JP5064950B2 - Novel photosensitive resin composition, photosensitive resin composition solution obtained therefrom, photosensitive film, insulating film, and printed wiring board with insulating film - Google Patents

Description

  Since this invention has photosensitivity, it can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or less), has high flexibility without using siloxane diamine, Photosensitive resin composition with excellent insulation reliability, solder heat resistance, and organic solvent resistance, small warpage of the substrate after curing, and excellent adhesion to the sealant, cured film, insulating film, and insulation obtained therefrom The present invention relates to a printed wiring board with a film.

  Polyimide resins are widely used in electrical and electronic applications because of their excellent heat resistance, electrical insulation reliability, chemical resistance, and mechanical properties. For example, it is used to form insulating films and protective coatings on semiconductor devices, base materials such as flexible circuit boards and integrated circuits, surface protective materials, and further, interlayer insulating films and protective films for fine circuits. .

  In particular, when used as a surface protection material for a flexible circuit board, a coverlay film obtained by applying an adhesive to a molded body such as a polyimide film has been used. When bonding this coverlay film on a flexible circuit board, there is a method in which an opening is provided in advance by a method such as punching in a terminal portion of a circuit or a joint portion with a component, and after aligning, a method of thermocompression bonding by a hot press or the like is used. It is common.

  However, it is difficult to provide a high-accuracy opening in a thin coverlay film, and since the alignment at the time of lamination is often performed manually, the positional accuracy is poor and the workability of the lamination is also poor. The cost was high.

  On the other hand, a liquid cover coat ink or the like may be used as a surface protection material for a circuit board. In particular, a liquid cover coat ink having a photosensitive function is preferably used when fine processing is required. Yes. As this liquid cover coat ink, a photosensitive ink mainly composed of an epoxy resin or the like (generally also referred to as a solder resist) is used. This ink has excellent electrical insulation reliability as an insulating material, but is flexible. Since the mechanical properties such as the above are poor and the curing shrinkage is large, when it is laminated on a thin and flexible circuit board such as a flexible circuit board, the warp of the board becomes large and it is difficult to use it for a flexible circuit board.

  In recent years, various proposals have been made as liquid cover coat inks that can exhibit flexibility and high electrical insulation reliability.

  For example, a photosensitive resin composition (for example, see Patent Document 1) containing a polyimide resin using siloxane diamine and a photosensitive resin composition made of a polyamic acid solution that is a polyimide precursor has been proposed (for example, (See Patent Documents 2-3).

  Also, a photosensitive resin composition comprising a urethane compound obtained by reacting a diisocyanate compound and a monovinyl monohydroxy compound having an alicyclic skeleton with a polycarbonate diol, which has excellent flexibility, photocurability and insulating properties and is capable of alkali development. Has been proposed (see, for example, Patent Documents 4 to 5).

In addition, it has excellent heat resistance, electrical properties, and photocurability, can be patterned by development with dilute aqueous alkali, is soluble in solvents, has a urethane bond in the main chain, and has a (meth) acryloyl group and a carboxyl group. There has been proposed an active energy ray-curable resin composition made of a polyimide resin having the following. (For example, refer to Patent Document 6).
JP 9-100350 A JP-A-2-50161 JP 2005-148611 A JP 2000-95837 A JP 2000-241969 JP 2000-344890

  However, in the above-mentioned Patent Document 1, when a polyimide-type photosensitive resin composition is used as a cover coat ink, since it is a high molecular weight polyimide solution, the solubility in a solvent is low and the concentration of the solute is increased. For example, when forming a coating film, it is necessary to volatilize a large amount of solvent, and there is a problem that productivity is poor. Moreover, in said patent documents 2-3, in addition to said problem, it has a photosensitive group in the side chain of polyamic acid, The high temperature (for the purpose of removing the photosensitive group and accelerating imidation reaction ( 300 ° C. or higher) is required, and there is a problem that it cannot be used as a protective insulating layer of a general printed wiring board.

  Moreover, in said patent documents 1-3, the solubility to the dilute alkaline aqueous solution generally used as a developing solution of the photosensitive ink for printed wiring boards is scarce, and the organic solvent type developing solution must be used. For this reason, there existed a problem that work environment and workability were bad. Furthermore, silicon diamine is used to introduce a flexible skeleton, and it is known that the flexibility and electrical insulation reliability of the cured film are greatly improved by using this, When used for an insulating coating, there is a problem of poor adhesion (adhesiveness) with the sealant resin. Furthermore, oligomers contained in siloxane diamine have problems such as inducing malfunction of semiconductors, and are becoming difficult to use.

  In the above-mentioned Patent Document 4, the electrical insulation reliability and heat resistance under high temperature and high humidity are poor as compared with the case where a polyimide type or polyamic acid type photosensitive resin composition is used as the cover coat ink. In Patent Document 5, a phosphoric ester-based additive type flame retardant is added for the purpose of imparting flame retardancy, and hydrolysis of this flame retardant causes a significant decrease in electrical insulation reliability, and in addition, curing. There were problems such as bleeding out of the flame retardant from the film and elution into an organic solvent or gold plating bath.

  In the above-mentioned Patent Document 6, a polyimide resin having a urethane bond in the main chain and having a (meth) acryloyl group and a carboxyl group has a low number average molecular weight, includes a rigid skeleton, and includes a soft segment having flexibility. Since it has a carboxyl group at the end of the main chain and a side chain at random, it has poor flexibility and large curing shrinkage, so it can be used as a protective insulating layer for thin and flexible circuit boards such as flexible circuit boards. There was a problem that could not be.

  In view of the above situation, the problem of the present invention is that it has photosensitivity, can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or less), and does not use siloxane diamine. To provide a photosensitive resin composition that is flexible, excellent in electrical insulation reliability, solder heat resistance, and organic solvent resistance, has low warpage of the substrate after curing, and has excellent adhesion to a sealant. is there.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using the following photosensitive resin composition.

  That is, the present invention includes (A) a polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain, a developing group at least in the side chain, and a photosensitive group at the end of the main chain, (B) A photosensitive resin composition comprising at least a photosensitive compound other than (A) having at least one photosensitive group, (C) a photopolymerization initiator, and (D) a thermosetting compound.

  It is preferable that the developable group of the (A) polyimide resin is a carboxyl group, and the photosensitive group of the (A) polyimide resin and (B) the photosensitive compound is a (meth) acryloyl group.

  The (A) polyimide resin is at least (a1) a hydroxyl-terminated etherimide oligomer represented by the following general formula (1), (a2) a polycarbonate diol represented by the following general formula (2), and (a3) the following general Dihydroxycarboxylic acid compound represented by formula (3), (a4) (compound having an isocyanate group and at least one (meth) acryloyl group in the molecule represented by the following general formula (4)) and / or (the following general formula It is also preferred that the compound is obtained by reacting a compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule represented by (5), and (a5) a diisocyanate compound represented by the following general formula (6).

（式中、Ｘは少なくとも１つのエーテル結合を有する４価の有機基を示し、Ｙは２価の有機基を示し、複数個のＲ_１はそれぞれ独立に２価の有機基を示す。ｐは０〜２０の整数である。）

(Wherein X represents a tetravalent organic group having at least one ether bond, Y represents a divalent organic group, and a plurality of R _{1 s} independently represent a divalent organic group. P represents It is an integer from 0 to 20.)

（式中、複数個のＲ_２はそれぞれ独立に２価の有機基を示す。ｑは１〜２０の整数である。）

(In the formula, plural R _{2 s} each independently represent a divalent organic group. Q is an integer of 1 to 20.)

（式中、Ｒ_３は２価の有機基を示す。）

(In the formula, R ₃ represents a divalent organic group.)

（式中、Ｒ_４は２価の有機基を示し、Ｒ_５は水素もしくは、アルキル基を示す。ｍは１〜３の整数である。）

(In the formula, R ₄ represents a divalent organic group, R ₅ represents hydrogen or an alkyl group, and m is an integer of 1 to 3.)

（式中、Ｒ_６は２価の有機基を示し、Ｒ_７は水素もしくは、アルキル基を示す。ｎは１〜３の整数である。）

(Wherein R ₆ represents a divalent organic group, R ₇ represents hydrogen or an alkyl group, and n is an integer of 1 to 3)

（式中Ｒ_８は２価の有機基である。）
また、前記（ａ１）水酸基末端エーテルイミドオリゴマーが、少なくとも、下記一般式（７）または下記一般式（８）で示される、分子内に少なくとも１つのエーテル結合を有するテトラカルボン酸二無水物と、下記一般式（９）で示されるアミノアルコールを反応させて得られることも好ましい。

(Wherein R ₈ is a divalent organic group.)
The (a1) hydroxyl group-terminated etherimide oligomer is at least a tetracarboxylic dianhydride having at least one ether bond in the molecule represented by the following general formula (7) or the following general formula (8): It is also preferable to obtain it by reacting an amino alcohol represented by the following general formula (9).

（式中、Ｒ_９は２価の有機基を示す。）

(In the formula, R ₉ represents a divalent organic group.)

（式中Ｒ_１０は２価の有機基である。）
また、前記（ａ１）水酸基末端エーテルイミドオリゴマーが、モル比で、（分子内に少なくとも１つのエーテル結合を有するテトラカルボン酸二無水物のモル数／アミノアルコールのモル数）＝０．２５〜０．７５の範囲内で反応させることも好ましい。

(In the formula, R ₁₀ is a divalent organic group.)
The (a1) hydroxyl group-terminated etherimide oligomer is in a molar ratio (number of moles of tetracarboxylic dianhydride having at least one ether bond in the molecule / number of moles of amino alcohol) = 0.25 to 0. It is also preferable to react within the range of .75.

  The (a1) hydroxyl group-terminated etherimide oligomer is preferably obtained by further reacting a diamino compound represented by the following general formula (10).

（式中Ｒ_１１は２価の有機基である。）
また、前記（ａ１）水酸基末端エーテルイミドオリゴマーが、モル比で、（分子内に少なくとも１つのエーテル結合を有するテトラカルボン酸二無水物のモル数）／（アミノアルコールのモル数＋ジアミノ化合物のモル数）＝０．２５〜１．０の範囲内で反応させて得られることも好ましい。

(In the formula, R ₁₁ is a divalent organic group.)
The (a1) hydroxyl group-terminated etherimide oligomer is in a molar ratio of (number of moles of tetracarboxylic dianhydride having at least one ether bond in the molecule) / (number of moles of amino alcohol + mol of diamino compound). Number) = 0.25 to 1.0. It is also preferable to obtain the reaction.

  The (A) polyimide resin has (a1) the number of moles of the hydroxyl-terminated etherimide oligomer (a1), (a2) the number of moles of polycarbonate diol (a2), and (a3) the number of moles of the dihydroxycarboxylic acid compound. Number of moles of (a3), (a4) (a compound having an isocyanate group and at least one (meth) acryloyl group in the molecule) and / or (a compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule) (A4), (a5) When the number of moles of the diisocyanate compound is (a5), [(a1) + (a2) + (a3)] / [(a4) + (a5)] = 0.5 to It is also preferably obtained by reacting within the range of [(a1) + (a2)] / (a3) = 0.1 to 5.0.

