol, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether acetate or the like, if necessary.

The thermosetting (curing) after development is preferably carried out for 1 to 2 hours while selecting the temperature and gradually increasing the temperature. It is preferable to perform thermosetting at 120-200 degreeC. When the heating temperature is raised stepwise, for example, it is preferable to perform heat treatment at 200 ° C. for 60 minutes after heat treatment at 120 ° C., 150 ° C., and 180 ° C. for 20 minutes.
Next, as shown in FIG. 2C, a lid 40 is provided on the rib 30 to form a hollow structure. The SAW filter hollow structure fabrication is completed through the above steps.

Here, the cover part 40 can be produced using, for example, a film obtained by previously forming the photosensitive resin composition of the present invention into a film. That is, the film-formed photosensitive resin composition can be attached to the upper portion of the rib 30 and then exposed, developed, and thermally cured to form the lid portion 40.
Moreover, adhesion | attachment with the cover part 40 and the rib part 30 can be performed by adhesion | attachment by the thermocompression bonding etc. which used the roll laminator, for example.
In addition, the cover part 40 may be comprised with materials other than the photosensitive resin composition of this invention. However, it is preferable that the cover part 40 is comprised with the material which is excellent in heat-and-moisture resistance and has a low water absorption rate. Moreover, as the lid portion 40, a sealing substrate such as ceramic can be used. The pattern formed by the photosensitive resin composition of the present invention is used at least as a rib material for forming a hollow structure of a SAW filter.

The SAW filter produced as described above is sealed with a sealing material. This sealing is generally performed in the following steps, but is not limited thereto.
(1) Set the SAW filter on the molding die.
(2) A solid sealing material tablet is set in the pot of the molding machine.
(3) The sealing material is melted under conditions of a mold temperature of 170 to 180 ° C., and pressure is applied to the mold (mold).
(4) The sealing of the SAW filter is completed by pressurizing for 30 to 120 seconds, opening the mold after the sealing material is thermally cured, and taking out the molded product.

At this time, the lid portion 40 and / or the rib portion 30 is required to have mold resistance at a mold temperature of 170 to 180 ° C. That is, when the cover part 40 and / or the rib part 30 are produced with the photosensitive resin composition, it is desirable that the cover part 40 and / or the rib part 30 are not deformed at a temperature of 170 to 180 ° C., and such characteristics. In order to obtain, it is preferable that the glass transition temperature of the cover part 40 and / or the rib part 30 is 180 degreeC or more. The elastic modulus at 180 ° C. is preferably 200 MPa or more, more preferably 300 MPa or more, and 350
It is particularly preferable that the pressure be at least MPa. The upper limit of the elastic modulus at 180 ° C. is not particularly limited, but is 10 GPa or less from a practical viewpoint.

  As described above, according to the present invention, in the SAW filter manufacturing process, a thick-film rib pattern can be collectively formed on a piezoelectric substrate by photolithography using a solvent developer, and further a photosensitive resin formed in a film form thereon. A hollow structure can be formed by sealing with a cured product of the composition (or a sealing substrate such as ceramic). Further, since the inside of the hollow space is moisture-proof by the surrounding resin composition, corrosion of the aluminum electrode can be suppressed.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. Moreover, in the following synthesis examples, the mass average molecular weight and the number average molecular weight of the polyamic acid were measured by gel permeation chromatography (GPC) and calculated by a calibration curve using standard polystyrene.

[Synthesis of polyamic acid]
(Synthesis Example 1)
To a 300 mL four-necked separable flask, 15 Versamine 551 (trade name, [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene, manufactured by Cognis Japan Co., Ltd.) .73 g (0.028 mol), 4,4′-diaminodiphenylsulfone 3.54 g (0.014 mol) and N-methylpyrrolidone 30.0 g were added and stirred at room temperature for 15 minutes. Next, a mixed solution of 22.10 g (0.043 mol) of 1,10- (decamethylene) bis (trimellitate) dianhydride and 30.00 g of N-methylpyrrolidone was added over 15 minutes. After completion of the addition, the resulting mixture was heated to 60 ° C. and stirred for 8 hours to obtain an N-methylpyrrolidone solution of polyamic acid. Solid content in the obtained solution was 40 mass%, the mass average molecular weight of polyamic acid was 29000, and dispersity (mass average molecular weight / number average molecular weight) was 1.7. “Versamine 551” is a diamine compound including a compound represented by the following formula (22) and / or a compound in which an unsaturated portion of the compound represented by the following formula (22) is hydrogenated.

