JP2010145522A - Photosensitive resin composition, saw filter and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is adaptable to solvent development, curable at low temperature, sufficiently low in water absorption, excellent in wet heat resistance, and also excellent in resolution even in a thick film, a cured product thereof having a high glass transition temperature. <P>SOLUTION: The photosensitive resin composition includes (A) a polyamic acid, (B) a polymerizable compound, and (C) a photopolymerization initiator. The polymerizable compound (B) includes a polymerizable compound having an amide bond and two or more ethylenic unsaturated groups per molecule. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a SAW filter, and a method for producing the same.

  In recent years, as semiconductor devices have been highly integrated and miniaturized, rapid increase in capacity and cost have been realized. Among them, SAW (Surface Acoustic Wave) filters used for removing noise from mobile phones are currently costly due to ceramic processing in manufacturing, and are downsized and low due to structural limitations. The problem of difficulty in turning is a problem (see Patent Documents 1 to 4 below).

JP 2001-244785 A JP-A-8-204482 JP 2003-8395 A JP 2004-64732 A

  In order to solve this problem, development of a photosensitive resin material that can be easily processed by photolithography is desired as a ceramic substitute material in order to achieve a reduction in manufacturing cost and a reduction in time (see Patent Document 3 and above). 4).

  The SAW filter has a comb-like aluminum electrode (referred to as an Inter Digital Transducer, IDT electrode) on the surface of the piezoelectric substrate, and the portion where the comb-like aluminum electrode is formed is a surface acoustic wave. It is necessary to be a hollow space in order to propagate. Therefore, in order for the photosensitive resin to replace ceramic, it is necessary to form a thick film in order to form a hollow space.

  In the SAW filter manufacturing process, the aluminum electrode may be exposed to a developer during photolithography. At this time, when an alkaline developer is used, there is a problem that the aluminum electrode corrodes, so that a photosensitive resin that can be developed with an organic solvent is demanded. Furthermore, in terms of preventing corrosion of the aluminum electrode, the photosensitive resin is required to have a low water absorption rate and excellent moisture resistance at high temperatures (hereinafter referred to as “moisture heat resistance”).

  Further, since the aluminum electrode is charged at a high temperature exceeding 200 ° C. and affects the characteristics of the product, a photosensitive resin that can be cured at a low temperature is required.

  As a photosensitive resin having high heat resistance and high reliability, a photosensitive polyimide material can be considered, but the curing temperature is as high as 250 to 350 ° C., and it is difficult to form a film having a thickness of 10 μm or more. There's a problem.

  On the other hand, as a photosensitive resin capable of forming a thick film of about 30 μm and having a curing temperature of about 150 ° C., an epoxy-based photosensitive resin can be given. However, epoxy-based photosensitive resins generally have a high water absorption rate and do not have sufficient moisture and heat resistance as compared with polyimide, so that there is a problem that corrosion of the aluminum electrode occurs due to moisture permeation at high temperatures.

  In order to solve these problems, development of a photosensitive resin capable of being cured at a low temperature of about 200 ° C., having a low water absorption rate, and capable of forming a thick film and developing a solvent has been underway. However, even though the above problems can be improved, new problems such as a decrease in the glass transition temperature of the cured product and a decrease in resolution during development have occurred. When the glass transition temperature is low, the hollow structure including the SAW element may cause hollow crushing when the resin is sealed, and the mold resistance tends to be insufficient. In addition, when the resolution is low, there arise problems that a fine pattern cannot be formed or a development residue is generated.

  The present invention has been made in order to solve the above-described conventional problems, and can be applied to solvent development, can be cured at low temperature, has a sufficiently low water absorption, excellent moisture and heat resistance, and a thickness. An object of the present invention is to provide a photosensitive resin composition excellent in resolution even in a film and having a high glass transition temperature in a cured product, a SAW filter using the same, and a method for producing the same.

  In order to achieve the above object, the present invention includes (A) a polyamic acid, (B) a polymerizable compound, and (C) a photopolymerization initiator, and the (B) polymerizable compound is a molecule. Provided is a photosensitive resin composition comprising a polymerizable compound having an amide bond and two or more ethylenically unsaturated groups therein.

  Such a photosensitive resin composition is particularly suitably used for forming SAW filters. By having the said structure containing the (A) polyamic acid which is a polyimide precursor, the said photosensitive resin composition has the water absorption rate low enough, and can obtain the outstanding heat-and-moisture resistance. Further, by using the above (A) polyamic acid, the cured resin can obtain excellent heat resistance and rigidity. In addition, the photosensitive resin composition having the above configuration can form a thick film with high resolution. Furthermore, the photosensitive resin composition includes a polymerizable compound having an amide bond and two or more ethylenically unsaturated groups in the molecule as the polymerizable compound (B), so that the resin after photocuring is sufficient. Solvent resistance can be expressed, and solvent development using an organic solvent becomes possible. The photosensitive resin composition can be cured at a relatively low temperature (for example, 200 ° C. or less) by containing a polymerizable compound having an amide bond and two or more ethylenically unsaturated groups in the molecule. In the SAW filter manufacturing process, charging of the aluminum comb electrode can be suppressed. Further, the photosensitive resin composition contains a polymerizable compound having an amide bond and two or more ethylenically unsaturated groups in the molecule, so that the cured product has a high glass transition temperature, and a sealing resin. Can sufficiently withstand the mold pressure.