  The (A) polyimide resin is preferably obtained by further reacting (a6) a compound having an epoxy group and at least one (meth) acryloyl group in the molecule, and (a7) a polybasic acid anhydride. .

  Further, the weight ratio of the component (A), the component (B), the component (C), and the component (D) in the photosensitive resin composition is such that the component (B) is based on 100 parts by weight of the component (A). The component (C) is preferably 0.1 to 20 parts by weight, and the component (D) is preferably 0.5 to 100 parts by weight.

  Another invention of the present invention is a photosensitive resin composition solution obtained by dissolving the photosensitive resin composition in an organic solvent.

  Another invention of the present invention is a photosensitive film obtained by applying and drying the above photosensitive resin composition on a substrate surface.

  Moreover, another invention of the present invention is an insulating film obtained by curing the photosensitive resin composition.

  Another invention of the present invention is a printed wiring board with an insulating film in which the printed resin board is coated with the photosensitive resin composition.

  Since the photosensitive resin composition of the present invention has photosensitivity, it can be finely processed, can be developed with a dilute alkaline aqueous solution, can be cured at a low temperature (200 ° C. or less), and without using siloxane diamine, It exhibits excellent flexibility, electrical insulation reliability, solder heat resistance, and organic solvent resistance, low warpage of the substrate after curing, and excellent adhesion to the sealant.

The composition of the present invention is as follows: (A) a polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain, a developing group at least in the side chain, and a photosensitive group at the end of the main chain; A photosensitive resin composition comprising at least one photosensitive compound other than (A) having at least one photosensitive group therein, (C) a photopolymerization initiator, and (D) a thermosetting compound. is there.
Hereinafter, each constituent material will be described.

<(A) Polyimide resin>
The polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain of the present invention, and having a developing group at least in the side chain and a photosensitive group at the end of the main chain has a weight average molecular weight of 10 in terms of polyethylene glycol. It is a polymer of 10,000 or less.
Here, the etherimide skeleton is a skeleton having an ether bond derived from a tetracarboxylic dianhydride having at least one ether bond in the molecule and at least one imide ring.

  A photosensitive resin composition comprising a polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain of the present invention, and having a developing group at least in the side chain and a photosensitive group at the main chain terminal is surprising. In particular, the present inventors have found that various characteristics are excellent, but it is speculated that this may be due to the following reasons. That is, since it has an etherimide skeleton in the main chain, it not only has excellent heat resistance and electrical insulation reliability derived from the imide skeleton, but also surprisingly, the flexibility of the molecular chain of the etherimide skeleton and the polycarbonate skeleton Due to the synergistic effect with the flexibility of the urethane bond, the flexibility of the molecular chain is excellent, and as a result, the degree of freedom of the developing group of the side chain and the photosensitive group of the terminal is improved, so that the solubility of the polyimide resin is increased. The probability that the photosensitive group contributes to the reaction is increased, and as a result, it is speculated that the developability and photosensitivity are excellent. In addition, since it has a developable group in the side chain, it increases the branch point of the main chain and decreases the orientation crystallinity of the molecule, thereby improving the solubility of the polyimide resin in the solvent, and further, such as epoxy resin and blocked isocyanate When a thermosetting compound is blended and heated, the thermosetting compound reacts with the developing group of the side chain and takes a three-dimensional cross-linked structure, improving solder heat resistance, chemical resistance, and electrical insulation reliability. I guess that. Moreover, since it has a photosensitive group at the end of the main chain, when taking a crosslinked structure by UV irradiation, it is speculated that the distance between the crosslinking points is increased and a flexible crosslinked structure is obtained. Further, since the polyimide resin of the present invention has an ether bond, it has high solubility in various solvents, and therefore can be easily produced without precipitation or precipitation even in the polymerization step.

  The polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain of the present invention, and having a developing group at least in the side chain and a photosensitive group at the end of the main chain is not particularly limited as long as it has these structures. Preferably, however, (a1) a hydroxyl-terminated etherimide oligomer represented by the following general formula (1), (a2) a polycarbonate diol represented by the following general formula (2), (a3) represented by the following general formula (3) (A4) (a compound having an isocyanate group and at least one (meth) acryloyl group in a molecule represented by the following general formula (4)) and / or (denoted by the following general formula (5) Compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule), (a5) dii represented by the following general formula (6) Cyanate compound, obtained by reacting.

（式中、Ｘは少なくとも１つのエーテル結合を有する４価の有機基を示し、Ｙは２価の有機基を示し、複数個のＲ_１はそれぞれ独立に２価の有機基を示す。ｐは０〜２０の整数である。）

(Wherein X represents a tetravalent organic group having at least one ether bond, Y represents a divalent organic group, and a plurality of R _{1 s} independently represent a divalent organic group. P represents It is an integer from 0 to 20.)

（式中、複数個のＲ_２はそれぞれ独立に２価の有機基を示す。ｑは１〜２０の整数である。）

(In the formula, plural R _{2 s} each independently represent a divalent organic group. Q is an integer of 1 to 20.)

（式中、Ｒ_３は２価の有機基を示す。）

(In the formula, R ₃ represents a divalent organic group.)

（式中、Ｒ_４は２価の有機基を示し、Ｒ_５は水素もしくは、アルキル基を示す。ｍは１〜３の整数である。）

(In the formula, R ₄ represents a divalent organic group, R ₅ represents hydrogen or an alkyl group, and m is an integer of 1 to 3.)

（式中、Ｒ_６は２価の有機基を示し、Ｒ_７は水素もしくは、アルキル基を示す。ｎは１〜３の整数である。）

(Wherein R ₆ represents a divalent organic group, R ₇ represents hydrogen or an alkyl group, and n is an integer of 1 to 3)

（式中Ｒ_８は２価の有機基である。）
＜（ａ１）水酸基末端エーテルイミドオリゴマー＞
本願発明の（ａ１）一般式（１）で示される水酸基末端エーテルイミドオリゴマーとは、主鎖末端に少なくとも１つの水酸基を有し、主鎖内部には、少なくとも１つのエーテル結合を有するテトラカルボン酸二無水物由来のエーテル結合と、少なくとも１つのイミド環を有する、重量平均分子量がポリエチレングリコール換算で１万以下のオリゴマーである。

(Wherein R ₈ is a divalent organic group.)
<(A1) Hydroxyl-terminated etherimide oligomer>
The (a1) hydroxyl group-terminated etherimide oligomer represented by the general formula (1) of the present invention is a tetracarboxylic acid having at least one hydroxyl group at the end of the main chain and at least one ether bond inside the main chain. An oligomer having an ether bond derived from dianhydride and at least one imide ring and having a weight average molecular weight of 10,000 or less in terms of polyethylene glycol.

  Although it will not specifically limit if it is these structures, Preferably, the tetracarboxylic dianhydride which has at least 1 ether bond in a molecule | numerator shown by following General formula (7) or following General formula (8), and the following It can be obtained by reacting the amino alcohol represented by the general formula (9).

（式中、Ｒ_９は２価の有機基を示す。）

(In the formula, R ₉ represents a divalent organic group.)

（式中Ｒ_１０は２価の有機基である。）
本願発明の一般式（７）または一般式（８）で示される水酸基末端エーテルイミドオリゴマーの原料として用いられる分子内に少なくとも１つのエーテル結合を有するテトラカルボン酸二無水物としては、例えば、３，３’,４,４’−オキシジフタル酸二無水物、３，３’,４,４’−ハイドロキノンジフタル酸二無水物、２，２− ビス[４−（３，４−ジカルボキシフェノキシ）フェニル]プロパン二無水物、２，２− ビス[４−（３，４−ジカルボキシフェノキシ）フェニル]ヘキサフルオロプロパン二無水物または４,４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルサルファイド−３，３’,４,４’−テトラカルボン酸二無水物等のテトラカルボン酸二無水物を用いることができる。

(In the formula, R ₁₀ is a divalent organic group.)
Examples of the tetracarboxylic dianhydride having at least one ether bond in the molecule used as a raw material for the hydroxyl-terminated etherimide oligomer represented by the general formula (7) or (8) of the present invention include, for example, 3, 3 ', 4,4'-oxydiphthalic dianhydride, 3,3', 4,4'-hydroquinone diphthalic dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl ] Propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride or 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide Tetracarboxylic dianhydrides such as 3,3 ′, 4,4′-tetracarboxylic dianhydride can be used.

  Particularly preferably, it can be obtained by using 3,3 ′, 4,4′-oxydiphthalic dianhydride or 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride. This is preferable in that the solubility of the hydroxyl-terminated etherimide oligomer in an organic solvent and the compatibility of the resulting polyimide resin with the photosensitive compound can be improved.

  Although it does not specifically limit as amino alcohol used as a raw material of the hydroxyl-terminated etherimide oligomer shown by General formula (9) of this invention, For example, 2-aminoethanol, 3-amino-1-propanol, 4-amino -1-butanol, 5-amino-1-pentanol, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- (4-aminophenyl) ethanol, 2-amino-m-cresol, 2-amino -P-cresol, 3-amino-o-cresol, 4-amino-o-cresol, 4-amino-m-cresol, 5-amino-o-cresol, 6-amino-m-cresol, 2-amino-1 , 2-diphenylethanol, 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-amino Down benzyl alcohol, 2-aminocyclohexanol, 4-aminocyclohexanol, it can be used 2-amino-cyclopentanol or 1-amino-1-cyclopentane methanol.

  Particularly preferably, by using 2-aminoethanol, 3-amino-1-propanol or 4-amino-1-butanol, the solubility of the resulting hydroxyl-terminated etherimide oligomer in an organic solvent can be improved. Is preferable.

  Moreover, when synthesizing the above hydroxyl-terminated etherimide oligomer, in addition to tetracarboxylic dianhydride having at least one ether bond in the molecule and amino alcohol, diamino represented by the following general formula (10) as a chain extender Compounds can also be used.