(Synthesis Example 2)
In a 300 mL four-neck separable flask, 12.89 g (0.052 mol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane and 0.11 g (0.001 mol) γ of m-aminophenol -Butyrolactone 10.0g was added and it stirred at 40 degreeC for 15 minutes. Next, a mixed solution of 16.4 g (0.053 mol) of 4,4′-oxydiphthalic dianhydride and 29.66 mL of γ-butyrolactone was added over 15 minutes. After completion of the addition, the temperature was raised to 60 ° C. and stirred for 5 hours to obtain a γ-butyrolactone solution of polyamic acid. Solid content in the obtained solution was 40 mass%, the mass average molecular weight of polyamic acid was 36000, and dispersity (mass average molecular weight / number average molecular weight) was 1.8.

(Molecular weight measurement)
The mass average molecular weight (Mw) and the number average molecular weight (Mn) of the polyamic acid synthesized in Synthesis Examples 1 to 3 are measured by gel permeation chromatography (GPC) and calculated by a calibration curve using standard polystyrene. It was. The GPC conditions are shown below.

(GPC conditions)
Detector: LV4000 UV Detector (manufactured by Hitachi, Ltd., trade name)
Pump: L6000 Pump (manufactured by Hitachi, Ltd., trade name)
C-R4A Chromatopack (manufactured by Shimadzu Corporation, trade name)
Column: Gelpack GL-S300MDT-5 (two in total) (manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: THF / DMF = 1/1 (volume ratio) + LiBr (0.03 mol / L) + H ₃ PO ₄ (0.06 mol / L)
Flow rate: 1 mL / min

[Examples 1 to 10 and Comparative Examples 1 and 2]
(A) Polyamic acid solution, (B) polymerizable compound, (C) thermopolymerizable compound, and (D) photopolymerization initiator synthesized in each of the above synthesis examples were respectively shown in Table 1 below. (Mass part) to obtain a solution of the photosensitive resin composition of Examples 1-10 and Comparative Examples 1-2. In addition, the number in Table 1 has shown the mass part of solid content. Moreover, each component in Table 1 is shown below.

Amide acrylate (synthetic product), TMCH-5R (trade name, urethane acrylic oligomer, manufactured by Hitachi Chemical Co., Ltd.), I-OXE01 (trade name, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime, manufactured by Ciba Specialty Chemicals Co., Ltd.), EA-6340 (trade name, tetrahydrophthalic anhydride-modified vinyl group-containing phenol type epoxy resin, manufactured by Nakamura Chemical Co., Ltd.)
HP-4032D (trade name, naphthalene skeleton bifunctional epoxy resin, manufactured by Dainippon Ink Co., Ltd.), Pd type oxazine (trade name, aromatic oxazine compound, Shikoku Kasei Kogyo Co., Ltd.)
Methylol-based thermopolymerizable compounds (total 5 types)

Here, the amide acrylate is synthesized by the following method.
In a 1-liter reaction vessel equipped with a thermometer and a stirrer, 380.0 g (2.0 mol) of 1,3-phenylenebisoxazoline and 228.0 g (1.0 mol) of bisphenol A were added and stirred at 150 ° C. for 10 hours. . Thereafter, 500 ppm of methoquinone and 140.0 g (2.0 mol) of methacrylic acid were added and stirred at 100 ° C. for 6 hours, 190 g of dimethylacetamide was added dropwise, and further stirred at 100 ° C. for 6 hours, and the acid value was 1.1 mgKOH / g. Then, stirring was stopped to obtain a solution of a compound (BPA-BDAM) represented by the following formula (23) which is a photopolymerizable unsaturated compound. The solid content of the obtained solution was 80% by mass.

<Evaluation of resolution>
The photosensitive resin composition solutions of Examples and Comparative Examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 90 ° C. for 5 minutes, and the dried photosensitive resin having a film thickness of 30 μm. A composition layer was formed. With respect to the test substrate on which this photosensitive resin composition layer was formed, the exposure amount was 200 mJ using a proximity exposure machine (trade name: UX-1000SM) manufactured by USHIO INC. Through a negative mask having an opening pattern with a hole diameter of 50 μmφ. The photosensitive resin composition layer was exposed at / cm ² . This test substrate was developed by being immersed in cyclohexanone, which is an organic solvent developer, for 7 minutes. The developed resist pattern was washed with propylene glycol monomethyl ether acetate, observed after drying, and the solvent resistance was evaluated based on the following criteria. The results are shown in Table 2.
A: The hole diameter is 50 μmφ and there is no residue after development.
B: The hole diameter is 50 μmφ, but there is a residue after development.
C: Hole diameter 50 μmφ is not open.