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３は各々独立に、２価の有機基を示し、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５及びＲ^６は各々独立に、水素原子、炭素数１〜４のアルキル基又はフェニル基を示す。］ In the photosensitive resin composition of the present invention, the polymerizable compound (B) is represented by the following general formula (1) as a polymerizable compound having an amide bond and two or more ethylenically unsaturated groups in the molecule. It is preferable that the compound is included.

[In the formula (1), R ¹ , R ² and R ³ each independently represents a divalent organic group, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ and R ⁶ each independently represent hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group is shown. ]

  Such a photosensitive resin composition contains a compound represented by the above general formula (1) as the polymerizable compound (B), so that more excellent resolution can be obtained and the cured product has a higher glass transition temperature. In addition, more sufficient mold resistance can be obtained.

［式（２）中、Ｘ^１は単結合、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＨ_２−、

のいずれかを示し、Ｒ^７及びＲ^８は各々独立に、水素原子、炭素数１〜６のアルキル基又はハロゲン原子を示し、ｍ１及びｎ１は各々独立に、１〜４の整数を示す。なお、ｍ１が２以上の場合、複数存在するＲ^７は同一でも異なっていてもよく、ｎ１が２以上の場合、複数存在するＲ^８は同一でも異なっていてもよい。］ In the general formula (1), R ¹ is a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a group represented by the following general formula (2). , R ² and R ³ are each independently a phenylene group which may have a substituent, a pyridylene group which may have a substituent or an alkylene group which may have 1 to 10 carbon atoms. Preferably there is.

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

R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m1 and n1 each independently represents an integer of 1 to 4. In addition, when m1 is 2 or more, a plurality of R ⁷ may be the same or different, and when n1 is 2 or more, a plurality of R ⁸ may be the same or different. ]

  In such a photosensitive resin composition, more excellent resolution can be obtained, and the cured product has a higher glass transition temperature, so that more sufficient mold resistance can be obtained.

  In the photosensitive resin composition of the present invention, the polymerizable compound (B) includes an oxazoline group-containing compound and a carboxyl group as a polymerizable compound having an amide bond and two or more ethylenically unsaturated groups in the molecule. It is preferable to include a di (meth) acrylate having an amide bond obtained by reacting the containing compound and / or the phenolic hydroxyl group-containing compound. Thereby, while the photosensitive resin composition can obtain more excellent resolution, the cured product has a higher glass transition temperature, and more sufficient mold resistance can be obtained.

［式（３）中、Ａｒ^１は下記一般式（４）又は下記一般式（５）で表される４価の有機基を示し、Ａｒ^２は下記一般式（６）、下記一般式（７）、下記一般式（８）又は下記一般式（９）で表される２価の有機基を示し、ｋは１以上の整数を示す。なお、ｋが２以上の場合、複数存在するＡｒ^１及びＡｒ^２はそれぞれ同一でも異なっていてもよい。］

［式（４）中、Ｘ^２は単結合、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＨ_２−、

（Ｒ^１３は炭素数５〜２０のアルキレン基を示す。）のいずれかを示し、Ｒ^１１及びＲ^１２は各々独立に、水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ２及びｎ２は各々独立に、１〜３の整数を示す。なお、ｍ２が２以上の場合、複数存在するＲ^１１は同一でも異なっていてもよく、ｎ２が２以上の場合、複数存在するＲ^１２は同一でも異なっていてもよい。］

［式（５）中、Ｘ^３は炭素数５〜２０のアルキレン基を示し、Ｒ^１４及びＲ^１５は各々独立に、水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ３及びｎ３は各々独立に、１〜３の整数を示す。なお、ｍ３が２以上の場合、複数存在するＲ^１４は同一でも異なっていてもよく、ｎ３が２以上の場合、複数存在するＲ^１５は同一でも異なっていてもよい。］

［式（６）中、Ｙ^１は単結合、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＨ_２−、

（Ｒ^１３は炭素数５〜２０のアルキレン基を示す。）のいずれかを示し、Ｒ^１６及びＲ^１７は各々独立に、水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｐ及びｑは各々独立に、１〜４の整数を示す。なお、ｐが２以上の場合、複数存在するＲ^１６は同一でも異なっていてもよく、ｑが２以上の場合、複数存在するＲ^１７は同一でも異なっていてもよい。］

［式（７）中、Ｚ^１は単結合、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＨ_２−、

（Ｒ^１３は炭素数５〜２０のアルキレン基を示す。）のいずれかを示し、Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は各々独立に、水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｒ、ｓ、ｔ及びｕは各々独立に、１〜４の整数を示す。なお、ｒが２以上の場合、複数存在するＲ^１８は同一でも異なっていてもよく、ｓが２以上の場合、複数存在するＲ^１９は同一でも異なっていてもよく、ｔが２以上の場合、複数存在するＲ^２０は同一でも異なっていてもよく、ｕが２以上の場合、複数存在するＲ^２１は同一でも異なっていてもよい。］