（式中Ｒ_１１は２価の有機基である。）
本願発明の一般式（１０）で示される水酸基末端エーテルイミドオリゴマーの鎖延長剤として用いられるジアミノ化合物としては、特に限定されるものではないが、例えば、ｍ−フェニレンジアミン、ｏ−フェニレンジアミン、ｐ−フェニレンジアミン、ビス（３−アミノフェニル）スルホン、ビス（４−アミノフェニル）スルホン、３，４’−ジアミノベンゾフェノン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニルメタン、３，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、ビス［４−（３−アミノフェノキシ）フェニル］メタン、ビス［４−（４−アミノフェノキシ）フェニル］メタン、２，２−ビス［４−（３−アミノフェノキシ）フェニル］プロパン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−[４−（４−アミノフェノキシフェニル）][４−（３−アミノフェノキシフェニル）] プロパン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（３−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、ビス［４−（３−アミノフェノキシ）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ポリテトラメチレンオキシド−ジ−ｐ−アミノベンゾエート、ポリ（テトラメチレン／３−メチルテトラメチレンエーテル）グリコールビス（４−アミノベンゾエート）、トリメチレン―ビス（４−アミノベンゾエート）、ｐ-フェニレン−ビス（４−アミノベンゾエート）、ｍ−フェニレン−ビス（４−アミノベンゾエート）、ビスフェノールＡ−ビス（４−アミノベンゾエート）、２，４−ジアミノ安息香酸、２，５−ジアミノ安息香酸、３，５−ジアミノ安息香酸、３，３’−ジアミノ−４，４’−ジカルボキシビフェニル、４，４’−ジアミノ−３，３’−ジカルボキシビフェニル、４，４’−ジアミノ−２，２’−ジカルボキシビフェニル、[ビス(４-アミノ-２-カルボキシ)フェニル]メタン、 [ビス(４-アミノ-３-カルボキシ)フェニル]メタン、[ビス(３-アミノ-４-カルボキシ)フェニル]メタン、 [ビス(３-アミノ-５-カルボキシ)フェニル]メタン、２，２−ビス[３−アミノ−４−カルボキシフェニル]プロパン、２，２−ビス[４−アミノ−３−カルボキシフェニル]プロパン、３，３’−ジアミノ−４，４’−ジカルボキシジフェニルエーテル、４，４’−ジアミノ−３，３’−ジカルボキシジフェニルエーテル、４，４’−ジアミノ−２，２’−ジカルボキシジフェニルエーテル、３，３’−ジアミノ−４，４’−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−３，３’−ジカルボキシジフェニルスルフォン、４，４’−ジアミノ−２，２’−ジカルボキシジフェニルスルフォン、２，３−ジアミノフェノール、２，４−ジアミノフェノール、２，５−ジアミノフェノール、３，５−ジアミノフェノール等のジアミノフェノール類、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、４，４’−ジアミノ−３，３’−ジヒドロキシビフェニル、４，４’−ジアミノ−２，２’−ジヒドロキシビフェニル、４，４’−ジアミノ−２，２’，５，５’−テトラヒドロキシビフェニル等のヒドロキシビフェニル化合物類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルメタン、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルメタン、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルメタン等のジヒドロキシジフェニルメタン類、２，２−ビス[３−アミノ−４−ヒドロキシフェニル]プロパン、２，２−ビス[４−アミノ−３−ヒドロキシフェニル]プロパン等のビス[ヒドロキシフェニル]プロパン類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルエーテル、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルエーテル等のヒドロキシジフェニルエーテル類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルスルフォン、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルフォン等のジヒドロキシジフェニルスルフォン類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルスルフィド、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルフィド等のジヒドロキシジフェニルスルフィド類、３，３’−ジアミノ−４，４’−ジヒドロキシジフェニルスルホキシド、４，４’−ジアミノ−３，３’−ジヒドロキシジフェニルスルホキシド、４，４’−ジアミノ−２，２’−ジヒドロキシジフェニルスルホキシド等のジヒドロキシジフェニルスルホキシド類、２，２−ビス[４−（４−アミノ−３−ヒドロキシフェノキシ）フェニル]プロパン等のビス［（ヒドロキシフェニル）フェニル］アルカン化合物類、４，４’−ビス（４−アミノ−３−ヒドキシフェノキシ）ビフェニル等のビス（ヒドキシフェノキシ）ビフェニル化合物類、２，２−ビス[４−（４−アミノ−３−ヒドロキシフェノキシ）フェニル]スルフォン等のビス[（ヒドロキシフェノキシ）フェニル]スルフォン化合物、４，４’−ジアミノ−３，３’−ジハイドロキシジフェニルメタン、４，４’−ジアミノ−２，２’−ジハイドロキシジフェニルメタン、２，２−ビス[３−アミノ−４−カルボキシフェニル]プロパン、４，４’−ビス（４−アミノ−３−ヒドキシフェノキシ）ビフェニル等のビス（ヒドキシフェノキシ）ビフェニル化合物類、１，２−ジアミノシクロヘキサン、１，３−ジアミノシクロヘキサン、１，４−ジアミノシクロヘキサン、１，４−シクロヘキサンビス（メチルアミン）、４，４’−ジアミノジシクロヘキシルメタン、（４−アミノ−３−メチルシクロヘキシル）メタン、５−アミノ−１，３，３−トリメチルシクロヘキサンメチルアミン、３（４），８（９）−ビス（アミノメチル）トリシクロ[５．２．１．０^２，６]デカン、２，５（６）−ビス（アミノメチル）ビシクロ[２．２．１]ヘプタン、１，３−ジアミノアダマンタン等の脂環族ジアミン類、テトラメチレンジアミン、ヘキサメチレンジアミン、１，１２−ジアミノドデカン等の脂肪族ジアミン類、ポリオキシエチレンジアミンまたはポリオキシプロピレンジアミン等のポリオキシオキシアルキレンジアミン類などを挙げることができる。

(In the formula, R ₁₁ is a divalent organic group.)
Although it does not specifically limit as a diamino compound used as a chain extender of the hydroxyl-terminated etherimide oligomer shown by General formula (10) of this invention, For example, m-phenylenediamine, o-phenylenediamine, p -Phenylenediamine, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,3 ' -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (3 -Aminophenoxy) phenyl] sulfone, [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- [4- (4-aminophenoxyphenyl)] [4- (3-amino Phenoxyphenyl)] propane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, Polytetramethylene oxide-di-p-aminobenzoate, poly (tetramethylene / 3-methyltetramethylene ether) glycol bis (4-aminobenzoate), trimethylene-bis (4-aminobenzoate), p-phenylene-bis (4 -Aminobenzoate), m-phenylene-bis (4-aminobenzoate), bisphenol A-bis (4-aminobenzoate), 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid Acid, 3,3′-diamino-4,4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2′-dicarboxybiphenyl, [Bis (4-amino-2-carboxy) phenyl] methane, [bis (4-amino-3-carboxy) phenyl] methane, [Bis (3-amino-4-carboxy) phenyl] methane, [bis (3-amino-5-carboxy) phenyl] methane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 2,2 -Bis [4-amino-3-carboxyphenyl] propane, 3,3'-diamino-4,4'-dicarboxydiphenyl ether, 4,4'-diamino-3,3'-dicarboxydiphenyl ether, 4,4 '-Diamino-2,2'-dicarboxydiphenyl ether, 3,3'-diamino-4,4'-dicarboxydiphenyl sulfone, 4,4'-diamino-3,3'-dicarboxydiphenyl sulfone, 4,4 '-Diamino-2,2'-dicarboxydiphenylsulfone, 2,3-diaminophenol, 2,4-diaminophenol, 2,5-diaminophenol, 3,5-diamino Diaminophenols such as phenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-2,2′-dihydroxy Hydroxyphenyl compounds such as biphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylmethane, 4,4′-diamino Dihydroxydiphenylmethanes such as −3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2- Bis [hydroxyphenyl] propanes such as bis [4-amino-3-hydroxyphenyl] propane, 3,3′-diamino-4, Hydroxydiphenyl ethers such as 4′-dihydroxydiphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 3,3′-diamino-4, Dihydroxydiphenyl sulfones such as 4′-dihydroxydiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfone, 3,3′- Dihydroxydiphenyl sulfides such as diamino-4,4′-dihydroxydiphenyl sulfide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfide, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfide, 3 , 3'-Diamino-4,4'-dihydride Dihydroxydiphenyl sulfoxides such as loxydiphenyl sulfoxide, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfoxide, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfoxide, 2,2-bis [4- Bis [(hydroxyphenyl) phenyl] alkane compounds such as (4-amino-3-hydroxyphenoxy) phenyl] propane, bis (hydrido) such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl Xyphenoxy) biphenyl compounds, bis [(hydroxyphenoxy) phenyl] sulfone compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, 4,4′-diamino-3, 3'-dihydroxydiphenylmethane, 4,4'-diamino-2,2'-diha Bis (hydroxyphenoxy) biphenyl compounds such as droxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,4-cyclohexanebis (methylamine), 4,4′-diaminodicyclohexylmethane, (4-amino-3-methyl) Cyclohexyl) methane, 5-amino-1,3,3-trimethylcyclohexanemethylamine, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 ^2,6 ] decane, 2 , 5 (6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-diaminoadamantane, etc. Diamines, tetramethylene diamine, hexamethylene diamine, 1,12-aliphatic diamines diamino dodecane, polyoxyethylene polyoxyalkylene diamines, such as polyoxyethylene diamine or polyoxypropylene diamines and the like.

  Particularly preferably, m-phenylenediamine, 3,3′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- ( 3-aminophenoxy) phenyl] methane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) Heat resistance and electrical insulation reliability of polyimide resin obtained by using aromatic diamine such as benzene), 1,4-bis (4-aminophenoxybenzene) or 1,3-bis (4-aminophenoxybenzene) It is preferable at the point which can improve.

  The raw materials represented by the above general formula (7), general formula (8), general formula (9) and general formula (10) may be used alone or in combination of two or more. You may do it. Moreover, you may use the raw material shown by General formula (7) and General formula (8) simultaneously.

  The method for synthesizing the hydroxyl-terminated etherimide oligomer represented by the general formula (1) of the present invention is a tetracarboxylic dianhydride having at least one ether bond in the molecule represented by the general formula (7) or the general formula (8). Product and amino alcohol represented by the general formula (9) in a molar ratio (number of moles of tetracarboxylic dianhydride having at least one ether bond in the molecule / number of moles of amino alcohol) = 0.25 It can be obtained by reacting within a range of 0.75, more preferably 0.3 to 0.7, and particularly preferably 0.4 to 0.6.

  By controlling the addition amount within the above range and reacting, it is preferable because the hydroxyl-terminated etherimide oligomer can be obtained without generation of unreacted products and by-products. When it is smaller than 0.25, a large amount of unreacted aminoethanol remains in the system, and when used in the photosensitive resin composition, heat resistance and electrical insulation reliability may be lowered. Moreover, when larger than 0.75, the yield of the target hydroxyl-terminated etherimide oligomer may become low.

  When the diamino compound represented by the general formula (10) is used as the chain extender, the reaction is carried out by adding tetracarboxylic dianhydride having at least one ether bond in the molecule and amino alcohol. Yes, but not limited to this. The added amount of the diamino compound is preferably (molar number of tetracarboxylic dianhydride having at least one ether bond in the molecule) / (molar number of amino alcohol + molar number of diamino compound) = It can be obtained by reacting in the range of 0.25 to 1.0, more preferably 0.3 to 0.9, and particularly preferably 0.4 to 0.8.