<Hollow retention>
The photosensitive resin composition solutions of Examples and Comparative Examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 90 ° C. for 5 minutes, and the dried photosensitive resin having a film thickness of 30 μm. A composition layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, the exposure amount using the proximity exposure machine (brand name: UX-1000SM) made from USHIO INC. Through the negative mask which has a lattice size 1mm □ opening pattern The photosensitive resin composition layer was exposed at 200 mJ / cm ² . This test substrate was developed and cured to obtain a cured film pattern having openings in a lattice pattern.
A film having a film thickness of 30 μm on which the photosensitive resin composition was formed was pasted to form a hollow structure.
Next, the photosensitive resin film in the form of a film was exposed at an exposure amount of 200 mJ / cm ² using a proximity exposure machine (trade name: UX-1000SM) manufactured by Ushio Electric. The test substrate was cured at 120 ° C. for 30 minutes, 170 ° C. for 30 minutes, and 240 ° C. for 60 minutes, and the cross-section of the cured lattice pattern was observed with a microscope. evaluated. The results are shown in Table 2.
A: The hollow part can be retained, and the cured film is not dripped at all. B: The hollow part is retained, but the film is slightly sagged. C: The film is dripped and the hollow part is removed. Crushed

<Measurement of elastic modulus at high temperature (mold pressure resistance)>
The photosensitive resin composition solutions of Examples and Comparative Examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 90 ° C. for 5 minutes, and the dried photosensitive resin having a film thickness of 30 μm. A composition layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, exposure of the photosensitive resin composition layer was carried out with the exposure amount of 200 mJ / cm < ² > using the proximity exposure machine (brand name: UX-1000SM) made by Ushio Electric. And photocured. The cured film of the obtained photosensitive resin composition was peeled off from the silicon substrate, and the elastic modulus of the peeled cured film was measured with a viscoelasticity tester (trade name: RSA-III, manufactured by TA instruments). The elastic modulus was measured under the conditions of test mode: tension, test temperature: room temperature to 300 ° C., heating rate: 5 ° C./min, test frequency: 1 Hz, and distance between chucks: 20 mm. These results are shown in Table 2.

<Evaluation of heat and humidity resistance>
The photosensitive resin composition solutions of Examples and Comparative Examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 90 ° C. for 5 minutes, and the dried photosensitive resin having a film thickness of 30 μm. A composition layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, exposure of the photosensitive resin composition layer was carried out with the exposure amount of 200 mJ / cm < ² > using the proximity exposure machine (brand name: UX-1000SM) made by Ushio Electric. And photocured. Thereafter, the photosensitive resin composition layer was cured by heating at 120 ° C. for 30 minutes and subsequently at 240 ° C. for 60 minutes. The test substrate was allowed to stand for 200 hours under the conditions of 121 ° C., 100% RH, and 2 atm. Then, the appearance of the cured film was visually evaluated, and the adhesion was in accordance with JIS K5400 (1990). It was evaluated in a test. The evaluation criteria are as follows. The results are shown in Table 2.

(appearance)
A: Turbidity, peeling, swelling, and cracks are not observed in the cured film.
B: Any one of slight turbidity, peeling, swelling and cracking is observed in the cured film.
C: Any one of turbidity, peeling, swelling, and cracks in the cured film is observed.

(Cross cut test)
The remaining mass after peeling the tape
A: 100/100 (no peeling)
B: ≧ 90/100 (1-10 mass peeling)
C: <90/100 (exfoliation is more than 10 squares)

DESCRIPTION OF SYMBOLS 10 ... Board | substrate, 20 ... Comb electrode, 30 ... Rib part, 32 ... Photosensitive resin composition layer, 40 ... Cover part 50 ... Wiring, 100 ... SAW filter.

Claims (10)