［式（８）中、Ｒ^２２は水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｖは１〜３の整数を示す。なお、ｖが２以上の場合、複数存在するＲ^２２は同一でも異なっていてもよい。］

［式（９）中、Ｚ^２は単結合又は２価の有機基を示し、Ｙ^２及びＹ^３は各々独立に炭素数５〜２０のアルキレン基を示す。］ Moreover, in the photosensitive resin composition of this invention, it is preferable that the said (A) polyamic acid contains the compound 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. Incidentally, when k is 2 or more, Ar ¹ and Ar ² existing in plural numbers may each 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 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. An alkoxy group, m2 and n2 each independently represent an integer of 1 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 Formula (5), X ³ represents an alkylene group having 5 to 20 carbon atoms, and R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, 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 1 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 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. An alkoxy group, p and q each independently represent an integer of 1 to 4; Incidentally, when p is 2 or more, R ¹⁶ there are a plurality may be the same or different, and when q is 2 or more, R ¹⁷ existing in plural numbers 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) indicates one ^of the R ^18, R ^{19, R 20} and ^{R 21} are each independently a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms A C1-C3 alkoxy group is shown, r, s, t, and u show the integer of 1-4 each independently. 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 a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, v is an integer of 1-3. 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. ]

  Such a photosensitive resin composition can further reduce the water absorption of the cured resin obtained by including a compound having a structure represented by the general formula (3) as (A) polyamic acid. Such a photosensitive resin composition is excellent in sensitivity at the time of exposure, and can form an image with a thick film with higher resolution.

［式（１０）中、Ｒ^２３は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｗ１は１〜４の整数を示す。なお、ｗ１が２以上の場合、複数存在するＲ^２３は同一でも異なっていてもよい。］

［式（１１）中、Ｒ^２４は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｗ２は１〜４の整数を示す。なお、ｗ２が２以上の場合、複数存在するＲ^２４は同一でも異なっていてもよい。］

［式（１２）中、Ｒ^２５は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｗ３は１〜４の整数を示す。なお、ｗ３が２以上の場合、複数存在するＲ^２５は同一でも異なっていてもよい。］ Here, Z ² in the general formula (9) is preferably a divalent organic group represented by the following general formula (10), the following general formula (11), or the following general formula (12). .

[In the formula (10), R ²³ represents a hydrogen atom, 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 1 to 4. Show. 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 a hydrogen atom, 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 1 to 4. Show. When w2 is 2 or more, a plurality of R ²⁴ may be the same or different. ]

Wherein ^{(12), R 25} is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 10 carbon atoms, w3 is an integer of 1 to 4 Show. In addition, when w3 is 2 or more, a plurality of R ²⁵ may be the same or different. ]

  Such a photosensitive resin composition is obtained by including a compound having at least one of the structures represented by the general formulas (10), (11), and (12) as the (A) polyamic acid. The water absorption rate of the resin cured product can be further reduced.

  The present invention also provides a SAW filter comprising a cured resin comprising the photosensitive resin composition of the present invention. In such a SAW filter, the resin cured product as a constituent material thereof is composed of the photosensitive resin composition of the present invention, so that the water absorption is sufficiently low, excellent moisture and heat resistance can be obtained, and corrosion of the electrode is achieved. Can be sufficiently suppressed. Moreover, it has a high glass transition temperature, excellent mold pressure resistance, and can sufficiently suppress hollow crushing.

  The present invention further comprises laminating a photosensitive resin composition layer comprising the above-described photosensitive resin composition of the present invention on a substrate, and irradiating a predetermined portion of the photosensitive resin composition layer with actinic rays to form an exposed portion. After photocuring, and then removing the portion other than the exposed portion of the photosensitive resin composition layer using an organic solvent-based developer, the exposed portion of the photosensitive resin composition layer is thermally cured. A method for producing a SAW filter including a step of forming a cured resin product is provided. According to such a production 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 a thick film with high resolution, and at a relatively low temperature. In addition to being cured at (for example, 200 ° C. or lower), a cured resin can be formed, and the cured product has a high glass transition temperature. Therefore, corrosion and charging of the electrode in the SAW filter manufacturing process, and hollow crushing during resin sealing can be sufficiently suppressed.

  According to the present invention, it can be applied to solvent development, can be cured at low temperature, has a sufficiently low water absorption rate, has excellent moisture and heat resistance, has a high glass transition temperature, and can form an image with high resolution with a thick film. A resin composition, a SAW filter using the same, and a method for producing the same can be provided.