  By controlling the addition amount within the above range and reacting, it is preferable because the molecular weight of the hydroxyl-terminated etherimide oligomer can be controlled within the optimum range. When it is smaller than 0.25, a large amount of unreacted material remains in the system, and thus when used in the photosensitive resin composition, the heat resistance and the electrical insulation reliability may be lowered. Moreover, when larger than 1.0, the molecular weight of a hydroxyl-terminated imide oligomer will become large, and when it uses for the photosensitive resin composition, developability may fall.

  In the hydroxyl-terminated etherimide oligomer, each component is dissolved in an organic solvent at 100 ° C. or lower, preferably 80 ° C. or lower, and then heated at 100 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 250 ° C. or lower. This can be obtained while proceeding with the imidization reaction. Various catalysts may be used in the imidization reaction.

Examples of the organic solvent used when the hydroxyl-terminated etherimide oligomer is reacted include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide. Acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or p -Phenol solvents such as cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) D Ter), methyltriglyme (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxy) Ethane), ethyl diglyme (bis (2-ethoxyethyl) ether), symmetric glycol diethers such as butyl diglyme (bis (2-butoxyethyl) ether), methyl acetate, ethyl acetate, isopropyl acetate, n-propyl Acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)), diethylene glycol Acetates such as nobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, Propylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol phenyl Ether, dipropylene glycol dimethyl ether, 1,3 It dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, also possible to use diethylene glycol monobutyl ether or solvent ethers such as ethylene glycol monoethyl ether. If necessary, low-boiling hexane, acetone, toluene, xylene and the like can be used in combination. The solvent may be used alone or in combination of two or more.
Among them, symmetric glycol diethers are particularly preferable because of high solubility of oligomers.

The amount of the organic solvent used in the reaction is preferably such that the solute weight concentration in the reaction solution is 5 wt% or more and 80 wt% or less, more preferably 10 wt% or more and 60 wt% or less. Is 15% by weight or more and 50% by weight or less, whereby a uniform and transparent hydroxyl-terminated etherimide oligomer solution can be obtained. When the solution concentration is 5% by weight or less, the contact efficiency of each component is deteriorated, the reaction is difficult to occur, and the reaction rate may be reduced. When the solution concentration is 80% by weight or more, each component is not completely dissolved in the organic solvent, a uniform reaction does not occur, and a desired structural substance may not be obtained.
The hydroxyl-terminated etherimide oligomer produced as described above is preferable because it can be handled as a hydroxyl-terminated etherimide oligomer solution as it is in the reaction solution so that it can be easily handled in the next step and the reaction can proceed uniformly. .

<(A2) Polycarbonate diol>
The (a2) polycarbonate diol of the present invention is a diol compound having a repeating unit having a carbonate skeleton represented by the general formula (2). For example, alkylene such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,12-dodecanediol, etc. It can be obtained by reacting a diol alone or in combination of two or more with a carbonate compound such as dialkyl carbonate, alkylene carbonate or diphenyl carbonate.

  Further, the number average molecular weight of the polycarbonate diol is preferably in the range of 500 to 5000, more preferably 750 to 2500 in terms of polystyrene, whereby the chemical resistance and flexibility of the resulting polyimide resin can be improved. This is preferable. When the number average molecular weight is less than 500, the flexibility of the obtained polyimide resin is lowered, and when it is 5000 or more, the developability may be lowered.

  Examples of the polycarbonate diol include trade names PCDL T-4671, T-4672, T-4691, T-4692, T-5650J, T-5651, T-5562, T-6601, T manufactured by Asahi Kasei Chemicals Corporation. -6002, Daicel Chemical Industries, Ltd. trade name Plaxel CD CD205, CD205PL, CD205HL, CD210, CD210PL, CD210HL, CD220, CD220PL, CD220HL, Kuraray Co., Ltd. trade names Kuraray Polyol C-1015N, C-1050, C -1065N, C-1090, C-2015N, C-2065N, C-2090, those sold by Nippon Polyurethane Industry Co., Ltd. under the trade names NIPPOLAN 981, 980R, 982R, etc. Or it can be used in combination of two or more.

<(A3) Dihydroxycarboxylic acid compound>
The (a3) dihydroxycarboxylic acid compound of the present invention is a compound having a carboxyl group and two hydroxyl groups in the molecule, represented by the general formula (3). For example, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (2-hydroxyethyl) propionic acid, 2,2-bis (3-hydroxymepropyl) propionic acid, 2,3-dihydroxy-2 -Methylpropionic acid, 2,2-bis (hydroxymethyl) butanoic acid, 2,2-bis (2-hydroxyethyl) butanoic acid, 2,2-bis (3-hydroxypropyl) butanoic acid, 2,3-dihydroxy Butanoic acid, 2,4-dihydroxy-3,3-dimethylbutanoic acid, 2,3-dihydroxyhexadecanoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2 , 6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, etc., and these may be used alone or as 2 It can be used in combination of at least class. By using these dihydroxycarboxylic acid compounds, the developability of the polyimide resin is improved, and the solder heat resistance, chemical resistance, and electrical insulation reliability are improved because a three-dimensional cross-linked structure is formed by reaction with the thermosetting compound. .

<(A4) Compound having (meth) acryloyl group>
Examples of the compound having an isocyanate group and at least one (meth) acryloyl group in the molecule represented by (a4) general formula (4) of the present invention include 2- (meth) acryloyloxyethyl isocyanate, 1,1- (Bisacryloyloxymethyl) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate and the like can be mentioned, and these can be used alone or in combination of two or more. As a compound which has an isocyanate group and at least 1 (meth) acryloyl group in said molecule | numerator, what is marketed by Showa Denko Co., Ltd. brand name Karenz AOI, MOI, BEI, EG is mentioned, for example. By using a compound having an isocyanate group and at least one (meth) acryloyl group in these molecules, the photosensitivity and chemical resistance of the polyimide resin are improved.

  Examples of the compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule represented by (a4) general formula (5) of the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meta) ) Acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, o-phenylphenol glycidyl ether (meth) acrylate, Polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4- Examples include droxyphenyl (meth) acrylate, 2- (4-hydroxyphenyl) ethyl (meth) acrylate, N-methylol acrylamide, 3,5-dimethyl-4-hydroxybenzyl acrylamide, and the like. The above can be used in combination. By using a compound having a hydroxyl group and at least one (meth) acryloyl group in these molecules, the photosensitivity and chemical resistance of the polyimide resin are improved.

<(A5) Diisocyanate compound>
The (a5) diisocyanate compound of the present invention is a compound having two isocyanate groups in the molecule represented by the general formula (6). For example, aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, tetramethylxylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, etc. Aliphatic diisocyanates such as alicyclic diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, and the like can be used alone or in combination of two or more. Among these diisocyanate compounds, preferably, tolylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate is used to improve the heat resistance and electrical insulation reliability of the resulting polyimide resin.

<(A) Ratio of components of polyimide resin>
The polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain of the present invention and having a developing group at least in the side chain and a photosensitive group at the terminal end of the main chain is at least (a1) a hydroxyl group Terminal etherimide oligomer, (a2) polycarbonate diol, (a3) dihydroxycarboxylic acid compound, (a4) (compound having an isocyanate group and at least one (meth) acryloyl group in the molecule) and / or (a hydroxyl group in the molecule) A compound having at least one (meth) acryloyl group) and (a5) a diisocyanate compound. The blending molar ratio of the components (a1), (a2), (a3), (a4), and (a5) is the same as the number of moles (a1), (a2), (a3), (a4), and ( In the case of a5), preferably, [(a1) + (a2) + (a3)] / [(a4) + (a5)] = 0.5 to 1.5, more preferably 0.75 to 1.25, particularly preferably 0.9 to 1.1.

  By controlling the addition amount within the above range and reacting, it is preferable because the molecular weight of the polyimide resin can be controlled within the optimum range. When it is smaller than 0.5 or larger than 1.5, a large amount of unreacted substances remain in the system, so that when used in the photosensitive resin composition, heat resistance and electrical insulation reliability may be lowered. is there.

  At this time, preferably, [(a1) + (a2)] / (a3) = 0.1 to 5.0, more preferably 0.2 to 3.0, and particularly preferably 0.3 to By reacting within the range of 2.0, it is preferable in order to balance the heat resistance, electrical insulation reliability, flexibility, and developability of the polyimide resin. If it is smaller than 0.1, the heat resistance, electrical insulation reliability and flexibility of the polyimide resin are lowered, and if it is larger than 5.0, the developability of the polyimide resin may be lowered.

  (A) The polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain of the present invention, a developing group at least in the side chain, and a photosensitive group at the terminal of the main chain is represented by the general formula (1). A residue obtained by removing two hydroxyl groups from the hydroxyl group-terminated etherimide oligomer shown, a residue obtained by removing two hydroxyl groups from a polycarbonate diol represented by the general formula (2), and a dihydroxy compound represented by the general formula (3) A residue obtained by removing two hydroxyl groups from a carboxylic acid compound and a residue obtained by removing two isocyanate groups from a diisocyanate compound represented by the general formula (6) are contained as repeating units in the main chain skeleton. Isocyanate from a compound having an isocyanate group and at least one (meth) acryloyl group in the molecule represented by (4) A copolymer having a terminal and a residue from which a hydroxyl group has been removed from a compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule represented by the general formula (5), The repeating unit in the main chain skeleton may be random copolymerization or block copolymerization.

<(A) Production method of polyimide resin>
(A) The method for producing a polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain of the present invention, a developing group at least in the side chain, and a photosensitive group at the main chain terminal is first described above. (A1) A hydroxyl group-terminated etherimide oligomer solution is produced, then (a2) a polycarbonate diol, (a3) a dihydroxycarboxylic acid compound, and (a4) a compound having an isocyanate group and at least one (meth) acryloyl group in the molecule And / or a method in which a compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule and (a5) a diisocyanate compound are simultaneously charged in a reaction vessel and reacted in an organic solvent, or the above (a1) hydroxyl-terminated ether Manufacture imide oligomer solution, then contains hydroxyl group Min was charged into a reaction vessel, while stirring in an organic solvent, but a method of reacting while dropwise component containing an isocyanate group, but are not limited to these methods. The reaction temperature at this time is preferably 50 ° C. or higher and 120 ° C. or lower, more preferably 60 ° C. or higher and 110 ° C. or lower, and particularly preferably 70 ° C. or higher and 100 ° C. or lower.

  It is preferable to control the reaction temperature within the above range because the molecular weight of the polyimide resin can be controlled to an optimal range. When the reaction temperature is 50 ° C. or lower, the reaction is difficult to proceed, the reaction time is prolonged, and the isocyanate group may be deactivated. When the reaction temperature is 120 ° C. or higher, the reaction is three-dimensional. There is a case where the crosslinking reaction proceeds and gelation occurs.

  At this time, the reaction can be carried out using the organic solvent added when the hydroxyl group-terminated etherimide oligomer solution is produced, or an organic solvent can be added and reacted.