(A) a polyamic acid,
(B) a photopolymerizable compound having an ethylenically unsaturated group;
(C) a thermopolymerizable compound having at least one methylol group or alkoxyalkyl group;
(D) a photopolymerization initiator;
A photosensitive resin composition containing,
(C) A photosensitive resin composition in which the thermally polymerizable compound having at least one methylol group or alkoxyalkyl group is a compound represented by the following general formula (2).
[In formula (2), two Y each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ^{3 to} R ⁶ each independently represents a monovalent organic group, and p1 and p2 Are each independently an integer of 1 to 4, and q1 and q2 are each independently an integer of 0 to 3. However, some carbon atoms of the alkyl group in Y may be substituted with oxygen atoms, and some or all of the hydrogen atoms in Y may be substituted with fluorine atoms. ] The photosensitive resin composition of Claim 1 in which the said (A) polyamic acid contains the polyamic acid which has a structure represented by following General formula (3).
[In the formula (3), Ar ¹ represents a tetravalent organic group represented by the following general formula (4) or the following general formula (5), and Ar ² represents the following general formula (6) or the following general formula (7 ), A divalent organic group represented by the following general formula (8) or the following general formula (9), and k represents an integer of 1 or more. When k is 2 or more, a plurality of Ar ¹ and Ar ² may be the same or different. ]
[In the formula (4), X ² represents a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,
(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. M2 and n2 each independently represent an integer of 0 to 3. In addition, when m2 is 2 or more, a plurality of R ¹¹ may be the same or different, and when n2 is 2 or more, a plurality of R ¹² may be the same or different. ]
Wherein (5), ^{X 3} represents an alkylene group having 5 to 20 carbon ^{atoms, R 14} and ^{R 15} each independently represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, m3 and n3 each independently represents an integer of 0 to 3. In addition, when m3 is 2 or more, a plurality of R ¹⁴ may be the same or different, and when n3 is 2 or more, a plurality of R ¹⁵ may be the same or different. ]
[In Formula (6), Y ¹ is a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,
(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹⁶ and R ¹⁷ each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. , P and q each independently represent an integer of 0 to 4. In addition, when p is 2 or more, a plurality of R ¹⁶ may be the same or different, and when q is 2 or more, a plurality of R ¹⁷ may be the same or different. ]
[In the formula (7), Z ¹ represents a single bond, —O—, —S—, —SO ₂ —, —CH ₂ —,
(R ¹³ represents an alkylene group having 5 to 20 carbon atoms), and R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are each independently an alkyl group having 1 to 6 carbon atoms or 1 to 1 carbon atoms. 3 represents an alkoxy group, and r, s, t and u each independently represents an integer of 0 to 4. When r is 2 or more, a plurality of R ¹⁸ may be the same or different. When s is 2 or more, a plurality of R ¹⁹ may be the same or different, and when t is 2 or more. The plurality of R ²⁰ may be the same or different, and when u is 2 or more, the plurality of R ²¹ may be the same or different. ]
Wherein ^{(8), R 22} represents an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, v is an integer of 0 to 3. When v is 2 or more, a plurality of R ²² may be the same or different. ]
Wherein (9), ^{Z 2} represents a single bond or a divalent organic group, ^{Y 2} and ^{Y 3} represents an alkylene group having 5 to 20 carbon atoms independently. ] The photosensitive resin composition according to claim 2 , wherein Z ² in the general formula (9) is a divalent organic group represented by the following general formula (10), (11), or (12).
Wherein ^{(10), R 23} represents an alkyl group, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 10 carbon atoms having 1 to 10 carbon atoms, w1 is an integer of 0-4. In addition, when w1 is 2 or more, a plurality of R ²³ may be the same or different. ]
[In the formula (11), R ²⁴ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w2 represents an integer of 0 to 4. When w2 is 2 or more, a plurality of R ²⁴ may be the same or different. ]
[In Formula (12), R ²⁵ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w3 represents an integer of 0 to 4. In addition, when w3 is 2 or more, a plurality of R ²⁵ may be the same or different. ] A laminating step of laminating a photosensitive resin composition layer comprising the photosensitive resin composition according to any one of claims 1 to 3 on a substrate;
An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray and photocuring the exposed portion;
A removal step of removing a portion other than the exposed portion of the photosensitive resin composition layer using a developer;
And a thermosetting step of thermosetting the exposed portion of the photosensitive resin composition layer to form a resin cured product. A cured product formed by curing the photosensitive resin composition according to any one of claims 1 to 3 on a rib pattern formed by the rib pattern forming method according to claim 4 is formed. An electronic component having a hollow structure. On a substrate, a laminating step of laminating the photosensitive resin composition layer composed of a photosensitive light-sensitive resin composition,
An exposure step of irradiating a predetermined portion of the photosensitive resin composition layer with an actinic ray and photocuring the exposed portion;