  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) a polyamic acid (hereinafter sometimes referred to as “component (A)”) and (B) a polymerizable compound (hereinafter sometimes referred to as “component (B)”). , (C) a photopolymerization initiator (hereinafter, referred to as “component (C)” in some cases), and the polymerization compound (B) having an amide bond and an ethylenically unsaturated group in the molecule It contains a chemical compound. 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′-benzophenonetetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Two 3,3 ′, 4,4′-biphenyl ether tetracarboxylic anhydride (4,4′-oxydiphthalic dianhydride), 2,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride Anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis [4- (3,4-dicarboxyl) Benzoyloxy) pheny ] Nonane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl ] Tridecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] tetradecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl ] Pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-methyldecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyl) Oxy) 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 dianhydride, etc. Can be 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 '-Tylene bis (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'-diaminodiph Nyl 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'-diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenyl sulfone, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfone, 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 3,3′-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-amino Phenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (4-aminophenyl) Enyl) 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, , 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, 1,1 -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) decafluoropropane 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, if an alkylene group having 5 to 20 carbon atoms is contained in either or both of the main chain of (a1) tetracarboxylic dianhydride component and (a2) diamine component, low temperature curability, flexibility, Low water absorption, low warpage, and resist wettability during thermocompression bonding can be realized.

  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, which causes a decrease in the heat resistance (5% mass reduction temperature) of the resin. Furthermore, when it has an ether bond, it is easy to absorb water and becomes 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.

（Ｒ^１３は炭素数５〜２０のアルキレン基を示す。）のいずれかを示し、Ｒ^１１及びＲ^１２は各々独立に、水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ２及びｎ２は各々独立に、１〜３の整数を示す。なお、ｍ２が２以上の場合、複数存在するＲ^１１は同一でも異なっていてもよく、ｎ２が２以上の場合、複数存在するＲ^１２は同一でも異なっていてもよい。 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 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. An alkoxy group, m2 and n2 each independently represent an integer of 1 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 a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. Furthermore, m3 and n3 each independently represent an integer of 1 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.

（Ｒ^１３は炭素数５〜２０のアルキレン基を示す。）のいずれかを示し、Ｒ^１６及びＲ^１７は各々独立に、水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｐ及びｑは各々独立に、１〜４の整数を示す。なお、ｐが２以上の場合、複数存在するＲ^１６は同一でも異なっていてもよく、ｑが２以上の場合、複数存在するＲ^１７は同一でも異なっていてもよい。 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 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. An alkoxy group, p and q each independently represent an integer of 1 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.

（Ｒ^１３は炭素数５〜２０のアルキレン基を示す。）のいずれかを示し、Ｒ^１８、Ｒ^１９、Ｒ^２０及びＲ^２１は各々独立に、水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｒ、ｓ、ｔ及びｕは各々独立に、１〜４の整数を示す。なお、ｒが２以上の場合、複数存在するＲ^１８は同一でも異なっていてもよく、ｓが２以上の場合、複数存在するＲ^１９は同一でも異なっていてもよく、ｔが２以上の場合、複数存在するＲ^２０は同一でも異なっていてもよく、ｕが２以上の場合、複数存在するＲ^２１は同一でも異なっていてもよい。 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 a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or A C1-C3 alkoxy group is shown, r, s, t, and u show the integer of 1-4 each independently. Note that when r is 2 or more, R ¹⁸ there are a plurality may be the same or different, when s is 2 or more, R ¹⁹ there are a plurality may be the same or different, 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 a hydrogen atom, 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 1 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 the general formula ^{(10), R 23} is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 10 carbon atoms, w1 is an integer of 1 to 4 Show. In addition, when w1 is 2 or more, a plurality of R ²³ may be the same or different.

In General Formula (11), R ²⁴ represents a hydrogen atom, 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 1 to 4. Show. When w2 is 2 or more, a plurality of R ²⁴ may be the same or different.

In General Formula (12), R ²⁵ represents a hydrogen atom, 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 1 to 4. Show. 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.

［式（１３）中、Ｘは炭素数５〜２０のアルキレン基を示す。］

[In Formula (13), X shows a C5-C20 alkylene group. ]

  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).

［式（１４）中、Ｙ^２及びＹ^３は各々独立に炭素数５〜２０のアルキレン基を示し、Ｒ^２３は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｗ１は１〜４の整数を示す。なお、ｗ１が２以上の場合、複数存在するＲ^２３は同一でも異なっていてもよい。］

[In Formula (14), Y ² and Y ³ each independently represent an alkylene group having 5 to 20 carbon atoms, R ²³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms. Or a C1-C3 alkoxy group is shown, and w1 shows the integer of 1-4. In addition, when w1 is 2 or more, a plurality of R ²³ may be the same or different. ]

［式（１５）中、Ｙ^２及びＹ^３は各々独立に炭素数５〜２０のアルキレン基を示し、Ｒ^２４は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｗ２は１〜４の整数を示す。なお、ｗ２が２以上の場合、複数存在するＲ^２４は同一でも異なっていてもよい。］

[In Formula (15), Y ² and Y ³ each independently represent an alkylene group having 5 to 20 carbon atoms, R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms. Or a C1-C3 alkoxy group is shown, w2 shows the integer of 1-4. When w2 is 2 or more, a plurality of R ²⁴ may be the same or different. ]

［式（１６）中、Ｙ^２及びＹ^３は各々独立に炭素数５〜２０のアルキレン基を示し、Ｒ^２５は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｗ３は１〜４の整数を示す。なお、ｗ３が２以上の場合、複数存在するＲ^２５は同一でも異なっていてもよい。］

[In Formula (16), Y ² and Y ³ each independently represent an alkylene group having 5 to 20 carbon atoms, R ²⁵ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms. Or a C1-C3 alkoxy group is shown, and w3 shows the integer of 1-4. 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.