As an organic solvent, the organic solvent illustrated at the time of the synthesis | combination of a hydroxyl-terminated etherimide oligomer can be used, for example. Among them, symmetric glycol diethers are particularly preferable because of high solubility of oligomers.
The amount of the organic solvent used in the reaction is preferably such that the solute weight concentration in the reaction solution is 20 wt% or more and 80 wt% or less, more preferably 30 wt% or more and 70 wt% or less. The viscosity of the resulting polyimide resin solution at 25 ° C. (E-type rotational viscometer) is 1000 mPa. s to 100,000 mPa.s Since it can control to the range of s, it is preferable. When the solution concentration is 20% by weight or less, the viscosity of the photosensitive resin composition obtained by blending this polyimide resin becomes low. When the solution concentration is 80% by weight or more, this polyimide resin is blended. In any case, it may be difficult to apply the photosensitive resin composition obtained on a substrate such as a printed wiring board.

  In the reaction, the (meth) acryloyl group of a compound having an isocyanate group and at least one (meth) acryloyl group in the molecule and / or a compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule For the purpose of preventing the thermal polymerization reaction, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether may be added.

  Furthermore, you may use the catalyst (Tin type | system | group, tertiary amine type | system | group) for promoting reaction as needed.

<(A) Polyimide resin having a photosensitive group introduced into the side chain>
The polyimide resin having an etherimide skeleton, a polycarbonate skeleton, and a urethane bond in the main chain of the present invention and having a developing group at least in the side chain and a photosensitive group at the terminal end of the main chain is at least (a1) a hydroxyl group A terminal etherimide oligomer, (a2) a polycarbonate diol, (a3) a dihydroxycarboxylic acid compound, (a4) a compound having an isocyanate group and at least one (meth) acryloyl group in the molecule, and / or a hydroxyl group in the molecule. A compound having at least one (meth) acryloyl group, and (a5) a polyimide resin obtained by reacting a diisocyanate compound (a6) a compound having an epoxy group and at least one (meth) acryloyl group in the molecule; And (a7) a polybasic acid anhydride can be reacted. That. This means that the carboxyl group of the side chain of the polyimide resin reacts with the epoxy group of the compound having at least one (meth) acryloyl group in the molecule, and a photosensitive group can be introduced into the side chain. Furthermore, it becomes possible to improve the photosensitivity of the polyimide resin. Furthermore, by introducing a secondary hydroxyl group produced by the reaction between a carboxyl group on the side chain of the polyimide resin and an epoxy group and a polybasic acid anhydride, the carboxyl group is introduced into the side chain at a location away from the main chain. When the thermosetting compound reacts with this carboxyl group, it has a three-dimensional cross-linking structure, which not only improves solder heat resistance, chemical resistance, and electrical insulation reliability, but also increases the distance between cross-linking points. Therefore, curing shrinkage when the polyimide resin is cured is reduced.

  Examples of the compound (a6) having an epoxy group and at least one (meth) acryloyl group in the molecule of the present invention include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, and 3,4-epoxy. Examples thereof include cyclohexylmethyl (meth) acrylate and bisphenol A diglycidyl ether mono (meth) acrylate, and these can be used alone or in combination of two or more. Among these compounds having an epoxy group and at least one (meth) acryloyl group in the molecule, preferably a polyimide resin obtained by using glycidyl (meth) acrylate or 3,4-epoxycyclohexylmethyl (meth) acrylate This improves the photosensitivity and electrical insulation reliability.

  The compounding amount of the compound having an epoxy group and at least one (meth) acryloyl group in the molecule is preferably a functional group equivalent ratio (the epoxy of the compound having an epoxy group and at least one (meth) acryloyl group in the molecule). Group / carboxyl group of side chain of polyimide resin) = 0.2 to 0.8.

  It is preferable to react by controlling the addition amount within the above range because the photosensitivity and crosslink density of the polyimide resin can be controlled within the optimum range.

  The reaction temperature at this time is preferably 60 ° C. or higher and 130 ° C. or lower, more preferably 70 ° C. or higher and 120 ° C. or lower, and particularly preferably 80 ° C. or higher and 110 ° C. or lower.

  Controlling the reaction temperature within the above range is preferable because side reactions can be suppressed and the reaction can proceed promptly. When the reaction temperature is 60 ° C. or lower, the reaction does not proceed easily and the reaction time becomes longer. When the reaction temperature is 110 ° C. or higher, the three-dimensional crosslinking reaction proceeds during the reaction and gelation may occur. is there.

  Further, if necessary, a catalyst for promoting the reaction (tertiary amine, triphenylphosphine, etc.) may be used.

  Examples of the (a7) polybasic acid anhydride of the present invention include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexa Examples include dicarboxylic anhydrides such as hydrophthalic anhydride, aromatic polycarboxylic anhydrides such as trimellitic anhydride and pyromellitic dianhydride, and these are used alone or in combination of two or more. it can. Among these polybasic acid anhydrides, gelation associated with three-dimensional crosslinking due to side reactions can be suppressed by using a dicarboxylic acid anhydride.

  The blending amount of the polybasic acid anhydride is preferably a functional group equivalence ratio (an acid anhydride group of the polybasic acid anhydride / a carboxyl group of the side chain of the polyimide resin and at least one (meth) ) Hydroxyl group formed by reaction of a compound having an acryloyl group) = 0.6 to 1.1.

  It is preferable to react by controlling the addition amount within the above range because the developability and crosslink density of the polyimide resin can be controlled within the optimum range.

  The reaction temperature at this time is preferably 60 ° C. or higher and 150 ° C. or lower, more preferably 70 ° C. or higher and 140 ° C. or lower, and particularly preferably 80 ° C. or higher and 130 ° C. or lower.

  Controlling the reaction temperature within the above range is preferable because side reactions can be suppressed and the reaction can proceed promptly. When the reaction temperature is 60 ° C. or lower, the reaction does not proceed easily and the reaction time becomes longer. When the reaction temperature is 150 ° C. or higher, the three-dimensional crosslinking reaction proceeds during the reaction and gelation may occur. is there.

  Further, if necessary, a catalyst for promoting the reaction (tertiary amine, triphenylphosphine, etc.) may be used.

<Photosensitive compounds other than (B) and (A)>
In the present invention, (B) a photosensitive compound other than (A) having at least one photosensitive group in the molecule has at least one (meth) acryloyl group in the molecule, and (meta) ) A compound in which an acryloyl group reacts to form a chemical bond.

  For example, ethoxylated bisphenol A di (meth) acrylate, ethoxylated bisphenol F di (meth) acrylate, polyethylene glycol di (meth) acrylate (n = 2-30), polypropylene glycol di (meth) acrylate (n = 2-30) ), 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethoxylated totimethylolpropane tri (meth) acrylate, propoxylated totimi Propanetri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, ethoxylated pentathritol tetra (meth) acrylate, propoxylated pentathritol tetra (meth) acrylate, caprolactone-modified ditrimethylolpropane tetra (meth) acrylate, ethoxy Dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto. In particular, the number of repeating units of EO (ethylene oxide) contained in one molecule of ethoxylated di (meth) acrylate is preferably in the range of 2-50, more preferably in the range of 2-40. By using the EO repeating unit in the range of 2 to 50, the solubility in an aqueous developer typified by an alkaline aqueous solution is improved, and the development time is shortened. In addition, stress hardly remains in the cured film obtained by curing the photosensitive resin composition. For example, among printed wiring boards, when laminated on a flexible printed wiring board based on a polyimide resin, the printed wiring board warps. Features such as being able to be suppressed.

  In particular, it is preferable to use the EO-modified di (meth) acrylate in combination with a photosensitive compound having 3 or more (meth) acrylic groups in order to improve photosensitivity and developability.

  Further, 2-hydroxy-3-phenoxypropyl (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, ω-carboxy-polycaprolactone mono (meth) acrylate, (meth) acrylic acid dimer, pentaesitol tris and Those having a hydroxyl group or a carbonyl group in the molecular structure skeleton such as tetra (meth) acrylate are also preferably used.

  In addition, any photosensitive compound such as an epoxy (meth) acrylate resin, a polybasic acid anhydride-modified epoxy (meth) acrylate resin, a urethane (meth) acrylate resin, or a polyester (meth) acrylate resin may be used.

<(C) Photopolymerization initiator>
Examples of the (C) photopolymerization initiator in the present invention include benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether and 1-hydroxycyclohexyl phenyl ketone, and ketal compounds such as benzyl dimethyl ketal and benzyl diethyl ketal; , 2′-diethoxyacetophenone, 2,2′-dibutoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) ) Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methyl Acetophenone compounds such as propane, benzophenone, o Methyl benzoylbenzoate, 3,3′-dimethyl-4-methoxybenzophenone, [4- (methylphenylthio) phenyl] phenylmethane, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) ) Benzophenone compounds such as benzophenone and 4-methoxy-4′-dimethylaminobenzophenone, thioxanthone compounds such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and 2,4-diethylthioxanthone, ethyl-4-dimethylaminobenzoate Aminobenzoate compounds such as 2-ethylhexyl-4-dimethylaminobenzoate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- Α-aminoalkyl such as 4-morpholinophenyl) butanone-1,2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one Phenone compounds, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Phosphine oxide compounds such as trimethylpentylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6 -(2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) Muesuteru compounds, etc. These can be used alone or in combinations of two or more.

<(D) Thermosetting compound>
The (D) thermosetting compound in the present invention is a compound that generates a crosslinked structure by heating and functions as a thermosetting agent. Examples include, but are not limited to, epoxy resins, isocyanate compounds, block isocyanate compounds, oxetane compounds, and the like. The said thermosetting compound can be used individually or in combination of 2 or more types. Among these, it is preferable to use an epoxy resin and a blocked isocyanate compound. By containing a thermosetting compound, heat resistance can be imparted to a cured film obtained by curing the photosensitive resin composition, and adhesion to a conductor such as a metal foil or a circuit board can be imparted.