A removal step of removing a portion other than the exposed portion of the photosensitive resin composition layer using a developer;
A thermosetting step of thermosetting the exposed portion of the photosensitive resin composition layer to form a cured resin, and a rib pattern forming method comprising :
The photosensitive resin composition comprises (A) a polyamic acid, (B) a photopolymerizable compound having an ethylenically unsaturated group, and (C) a thermopolymerizable compound having at least one methylol group or alkoxyalkyl group. (D) The formation method of a rib pattern containing a photoinitiator. (C) The rib pattern formation method according to claim 6, wherein the thermopolymerizable compound having at least one methylol group or alkoxyalkyl group is a compound represented by the following general formula (1).
[In the formula (1), X represents a single bond or an n-valent organic group, R ¹ And R ² Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 4, p represents an integer of 1 to 4, q represents an integer of 0 to 3, p and The sum of q is 4. In addition, when q and / or n is 2 or more, a plurality of Rs exist. ¹ Each may be the same or different, and when p and / or n is 2 or more, a plurality of Rs are present. ² May be the same or different. ] (C) The rib pattern forming method according to claim 7, wherein the thermally polymerizable compound having at least one methylol group or alkoxyalkyl group is a compound represented by the following general formula (2).
[In Formula (2), two Y's each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; ³ ~ R ⁶ Each independently represents a monovalent organic group, p1 and p2 are each independently an integer of 1 to 4, and q1 and q2 are each independently an integer of 0 to 3. However, some carbon atoms of the alkyl group in Y may be substituted with oxygen atoms, and some or all of the hydrogen atoms in Y may be substituted with fluorine atoms. ]   The said (A) polyamic acid contains the polyamic acid which has a structure represented by following General formula (3), The formation method of the rib pattern as described in any one of Claims 6-8.
[In the formula (3), Ar ¹ Represents a tetravalent organic group represented by the following general formula (4) or the following general formula (5), Ar ² Represents a divalent organic group represented by the following general formula (6), the following general formula (7), the following general formula (8), or the following general formula (9), and k represents an integer of 1 or more. When k is 2 or more, there are a plurality of Ar ¹ And Ar ² May be the same or different. ]
[In formula (4), X ² Is a single bond, -O-, -S-, -SO ₂ -, -CH ₂ −,
(R ¹³ Represents an alkylene group having 5 to 20 carbon atoms. ) And R ¹¹ And R ¹² Each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and m2 and n2 each independently represents an integer of 0 to 3. When m2 is 2 or more, there are a plurality of R ¹¹ May be the same or different, and when n2 is 2 or more, a plurality of R ¹² May be the same or different. ]
[In Formula (5), X ³ Represents an alkylene group having 5 to 20 carbon atoms, and R ¹⁴ And R ¹⁵ Each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and m3 and n3 each independently represents an integer of 0 to 3. When m3 is 2 or more, there are a plurality of R ¹⁴ May be the same or different, and when n3 is 2 or more, a plurality of R ¹⁵ May be the same or different. ]
[In formula (6), Y ¹ Is a single bond, -O-, -S-, -SO ₂ -, -CH ₂ −,
(R ¹³ Represents an alkylene group having 5 to 20 carbon atoms. ) And R ¹⁶ And R ¹⁷ Each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and p and q each independently represents an integer of 0 to 4. When p is 2 or more, there are a plurality of R ¹⁶ May be the same or different, and when q is 2 or more, a plurality of Rs are present. ¹⁷ May be the same or different. ]
[In formula (7), Z ¹ Is a single bond, -O-, -S-, -SO ₂ -, -CH ₂ −,
(R ¹³ Represents an alkylene group having 5 to 20 carbon atoms. ) And R ¹⁸ , R ¹⁹ , R ²⁰ And R ²¹ Each independently represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and r, s, t and u each independently represents an integer of 0 to 4. When r is 2 or more, there are a plurality of R ¹⁸ May be the same or different, and when s is 2 or more, a plurality of Rs are present. ¹⁹ May be the same or different, and when t is 2 or more, a plurality of Rs are present. ²⁰ May be the same or different, and when u is 2 or more, a plurality of Rs are present. ²¹ May be the same or different. ]
[In formula (8), R ²² Represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and v represents an integer of 0 to 3. When v is 2 or more, there are a plurality of R ²² May be the same or different. ]
[In formula (9), Z ² Represents a single bond or a divalent organic group, Y ² And Y ³ Each independently represents an alkylene group having 5 to 20 carbon atoms. ]   Z in the general formula (9) ² The method for forming a rib pattern according to claim 9, wherein is a divalent organic group represented by the following general formula (10), (11) or (12).
[In formula (10), R ²³ Represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w1 represents an integer of 0 to 4. If w1 is 2 or more, there are multiple Rs ²³ May be the same or different. ]
[In formula (11), R ²⁴ Represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w2 represents an integer of 0 to 4. If w2 is 2 or more, there are multiple Rs ²⁴ May be the same or different. ]
[In formula (12), R ²⁵ Represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and w3 represents an integer of 0 to 4. If w3 is 2 or more, there are multiple Rs ²⁵ May be the same or different. ]