  (A) The polyamic acid used in the present invention is composed of (a1) a tetracarboxylic dianhydride component and (a1) a tetracarboxylic dianhydride component, as described above, from the viewpoint of improving low-temperature curability (for example, 200 ° C. or less), low water absorption and moist heat resistance. a2) A compound obtained by a reaction with a diamine component, preferably having a C5-C20 alkylene group in the main chain, and more preferably a compound having a C6-C16 alkylene group. Particularly preferred is a compound having an alkylene group having 7 to 14 carbon atoms. 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.

  In the photosensitive resin composition, the content of the (A) polyamic acid is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the (A) component and the (B) component, and 30 to 60 More preferably, it is part by mass. 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.

  In the photosensitive resin composition of the present invention, the polymerizable compound (B) contains a polymerizable compound having an amide bond and two or more ethylenically unsaturated groups. In the polymerizable compound having an amide bond and two or more ethylenically unsaturated groups, the number of amide bond groups in the molecule is preferably 2 to 12, and more preferably 4 to 8. In the polymerizable compound having an amide bond and two or more ethylenically unsaturated groups, the number of ethylenically unsaturated groups in the molecule is preferably 2 to 6. By satisfying these conditions, the polymerizable compound having an amide bond and two or more ethylenically unsaturated groups tends to improve the balance between compatibility with (A) polyamic acid and developability. If the number of amide groups in the molecule is less than 2, the glass transition temperature of the cured product tends to decrease, and if it exceeds 12, the developability tends to decrease. Moreover, there exists a tendency for developability to fall that the number of ethylenically unsaturated groups in a molecule is less than two.

  The polymerizable compound having an amide bond and two or more ethylenically unsaturated groups in the molecule is preferably a compound represented by the following general formula (1).

［式（１）中、Ｒ^１、Ｒ^２及びＲ^３は各々独立に、２価の有機基を示し、Ｒ^４は水素原子又はメチル基を示し、Ｒ^５及びＲ^６は各々独立に、水素原子、炭素数１〜４のアルキル基又はフェニル基を示す。］

Wherein ^{(1), R 1, R} 2 and ^{R 3} each independently represent a divalent organic group, ^{R 4} represents a hydrogen atom or a methyl group, ^{R 5} and ^{R 6} each independently, 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 (1) 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 represents a divalent organic group, but a phenylene group which may have a substituent, a pyridylene group which may have a substituent, or a branched chain having 1 to 10 carbon atoms. It is preferably an alkylene group which may be used. R ⁵ and R ⁶ 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 occur, which is not preferable. In some cases, the reaction may be carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, or dimethylsulfoxide.

  Moreover, (B) polymeric compound may contain other polymeric compounds other than the polymeric compound which has an amide bond and two or more ethylenically unsaturated groups in the molecule | numerator mentioned above. Other polymerizable compounds include, for example, compounds obtained by reacting polyhydric alcohols with α, β-unsaturated carboxylic acids, bisphenol A (meth) acrylate compounds, and glycidyl group-containing compounds with α, β-unsaturated compounds. Examples thereof include compounds obtained by reacting carboxylic acids, urethane monomers or urethane oligomers such as (meth) acrylate compounds having a urethane bond, nonylphenoxypolyethyleneoxyacrylate, phthalic acid-based 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.

  Here, “EO” represents ethylene oxide, and an EO-modified compound represents one having a block structure of an ethylene oxide group. “PO” represents propylene oxide, and a PO-modified compound has a propylene oxide group block structure.

  Examples of the compound obtained by reacting the glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include, for example, an epoxy resin (a) such as a novolac type epoxy resin, a bisphenol type epoxy resin, and a salicylaldehyde type epoxy resin; Examples thereof include an epoxy acrylate compound obtained by reacting (meth) acrylic acid (b). 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.) is commercially available.

  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.

  These can be used alone or in combination of two or more.

  (B) In the polymerizable compound, the content of the polymerizable compound having an amide bond and two or more ethylenically unsaturated groups in the molecule is from the viewpoint of making the resolution, low water absorption and heat-and-moisture resistance better. (B) It is preferable that it is 40 mass% or more on the basis of the polymeric compound whole quantity, It is more preferable that it is 50 mass% or more, It is still more preferable that it is 60 mass% or more.

  In the photosensitive resin composition, the content of the polymerizable compound (B) is preferably 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). More preferably, it is 70 parts by mass. When the content is less than 20 parts by mass, the resolution 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, it exists in the tendency for heat-and-moisture resistance to fall.

  The photopolymerization initiator as component (C) in the present invention is not particularly limited as long as it generates free radicals by actinic rays. For example, aromatic ketones, acylphosphine oxides, oxime esters, quinones, Examples include benzoin ether 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 the 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.