  The epoxy resin is a compound containing at least two epoxy groups in the molecule. For example, as a bisphenol A type epoxy resin, product names jER828, jER1001, jER1002, and ADEKA manufactured by Japan Epoxy Resin Co., Ltd. Adeka Resin EP-4100E, Adeka Resin EP-4300E, trade names RE-310S and RE-410S manufactured by Nippon Kayaku Co., Ltd., trade names Epicron 840S, Epicron 850S, Epicron 1050 and Epicron 7050 manufactured by Dainippon Ink, Inc. The product names Epototo YD-115, Epototo YD-127, Epototo YD-128, and bisphenol F type epoxy resins manufactured by Toto Kasei Co., Ltd. are trade names jER806 and jER8 manufactured by Japan Epoxy Resin Co. 7. Trade names Adeka Resin EP-4901E, Adeka Resin EP-4930, Adeka Resin EP-4950, manufactured by Adeka Co., Ltd., trade names RE-303S, RE-304S, RE-403S, RE-404S, manufactured by Nippon Kayaku Co., Ltd. Product names Epicron 830 and Epicron 835 manufactured by Nippon Ink Co., Ltd. Product names Epototo YDF-170, Epototo YDF-175S, Epototo YDF-2001, and Bisphenol S type epoxy resin manufactured by Toto Kasei Co., Ltd. Trade name Epiklon EXA-1514 manufactured by Japan, Hydrogenated bisphenol A type epoxy resin includes Japan Epoxy Resin Co., Ltd. trade names jERYX8000, jERYX8034, jERYL7170, ADEKA Co., Ltd. trade names Adeka Resin P-4080E, Dainippon Ink Co., Ltd. trade name Epicron EXA-7015, Toto Kasei Co., Ltd. trade name Epototo YD-3000, Epototo YD-4000D, biphenyl type epoxy resin, manufactured by Japan Epoxy Resin Co., Ltd. Trade names jERYX4000, jERYL6121H, jERYL6640, jERYL6677, trade names NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and phenoxy type epoxy resins include trade names jER1256, jER4250, jER4275 and naphthalene manufactured by Japan Epoxy Resins As the type epoxy resin, trade names “Epicron HP-4032”, “Epicron HP-4700”, “Epicron HP-4200” manufactured by Dainippon Ink Co., Ltd., “NC-” manufactured by Nippon Kayaku Co., Ltd. As 7000L, phenol novolac type epoxy resin, trade names jER152 and jER154 manufactured by Japan Epoxy Resin Co., Ltd., trade name EPPN-201-L manufactured by Nippon Kayaku Co., Ltd., trade name Epicron N- manufactured by Dainippon Ink Co., Ltd. 740, Epicron N-770, Toto Kasei Co., Ltd. trade name Epototo YDPN-638, Cresol novolac type epoxy resin, Nippon Kayaku Co., Ltd. trade names EOCN-1020, EOCN-102S, EOCN-103S, EOCN -104S, trade names manufactured by Dainippon Ink Co., Ltd. Epicron N-660, Epicron N-670, Epicron N-680, Epicron N-695, and Trisphenolmethane type epoxy resin are trade names of Nippon Kayaku Co., Ltd. EPPN-501H, EPP -501HY, EPPN-502H, dicyclopentadiene type epoxy resin, Nippon Kayaku Co., Ltd. trade name XD-1000, Dainippon Ink Co., Ltd. trade name Epicron HP-7200, amine type epoxy resin, Toto Kasei Co., Ltd. trade names Epototo YH-434, Epototo YH-434L, and flexible epoxy resins include trade names jER871, jER872, jERYL7175, jERYL7217, manufactured by Dainippon Ink, Inc. As the name Epicron EXA-4850, urethane-modified epoxy resin, trade names of Adeka Resin EPU-6, Adeka Resin EPU-73, Adeka Resin EPU-78-11 manufactured by ADEKA Corporation, and ADE Co., Ltd. as ADE Co., Ltd. Product names Adeka Resin EPR-4023, Adeka Resin EPR-4026, Adeka Resin EPR-1309, and chelate-modified epoxy resins manufactured by A include Adeka Resin EP-49-10, Adeka Resin EP-49-20, etc., manufactured by ADEKA Corporation. It is done.

  The blocked isocyanate compound is a compound that is inactive at room temperature, and is heated to dissociate a blocking agent such as oximes, diketones, phenols, caprolactams, and regenerate isocyanate groups. As the hexamethylene diisocyanate block isocyanate, trade names Duranate 17B-60PX, Duranate TPA-B80E, Duranate MF-B60X, Duranate MF-K60X, Duranate E402-B80T manufactured by Asahi Kasei Chemicals Co., Ltd. Name Takenate B-830, Takenate B-815N, Takenate B-846N, Takenate B-882N, trade names of Nippon Polyurethane Industry Co., Ltd. Coronate AP-M, Coronate 2503, Co Sulfonates 2507, Coronate 2513, Coronate 2515, include Millionate MS-50 and the like.

  Although it does not specifically limit as a hardening | curing agent of the said thermosetting compound in the photosensitive resin composition of this invention, For example, phenol resins, such as a phenol novolak resin, a cresol novolak resin, a naphthalene type phenol resin, an amino resin, and a urea resin , Melamine, dicyandiamide and the like, and these can be used alone or in combination of two or more.

  Further, the curing accelerator is not particularly limited, but for example, phosphine compounds such as triphenylphosphine; amine compounds such as tertiary amine, trimethanolamine, triethanolamine and tetraethanolamine; 1,8- Borate compounds such as diaza-bicyclo [5,4,0] -7-undecenium tetraphenylborate, imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-un Imidazoles such as decylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole; 2-methylimidazoline, 2- Ethyl imidazoline, 2 Imidazolines such as isopropylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; 2,4-diamino-6- [2′-methylimidazolyl- ( 1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2 ′ Examples include azine-based imidazoles such as -ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, and these can be used alone or in combination of two or more.

<Photosensitive resin composition>
The blending amount of the component (A), the component (B), the component (C), and the component (D) in the photosensitive resin composition of the present invention is preferably (B) with respect to 100 parts by weight of the component (A). The component is 5 to 500 parts by weight, the component (C) is 0.1 to 20 parts by weight, and the component (D) is 0.5 to 100 parts by weight.

By mix | blending in the said range, the photosensitivity of the photosensitive resin composition, the heat resistance of a cured film, chemical resistance, a softness | flexibility, and electrical insulation reliability improve.
When the component (A) has a blending amount within the above range, the photosensitivity of the photosensitive resin composition, the solubility in an aqueous developer typified by an alkaline aqueous solution is lowered, and the heat resistance and flexibility of the cured film are reduced. , Chemical resistance, and electrical insulation reliability may be reduced. In addition, when the blending amount is in the above range or more, when the photosensitive resin composition is applied onto a substrate such as a printed wiring board and dried, stickiness of the coating film after drying occurs, Contamination and cracking of the coating film may occur. Therefore, by setting the addition amount within the above range, it becomes possible to adjust various characteristics of the photosensitive resin composition to an optimal range.
When the blending amount of the component (B) is not more than the above range, it may be difficult to obtain contrast when the photosensitive resin composition is exposed and developed. Moreover, in the case of the compounding quantity more than the said range, the coating film after exposure of the photosensitive resin composition will become weak, and a crack may generate | occur | produce. Therefore, by making the addition amount within the above range, it becomes possible to adjust the resolution and the suitability of the production process of the photosensitive resin composition to an optimum range.
When the amount of component (C) is not more than the above range, the curing reaction of the photosensitive compound during light irradiation hardly occurs and curing may be insufficient. Moreover, in the case of the compounding quantity more than the said range, the hardening reaction of the photosensitive compound at the time of light irradiation may progress too much, and may be in an overexposed state. Therefore, it becomes possible to advance the photocuring reaction of the photosensitive resin composition efficiently by making the addition amount within the above range.
When the component (D) has a blending amount not more than the above range, the heat resistance, flexibility, chemical resistance and electrical insulation reliability of the cured film of the photosensitive resin composition may be lowered. In addition, when the blending amount is in the above range or more, when the photosensitive resin composition is applied onto a substrate such as a printed wiring board and dried, the thermosetting reaction is accelerated during drying, and is typically represented by an alkaline aqueous solution. In some cases, the solubility in an aqueous developer is reduced. Therefore, by making the addition amount within the above range, the thermosetting reaction of the photosensitive resin composition is controlled and the heat resistance, chemical resistance and electrical insulation reliability of the cured film of the photosensitive resin composition are improved. Is possible.

  In the photosensitive resin composition of the present invention, an inorganic filler can be used for the purpose of improving the adhesion and the hardness of the cured film. The inorganic filler is not particularly limited, and examples thereof include barium sulfate, barium titanate, talc, ultrafine anhydrous silica, synthetic silica, natural silica, calcium carbonate, magnesium carbonate, aluminum oxide, aluminum hydroxide and the like. These can be used alone or in combination of two or more.

  In the photosensitive resin composition of the present invention, additives such as an antifoaming agent, a leveling agent, a flame retardant, a colorant, an adhesion imparting agent, and a polymerization inhibitor can be used as necessary. These additives are not particularly limited. For example, as an antifoaming agent, a silicon compound, an acrylic compound, as a leveling agent, a silicon compound, an acrylic compound, and as a flame retardant, a phosphate ester Compounds, phosphazene compounds, colorants include phthalocyanine compounds, azo compounds, carbon black, titanium oxide, and adhesion promoters include silane coupling agents, triazole compounds, tetrazole compounds, triazine compounds, polymerization Examples of the inhibitor include hydroquinone and hydroquinone monomethyl ether, and these can be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention is highly soluble in various organic solvents, such as sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide systems such as N, N-dimethylformamide and N, N-diethylformamide. Solvents, acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or Phenolic solvents such as p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolactone, methylmonoglyme (1,2-dimethoxyethane), methyldiglyme (bis (2-methoxyether) ) Ether), Methyl Trigura (1,2-bis (2-methoxyethoxy) ethane), methyltetraglyme (bis [2- (2-methoxyethoxyethyl)] ether), ethyl monoglyme (1,2-diethoxyethane), ethyldigig Symmetric glycol diethers such as lime (bis (2-ethoxyethyl) ether), butyldiglyme (bis (2-butoxyethyl) ether), γ-butyrolactone, N-methyl-2-pyrrolidone, methyl acetate, ethyl acetate , Isopropyl acetate, n-propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate (also known as carbitol acetate, 2- (2-butoxyethoxy) ethyl acetate)) Acetates such as diethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, Dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripylene glycol n-propyl ether, propylene glycol Phenyl ether, dipropylene glycol Methyl ether, 1,3-dioxolane, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, a solvent may be used ethers such as ethylene glycol monoethyl ether. If necessary, low-boiling hexane, acetone, toluene, xylene and the like can be used in combination.

  Among these, symmetric glycol diethers are particularly preferable because the solubility of the photosensitive resin composition is high.

  The amount of the organic solvent used in the photosensitive resin composition solution of the present invention is preferably 100 parts by weight of the total solid content of the component (A), the component (B), the component (C), and the component (D). The organic solvent is 10 parts by weight or more and 100 parts by weight or less.

  By adjusting the solid content of the photosensitive resin composition solution within the above range, the viscosity of the photosensitive resin composition can be controlled within the optimum range when coating, and the film thickness after coating and drying is reduced. The rate is reduced.

  The photosensitive resin composition of the present invention is obtained by uniformly mixing the components (A) to (D). As a method of uniformly mixing, for example, a general kneading apparatus such as a three roll or bead mill apparatus may be used for mixing. Moreover, when the viscosity of a solution is low, you may mix using a general stirring apparatus.