  (C) A photoinitiator may be synthesize | combined by a conventional method and a commercially available thing may be obtained. Examples of the available (C) photopolymerization initiator include Irgacure-369, Irgacure-907, Irgacure-651, Irgacure-819, Irgacure-OXE-01 (all of these are manufactured by Ciba Specialty Chemicals, Inc., Product name).

  Among the above-described (C) photopolymerization initiators, acylphosphine oxide is particularly preferable from the viewpoint of improving photocurability and increasing sensitivity. As the acylphosphine oxide, a compound represented by the following general formula (18) is preferable.

In the above formula (18), R ³¹ , R ³² and R ³³ each independently represent a monovalent organic group, and h, i and j each independently represents an integer of 0 to 5. Here, the monovalent organic group represented by R ³¹ , R ³² and R ³³ is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms. Such a hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 20 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms. Moreover, as a combination of h, i, and j, it is preferable that h is 0, i is 0, and j is 3.

  The compound represented by the general formula (18) is commercially available, for example, as Irgacure-819 (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.).

  (C) The photoinitiator mentioned above can be used individually by 1 type or in combination of 2 or more types. In the present invention, it is particularly preferable to use acylphosphine oxide and oxime esters in combination from the viewpoint of improving the resist shape.

  In the photosensitive resin composition, the content of (C) the photopolymerization initiator is preferably 1 to 20% by mass, preferably 1 to 10% by mass based on the total solid content of the photosensitive resin composition. It is more preferable. (C) When the content of the photopolymerization initiator is out of the above range, the sensitivity of the photosensitive resin composition is decreased or the compatibility is decreased as compared with the case where the content is in the above range. There is a tendency.

  Moreover, you may add (D) crosslinking agent further to the photosensitive resin composition of this invention. (D) Although it does not restrict | limit especially as a crosslinking agent, An epoxy compound, a blocked isocyanate compound, an oxazine compound, a methylol compound, a melamine compound, etc. are mentioned. Specifically, HP-4032D (trade name, manufactured by Dainippon Ink Industries, Ltd., naphthalene type epoxy resin) is preferable as the epoxy compound. Specifically, BL-3175 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., blocked isocyanate) is preferable as the blocked isocyanate compound. As the oxazine compound, Pd-type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.) is preferable. As the methylol compound, TML-BPAF (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) is preferable. As the melamine compound, Nicalac MW-30HM (trade name, manufactured by Sanwa Chemical Co., Ltd.) is preferable. When these cross-linking agents are added, the adhesiveness of the cured photosensitive resin composition to the substrate can be further improved, the cross-linking density is improved, and the rigidity and heat-and-moisture resistance are improved. These (D) crosslinking agents are used individually by 1 type or in mixture of 2 or more types.

  When (D) a crosslinking agent is contained in the photosensitive resin composition, the content is preferably 5 to 40 parts by mass, and 10 to 30 parts by mass with respect to 100 parts by mass of (A) polyamic acid. More preferably. (D) When content of a crosslinking agent remove | deviates from the said range, compared with the case where content is in the said range, there exists a tendency for the cured film after a hardening (hardening) to become weak or for resolution to fall.

  Further, (E) a sensitizer can be further added to the photosensitive resin composition of the present invention. Examples of the (E) sensitizer include Michler's ketone, 4,4-diethylaminobenzophenone, 3,3′-carbonylbis (diethylaminocoumarin) and the like. (E) As a sensitizer, from the viewpoints of sensitivity of the photosensitive resin composition and compatibility with a solvent, coumarins are preferable, and coumarin 102 (trade name, manufactured by Acros Corporation) is particularly preferable. These (E) sensitizers are used individually by 1 type or in mixture of 2 or more types.

  The content of the (E) sensitizer in the photosensitive resin composition is preferably 0.1 to 1% by mass based on the total solid content 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 invention comprises the above-mentioned (A) polyamic acid, (B) polymerizable compound, (C) photopolymerization initiator, (D) cross-linking agent used as necessary, and as necessary. The (E) sensitizer used in the above 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.

(SAW filter and manufacturing method thereof)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the SAW filter 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 with the resin cured material which consists of the photosensitive resin composition of this invention.

  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 manufactured using what formed into a film the photosensitive resin composition of this invention previously, for example. 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 moisture-heat resistance and has a low water absorption rate. Further, 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. The 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 is not deformed at a temperature of 170 to 180 ° C. 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. Further, the elastic modulus at 180 ° C. is preferably 100 MPa or more, more preferably 200 MPa or more, and particularly preferably 300 MPa or more. 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 weight average molecular weight and 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 weight average molecular weight of polyamic acid was 29000, and dispersity (weight average molecular weight / number average molecular weight) was 1.7. “Versamine 551” is a diamine compound including a compound represented by the following formula (19) and / or a compound in which an unsaturated portion of the compound represented by the following formula (19) is hydrogenated.

(Synthesis Example 2)
To a 300 mL four-necked separable flask, 19.61 g (0.035 mol) of Versamine 551 and 30 g of N-methylpyrrolidone were added and stirred at room temperature for 15 minutes. Next, a mixed solution of 20.39 g (0.039 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 weight average molecular weight of polyamic acid was 33000, and dispersity (weight average molecular weight / number average molecular weight) was 3.4.

(Synthesis Example 3)
In a 300 mL four-necked separable flask, 12.89 g (0.052 mol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane, 0.11 g (0.001 mol) of m-aminophenol, Then, 10.0 g of γ-butyrolactone was added and stirred at 40 ° C. 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 weight average molecular weight of polyamic acid was 36000, and dispersity (weight average molecular weight / number average molecular weight) was 1.8.

(Synthesis Example 4)
In a 1 L four-necked separable flask, 128.90 g (0.42 mol) of 2,2-bis- [4- (4-aminophenoxy) phenyl] propane, 20.00 g (0.10 mol) of 1,12-dodecanediamine ), 1.09 g (0.01 mol) of m-aminophenol and 100.0 g of γ-butyrolactone were added and stirred at 50 ° C. for 15 minutes. Next, a mixed solution of 164.40 g (0.53 mol) of 4,4′-oxydiphthalic dianhydride and 371.6 g 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 weight average molecular weight of polyamic acid was 32000, and dispersity (weight average molecular weight / number average molecular weight) was 2.0.

(Molecular weight measurement)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyamic acid synthesized in Synthesis Examples 1 to 4 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 1-5 and Comparative Examples 1-5]
(A) A solution of polyamic acid synthesized in each of the above synthesis examples, (B) a polymerizable compound, and (C) a photopolymerization initiator were mixed at a blending ratio (parts by mass) shown in Table 1 below, respectively. The solution of the photosensitive resin composition of Examples 1-5 and Comparative Examples 1-5 was obtained. In addition, the number in Table 1 has shown the mass part of solid content. Moreover, each component in Table 1 is shown below.

BPA-BDAM (synthetic product, amide acrylate),
TMCH-5R (trade name, urethane acrylic oligomer synthesized from trimethylhexamethylene diisocyanate, cyclohexanedimethanol, and 2-hydroxyethyl methacrylate, manufactured by Hitachi Chemical Co., Ltd.),
FA-129A (trade name, 1,9-nonanediol diacrylate, manufactured by Hitachi Chemical Co., Ltd.),
DPE-6A (trade name, dipentaerythritol hexaacrylate, manufactured by Kyoeisha Chemical Co., Ltd.),
EA-6340 (trade name, acid-modified epoxy acrylate, manufactured by Nakamura Chemical Co., Ltd.),
I-819 (trade name, bisacylphosphine oxide, manufactured by Ciba Specialty Chemicals Co., Ltd.).

  Here, BPA-BDAM is synthesized by the following method. Into 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. did. Thereafter, methoquinone (500 ppm) 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 the mixture was further stirred at 100 ° C. for 6 hours. When 1 mg KOH / g was reached, stirring was stopped to obtain a solution of a compound (BPA-BDAM) represented by the following formula (20) which is a photopolymerizable unsaturated compound. The solid content of the obtained solution was 80% by mass.

<Evaluation of solvent 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 110 ° C. for 5 minutes, and the film thickness after drying was 30 μm and the size was 10 mm × A 10 mm photosensitive resin 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 by the exposure amount of 600 mJ / cm < ² > using the proximity exposure machine (brand name: UX-1000SM) made by Ushio Electric. And photocured. Next, the silicon substrate on which the cured film of the photosensitive resin composition layer was formed was cut into a 1 cm square to obtain a test piece. By immersing this test piece in cyclohexanone, which is an organic solvent-based developer, and confirming the presence or absence of peeling and swelling of the photosensitive resin composition layer (resist) after photocuring, the solvent resistance is based on the following criteria Sex was evaluated. The results are shown in Table 2.
A: There is no peeling and swelling of the resist even after 5 minutes.
B: The resist peeled and / or swelled during 1 to 5 minutes.
C: The resist peeled and / or swollen within 1 minute.

<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 110 ° C. for 5 minutes, and the photosensitive resin having a film thickness of 30 μm after drying. A composition layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, exposure amount 600mJ using the proximity exposure machine (brand name: UX-1000SM) by USHIO INC. Through a negative mask which has an opening pattern with a hole diameter of 80 μmφ. The photosensitive resin composition layer was exposed at / cm ² . The test substrate was developed by being immersed in cyclohexanone, which is an organic solvent developer, for 5 minutes. The resist pattern after development was observed, and the solvent resistance was evaluated based on the following criteria. The results are shown in Table 2.
A: A hole diameter of 80 μm is opened and there is no residue after development.
B: Although the hole diameter is 80 μmφ, there is a residue after development.
C: Hole diameter 80 μmφ is not open.