  After preparing the photosensitive resin composition of the present invention directly or after preparing the photosensitive resin composition solution, a pattern can be formed as follows. First, the photosensitive resin composition is applied onto a substrate and dried to remove the organic solvent. The substrate can be applied by screen printing, roller coating, curtain coating, spray coating, spin coating using a spinner, or the like. The coating film (preferably having a thickness of 5 to 100 μm) is dried at 120 ° C. or less, preferably 40 to 100 ° C. After drying, a negative photomask is placed on the dried coating film and irradiated with actinic rays such as ultraviolet rays, visible rays, and electron beams. Next, the pattern can be obtained by washing the unexposed portion with a developing solution using various methods such as shower, paddle, dipping or ultrasonic waves. Since the time until the pattern is exposed varies depending on the spray pressure and flow velocity of the developing device and the temperature of the developer, it is preferable to find the optimum device conditions as appropriate.

  As the developer, an aqueous alkali solution is preferably used. The developer is water-soluble such as methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone and the like. An organic solvent may be contained. Examples of the alkaline compound that gives the alkaline aqueous solution include hydroxides, carbonates, hydrogen carbonates, amine compounds, and the like of alkali metals, alkaline earth metals, or ammonium ions, specifically sodium hydroxide. , Potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium Hydroxide, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylethanolamine, triethanolamine, triisopropanolamine, trii Propylamine and the like, aqueous solution compound other than this as long as it exhibits basicity can also be used. The concentration of the alkaline compound that can be suitably used in the development step of the photosensitive resin composition of the present invention is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight. Further, the temperature of the developer depends on the composition of the photosensitive resin composition and the composition of the developer, and is generally 0 ° C. or higher and 80 ° C. or lower, more generally 20 ° C. or higher and 50 ° C. or lower. It is preferable to use it.

  The pattern formed by the development step is rinsed to remove unnecessary developer residue. Examples of the rinsing liquid include water and acidic aqueous solutions.

  Next, a cured film rich in heat resistance can be obtained by performing a heat curing treatment. Although a cured film is determined in consideration of wiring thickness etc., it is preferable that thickness is about 2-50 micrometers. The final curing temperature at this time is desired to be cured by heating at a low temperature for the purpose of preventing oxidation of the wiring and the like and not reducing the adhesion between the wiring and the substrate. The heat curing temperature at this time is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and particularly preferably 130 ° C. or higher and 190 ° C. or lower. When the final heating temperature becomes high, the wiring may be oxidized and deteriorated.

  A pattern comprising a cured film formed from the photosensitive resin composition of the present invention is excellent in heat resistance, electrical and mechanical properties, and is particularly excellent in flexibility. For example, the insulating film of the present invention preferably has a thickness of about 2 to 50 μm and a resolution of at least 10 μm after photocuring, and particularly a resolution of about 10 to 1000 μm. For this reason, the insulating film of the present invention is particularly suitable as an insulating material for a high-density flexible substrate. Furthermore, it is used for various photo-curing type wiring coating protective agents, photosensitive heat-resistant adhesives, electric wire / cable insulation coatings, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Synthesis Example 1)
In a reaction vessel, 14.58 g (0.028 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3.42 g (0.056 mol) of 2-aminoethanol, The mixture was charged into 72 g of 2-bis (2-methoxyethoxy) ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. The solution was cooled to room temperature, and polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0. 135 mol), 51.56 g (0.250 mol) of norbornene diisocyanate, 7.76 g (0.050 mol) of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK), 1,2-bis (2-methoxy) Ethoxy) ethane (49.55 g), dibutyltin dilaurate (0.182 g), and hydroquinone monomethyl ether (0.182 g) were added, and the mixture was heated to 80 ° C. under an air stream and stirred uniformly for 5 hours. Thus, a polyimide resin solution (number average molecular weight was 14700 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 61% by weight, and the viscosity of the solution was 160 poise at 23 ° C. This synthetic resin is abbreviated as resin A.

(Synthesis Example 2)
In a reaction vessel, 8.69 g (0.028 mol) of 3,3 ′, 4,4′-oxydiphthalic dianhydride and 3.42 g (0.056 mol) of 2-aminoethanol were mixed with 1,2-bis (2-methoxyethoxy). ) 48.44 g of ethane was added, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. The solution was cooled to room temperature, and polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0. 135 mol), 51.56 g (0.250 mol) of norbornene diisocyanate, 7.76 g (0.050 mol) of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK), 1,2-bis (2-methoxy) Ethoxy) ethane (69.18 g), dibutyltin dilaurate (0.176 g), and hydroquinone monomethyl ether (0.176 g) were added, and the mixture was heated to 80 ° C. under an air stream and stirred uniformly for 5 hours. Thus, a polyimide resin solution (number average molecular weight was 15600 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 61% by weight, and the viscosity of the solution was 170 poise at 23 ° C. This synthetic resin is abbreviated as resin B.

(Synthesis Example 3)
In a reaction vessel, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride 40.42 g (0.078 mol), 1,3-bis (3-aminophenoxy) benzene 11.35 g (0.039 mol) and 4.75 g (0.078 mol) of 2-aminoethanol were added to 131.88 g of 1,2-bis (2-methoxyethoxy) ethane, and the temperature was raised to 130 ° C. under a nitrogen stream. Stirred uniformly over time. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. The solution was cooled to room temperature, and polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0. 135 mol), 51.56 g (0.250 mol) of norbornene diisocyanate, 7.76 g (0.050 mol) of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK), 1,2-bis (2-methoxy) Ethoxy) ethane (15.35 g), dibutyltin dilaurate (0.221 g) and hydroquinone monomethyl ether (0.221 g) were added, and the mixture was heated to 80 ° C. under an air stream and stirred uniformly for 5 hours. Thus, a polyimide resin solution (number average molecular weight was 13900 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 61% by weight, and the viscosity of the solution was 150 poise at 23 ° C. This synthetic resin is abbreviated as resin C.

(Synthesis Example 4)
In a reaction vessel, 14.58 g (0.028 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3.42 g (0.056 mol) of 2-aminoethanol, The mixture was charged into 72 g of 2-bis (2-methoxyethoxy) ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. This solution was cooled to room temperature, polycarbonate diol (Asahi Kasei Chemicals Corporation, trade name PCDL T5651, number average molecular weight: 1000) 42.5 g (0.0425 mol), polyoxyalkylene diol (Asahi Kasei Fibers Corporation, trade name) PTXG1000, number average molecular weight: 1000) 42.5 g (0.0425 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0.135 mol), norbornene diisocyanate 51.56 g (0.250 mol), 2-methacryloyloxy Ethyl isocyanate (made by Showa Denko KK, trade name Karenz MOI) 7.76 g (0.050 mol), 1,2-bis (2-methoxyethoxy) ethane 49.55 g, dibutyltin dilaurate 0.182 g, hydroquinone monomethyl ester Was charged ether 0.182 g, was 5 hours uniformly stirred by heating to 80 ° C. under an air stream. Thus, a polyimide resin solution (number average molecular weight was 14500 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 61% by weight, and the viscosity of the solution was 150 poise at 23 ° C. This synthetic resin is abbreviated as resin D.

(Synthesis Example 5)
In a reaction vessel, 14.58 g (0.028 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3.42 g (0.056 mol) of 2-aminoethanol, The mixture was charged into 72 g of 2-bis (2-methoxyethoxy) ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. The solution was cooled to room temperature, and polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0. 135 mol), norbornene diisocyanate 51.56 g (0.250 mol), 1,1- (bisacryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko KK, trade name Karenz BEI) 11.96 g (0.050 mol), 1,2 -46.75 g of bis (2-methoxyethoxy) ethane, 0.178 g of dibutyltin dilaurate and 0.178 g of hydroquinone monomethyl ether were added, and the mixture was heated to 80 ° C. under an air stream and stirred uniformly for 5 hours. Thus, a polyimide resin solution (number average molecular weight was 15200 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 61% by weight, and the viscosity of the solution was 160 poise at 23 ° C. This synthetic resin is abbreviated as Resin E.

(Synthesis Example 6)
In a reaction vessel, 14.58 g (0.028 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3.42 g (0.056 mol) of 2-aminoethanol, The mixture was charged into 72 g of 2-bis (2-methoxyethoxy) ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. The solution was cooled to room temperature, and polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0. 135 mol), 61.87 g (0.300 mol) of norbornene diisocyanate, 6.51 g (0.050 mol) of 2-hydroxyethyl methacrylate, 55.59 g of 1,2-bis (2-methoxyethoxy) ethane, 0.191 g of dibutyltin dilaurate Then, 0.191 g of hydroquinone monomethyl ether was added, and the mixture was heated to 80 ° C. under an air stream and stirred uniformly for 5 hours. In this way, a polyimide resin solution (number average molecular weight was 14800 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 61% by weight, and the viscosity of the solution was 160 poise at 23 ° C. This synthetic resin is abbreviated as resin F.

(Synthesis Example 7)
In a reaction vessel, 14.58 g (0.028 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3.42 g (0.056 mol) of 2-aminoethanol, The mixture was charged into 72 g of 2-bis (2-methoxyethoxy) ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. The solution was cooled to room temperature, and polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0. 135 mol), 61.87 g (0.300 mol) of norbornene diisocyanate, 9.90 g (0.050 mol) of 1,4-cyclohexanedimethanol monoacrylate, 57.85 g of 1,2-bis (2-methoxyethoxy) ethane, dibutyltin 0.195 g of dilaurate and 0.195 g of hydroquinone monomethyl ether were added, and the mixture was heated to 80 ° C. under an air stream and stirred uniformly for 5 hours. In this way, a polyimide resin solution (number average molecular weight was 15000 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 61% by weight, and the viscosity of the solution was 160 poise at 23 ° C. This synthetic resin is abbreviated as resin G.

(Synthesis Example 8)
In a reaction vessel, 14.58 g (0.028 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3.42 g (0.056 mol) of 2-aminoethanol, The mixture was charged into 72 g of 2-bis (2-methoxyethoxy) ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. The solution was cooled to room temperature, and polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0. 135 mol), 51.56 g (0.250 mol) of norbornene diisocyanate, 7.76 g (0.050 mol) of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK), 1,2-bis (2-methoxy) Ethoxy) ethane (49.55 g), dibutyltin dilaurate (0.182 g), and hydroquinone monomethyl ether (0.182 g) were added, and the mixture was heated to 80 ° C. under an air stream and stirred uniformly for 5 hours. The solution was cooled to room temperature, charged with 7.68 g (0.054 mol) of glycidyl methacrylate and 0.547 g of triphenylphosphine, heated to 100 ° C. under an air stream, and uniformly stirred for 5 hours. The solution was cooled to room temperature, charged with 6.57 g (0.043 mol) of tetrahydrophthalic anhydride, heated to 100 ° C. under an air stream, and stirred uniformly for 3 hours. In this way, a polyimide resin solution (number average molecular weight was 15800 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 63% by weight, and the viscosity of the solution was 170 poise at 23 ° C. This synthetic resin is abbreviated as resin H.