<Measurement of glass transition temperature and elastic modulus>
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 110 ° C. for 5 minutes, and the photosensitive resin having a film thickness of 30 μm after drying. 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 by the exposure amount of 600 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 layer was peeled from the silicon substrate, and the glass transition temperature (Tg) of the peeled cured film was measured with TMA-120 manufactured by Seiko. The glass transition temperature was measured under the conditions of Extension: 10 g, 5 ° C./min, sample size: 1 cm length × 2 mm width. Moreover, the elastic modulus of the peeled cured film was measured with a viscoelasticity tester (manufactured by TA instruments, trade name: RSA-III). 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 110 ° C. for 5 minutes, and the photosensitive resin having a film thickness of 30 μm after drying. 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 by the exposure amount of 600 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 40 minutes and then at 200 ° 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 adhesiveness 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 greater than 10 squares).

<Measurement of water absorption rate>
Using the applicator, the solutions of the photosensitive resin compositions of Examples and Comparative Examples were uniformly applied on a glass plate having a thickness of 1 mm, dried on a hot plate at 110 ° C. for 5 minutes, and the film thickness after drying was 30 μm. The photosensitive resin 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 by the exposure amount of 600 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 40 minutes and then at 200 ° C. for 60 minutes. This test substrate was immersed in purified water for 24 hours, the water absorption was determined from the change in mass before and after immersion according to the following formula (I), and the water absorption was evaluated from the value based on the following criteria. The results are shown in Table 2.
Water absorption (%) = (cured film mass after immersion−cured film mass before immersion) / (cured film mass before immersion) × 100 (I)
A: Water absorption <0.8%.
B: 0.8% ≦ water absorption ≦ 1.2%.
C: Water absorption> 1.2%.

It is a schematic cross section which shows suitable one Embodiment of the SAW filter of this invention. (A)-(c) is process drawing which shows suitable one Embodiment of the manufacturing method of the SAW filter of this invention.

Explanation of symbols

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 (9)

(A) a polyamic acid, (B) a polymerizable compound, and (C) a photopolymerization initiator,
The photosensitive resin composition in which the said (B) polymeric compound contains the polymeric compound which has an amide bond and two or more ethylenically unsaturated groups in a molecule | numerator. The said (B) polymeric compound contains the compound represented by following General formula (1) as a polymeric compound which has an amide bond and two or more ethylenically unsaturated groups in the said molecule | numerator. Photosensitive resin composition.

[In the formula (1), R ¹ , R ² and R ³ each independently represents a divalent organic group, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ and R ⁶ each independently represent hydrogen. An atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group is shown. ] In the general formula (1), R ¹ is a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a group represented by the following general formula (2). ² and R ³ are each independently a phenylene group which may have a substituent, a pyridylene group which may have a substituent, or an alkylene group which may have 1 to 10 carbon atoms, The photosensitive resin composition of Claim 2.

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

R ⁷ and R ⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a halogen atom, and m1 and n1 each independently represents an integer of 1 to 4. In addition, when m1 is 2 or more, a plurality of R ⁷ may be the same or different, and when n1 is 2 or more, a plurality of R ⁸ may be the same or different. ]   As the polymerizable compound in which the polymerizable compound (B) has an amide bond and two or more ethylenically unsaturated groups in the molecule, an oxazoline group-containing compound, a carboxyl group-containing compound, and / or a phenolic hydroxyl group-containing compound are used. The photosensitive resin composition as described in any one of Claims 1-3 containing the di (meth) acrylate which has an amide bond obtained by making it react. The photosensitive resin composition as described in any one of Claims 1-4 in which the said (A) polyamic acid contains the compound 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 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. An alkoxy group, m2 and n2 each independently represent an integer of 1 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 Formula (5), X ³ represents an alkylene group having 5 to 20 carbon atoms, and R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, 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 1 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 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. An alkoxy group, p and q each independently represent an integer of 1 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 a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or A C1-C3 alkoxy group is shown, r, s, t, and u show the integer of 1-4 each independently. Note that when r is 2 or more, R ¹⁸ there are a plurality may be the same or different, when s is 2 or more, R ¹⁹ there are a plurality may be the same or different, 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 a hydrogen atom, an alkyl group or an alkoxy group having 1 to 3 carbon atoms having 1 to 6 carbon atoms, v is an integer of 1-3. 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 Z ² in the general formula (9) is a divalent organic group represented by the following general formula (10), the following general formula (11), or the following general formula (12). Photosensitive resin composition.

[In the formula (10), R ²³ represents a hydrogen atom, 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 1 to 4. Show. 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 a hydrogen atom, 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 1 to 4. Show. When w2 is 2 or more, a plurality of R ²⁴ may be the same or different. ]

[In the formula (12), R ²⁵ represents a hydrogen atom, 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 1 to 4. Show. In addition, when w3 is 2 or more, a plurality of R ²⁵ may be the same or different. ]   The photosensitive resin composition as described in any one of Claims 1-6 used for formation of a SAW filter.   A SAW filter comprising a cured resin product comprising the photosensitive resin composition according to claim 1.   A photosensitive resin composition layer made of the photosensitive resin composition according to any one of claims 1 to 7 is laminated on a substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays. Then, the exposed portion is photocured, and then the portion other than the exposed portion of the photosensitive resin composition layer is removed using an organic solvent-based developer, and then the exposed portion of the photosensitive resin composition layer is removed. A method for producing a SAW filter, comprising a step of thermally curing to form a cured resin.

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