(Synthesis Example 9)
In a reaction vessel, 14.58 g (0.028 mol) of 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 3.42 g (0.056 mol) of 2-aminoethanol, The mixture was charged into 72 g of 2-bis (2-methoxyethoxy) ethane, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. The solution was cooled to room temperature, and polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name: PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) butanoic acid 20 g (0. 135 mol), 51.56 g (0.250 mol) of norbornene diisocyanate, 7.76 g (0.050 mol) of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK), 1,2-bis (2-methoxy) Ethoxy) ethane (49.55 g), dibutyltin dilaurate (0.182 g), and hydroquinone monomethyl ether (0.182 g) were added, and the mixture was heated to 80 ° C. under an air stream and stirred uniformly for 5 hours. The solution was cooled to room temperature, charged with 10.59 g (0.054 mol) of 3,4-epoxycyclohexylmethyl methacrylate (trade name Cyclomer M100, manufactured by Daicel Chemical Industries, Ltd.) and 0.547 g of triphenylphosphine, and air The temperature was raised to 100 ° C. under an air stream, and uniform stirring was performed for 5 hours. The solution was cooled to room temperature, charged with 6.57 g (0.043 mol) of tetrahydrophthalic anhydride, heated to 100 ° C. under an air stream, and stirred uniformly for 3 hours. In this way, a polyimide resin solution (number average molecular weight was 16000 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 63% by weight, and the viscosity of the solution was 170 poise at 23 ° C. This synthetic resin is abbreviated as Resin I.

(Synthesis Example 10)
In a reaction vessel, 8.23 g (0.028 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and 3.42 g (0.056 mol) of 2-aminoethanol were added to 1,2-bis (2- Methoxyethoxy) ethane was charged in 72 g, heated to 130 ° C. under a nitrogen stream, and stirred uniformly for 1 hour. Next, the temperature was raised to 180 ° C. and heated under reflux for 2 hours to carry out an imidization reaction. At this time, the reactive organism was not dissolved in 1,2-bis (2-methoxyethoxy) ethane and was obtained as a precipitate. This precipitate was collected by filtration and dried under reduced pressure to obtain 11.50 g of a hydroxyl group-terminated imide oligomer powder.

  11.50 g of the above hydroxyl group-terminated imide oligomer powder synthesized in the reaction vessel, polycarbonate diol (manufactured by Asahi Kasei Chemicals Corporation, trade name PCDL T5651, number average molecular weight: 1000) 85 g (0.085 mol), 2,2-bis (hydroxymethyl) ) Butanoic acid 20 g (0.135 mol), norbornene diisocyanate 51.56 g (0.250 mol), 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name Karenz MOI) 7.76 g (0.050 mol), 1, 2-bis (2-methoxyethoxy) ethane (117.21 g), dibutyltin dilaurate (0.176 g), and hydroquinone monomethyl ether (0.176 g) were added, and the mixture was heated to 80 ° C. in an air stream and stirred uniformly for 5 hours. In this way, a polyimide resin solution (number average molecular weight was 14000 in terms of polyethylene glycol) was obtained. The solid content concentration of this solution was 61% by weight, and the viscosity of the solution was 150 poise at 23 ° C. This synthetic resin is abbreviated as Resin J.

(Examples 1-11, Comparative Example 1)
A photosensitive compound, a photopolymerization initiator, a thermosetting compound, and an organic solvent were added to the polyimide resins obtained in Synthesis Examples 1 to 10 to prepare a photosensitive resin composition. The compounding amount and the kind of raw material in the resin solid content of each constituent raw material are described in Tables 1-3. In addition, 1,2-bis (2-methoxyethoxy) ethane which is a solvent in the table is the total amount of solvent including the solvent and the like contained in the above synthetic resin solution and the like.

  The photosensitive resin composition was first mixed with a general stirring device equipped with a stirring blade, and the solution was passed twice with a three-roll mill to obtain a uniform solution. When the particle diameter was measured with a grindometer, all were 10 μm or less. The following evaluation was carried out by completely defoaming the foam in the solution with a defoaming device. The evaluation results are shown in Tables 4-5.

(Preparation of coating film on polyimide film)
The above photosensitive resin composition was cast and applied to an area of 100 mm × 100 mm on a 75 μm polyimide film (manufactured by Kaneka Corporation: trade name 75 NPI) using a Baker type applicator so that the final dry thickness was 25 μm. After drying at 80 ° C. for 20 minutes, a negative photomask having a line width / space width of 50 mm × 50 mm = 100 μm / 100 μm was placed and exposed to UV light at 300 mJ / cm 2 under reduced pressure for exposure. This photosensitive film was spray-developed for 90 seconds at a discharge pressure of 1.0 kgf / mm 2 using a solution in which a 1.0 wt% sodium carbonate aqueous solution was kept at 30 ° C. After the development, the film was washed purely and sufficiently, and then dried by heating in an oven at 150 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

(Photosensitive)
The evaluation of the photosensitivity of the photosensitive resin composition was determined by observing the surface of the cured film obtained in the above item (Preparation of coating film on polyimide film).
◯: Clear line width / space width = 100/100 μm photosensitive pattern is drawn on the polyimide film surface, no line shaking occurs due to peeling of the line part, and there is no residual residue in the space part thing.
Δ: A clear photosensitive pattern having a line width / space width = 100/100 μm is drawn, and the line portion is shaken due to peeling, but there is no undissolved residue in the space portion.
×: Clear line width / space width = 100/100 μm photosensitive pattern is not drawn, and dissolution residue is generated in the space portion.

(Coating film adhesion)
The adhesive strength of the cured film of the photosensitive resin composition obtained in the above item (Preparation of coating film on polyimide film) was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Solvent resistance)
The solvent resistance of the cured film of the photosensitive resin composition obtained in the above item (preparation of coating film on polyimide film) was evaluated. In the evaluation method, the film was dipped in methyl ethyl ketone at 25 ° C. for 15 minutes and then air-dried, and the state of the film surface was observed.
○: There is no abnormality in the coating film.
X: Abnormality such as swelling or peeling occurs in the coating film.

(Flexibility)
A cured film laminated film of a photosensitive resin composition was prepared on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the above item (Preparation of a coating film on a polyimide film). The cured film laminated film was cut into a 30 mm × 10 mm strip, bent 10 times at 180 ° at 15 mm, and the coating film was visually confirmed to check for cracks.
○: The cured film has no cracks.
Δ: The cured film has some cracks.
X: The cured film has cracks.

(Warpage amount)
Using the Baker type applicator, the photosensitive resin composition was cast and applied to a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) to an area of 100 mm × 100 mm so that the final dry thickness was 25 μm. Dry at 80 ° C. for 20 minutes. The entire surface was exposed to 300 mJ / cm 2 of ultraviolet light under reduced pressure. This photosensitive film was spray-developed at a discharge pressure of 1.0 kgf / mm 2 using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. However, since the entire surface was exposed, no change in the film area was observed. After the development, the film was washed purely and sufficiently, and then dried by heating in an oven at 150 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

  The cured film was cut into a film having an area of 50 mm × 50 mm and placed on a smooth table so that the coating film was on the upper surface, and the warp height of the film edge was measured. A schematic diagram of the measurement site is shown in FIG. The smaller the amount of warpage on the polyimide film surface, the smaller the stress on the surface of the printed wiring board and the lower the amount of warping of the printed wiring board. The warp amount is preferably 5 mm or less.

(Solder heat resistance)
The photosensitive resin composition was cast and applied to an area of 100 mm × 100 mm on a 75 μm polyimide film (manufactured by Kaneka Corporation: trade name 75 NPI) using a Baker type applicator so that the final dry thickness was 25 μm. After drying at 80 ° C. for 20 minutes, a negative photomask having a line width / space width of 50 mm × 50 mm = 100 μm / 100 μm was placed and exposed to UV light at 300 mJ / cm 2 under reduced pressure for exposure. This photosensitive film was spray-developed at a discharge pressure of 1.0 kgf / mm 2 using a solution obtained by heating a 1.0 wt% sodium carbonate aqueous solution to 30 ° C. After the development, the film was washed purely and sufficiently, and then dried by heating in an oven at 150 ° C. for 60 minutes to prepare a cured film of the photosensitive resin composition.

The coated film was floated so that the surface coated with the cured film of the photosensitive resin composition was in contact with a solder bath completely dissolved at 260 ° C., and then pulled up 10 seconds later. The operation was performed three times, and the adhesive strength of the cured film was evaluated by a cross-cut tape method according to JIS K5400.
○: No peeling by cross-cut tape method.
Δ: 95% or more of the cells remain.
X: The remaining amount of the mesh is less than 80%.

(Insulation reliability)
A comb-shaped pattern of line width / space width = 100 μm / 100 μm on a flexible copper-laminated laminate (copper foil thickness 12 μm, polyimide film is Apical 25 NPI manufactured by Kaneka Corporation, and copper foil is bonded with a polyimide adhesive) After being prepared and immersed in a 10% by volume sulfuric acid aqueous solution for 1 minute, the surface of the copper foil was treated by washing with pure water. Then, the cured film of the photosensitive resin composition was produced on the comb pattern by the method similar to the production method of the cured film on a polyimide film, and the test piece was adjusted. A 100 V direct current was applied to both terminals of the test piece in an environmental test machine at 85 ° C. and 85% RH, and changes in the insulation resistance value and occurrence of migration were observed.
◯: A resistance value of 10 9 or more after 1000 hours from the start of the test and no occurrence of migration, dendrite, copper discoloration, etc.
X: The occurrence of migration, dendrite, discoloration of copper, etc. in 1000 hours or more after starting the test.

(Wettability)
A cured film laminated film of a photosensitive resin composition was prepared on the surface of a 25 μm-thick polyimide film (Apical 25NPI manufactured by Kaneka Corporation) in the same manner as the above item (Preparation of a coating film on a polyimide film). Using this cured film, the wettability of the coating film surface was evaluated according to JIS K6768. The better the wettability of the cured coating film surface, the higher the value of the wetting index and the better the adhesion with the sealant resin. The wetting index is preferably 36 or more.

(Comparative Example 2)
In a reaction vessel, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride 25.06 g (0.085 mol), N-methyl-2-pyrrolidone 108 g, hydroquinone 1.20 g, 4-methoxyhydroquinone 1.20 g And cooled with dry ice / methanol (−30 ° C.) while passing dry air, 3,5-diaminobenzoic acid ethyl methacrylate 6.00 g (0.023 mol), diaminopolysiloxane (Shin-Etsu Chemical) 54.0 g (0.062 mol) manufactured by Co., Ltd., trade name KF-8010) was added over 5 minutes, and the apparatus and the instrument were washed with 40 g of N-methyl-2-pyrrolidone. The outside was cooled and stirred uniformly at 25 ° C. for 30 hours to obtain a polyamic acid solution. Next, 472 g of NMP was added, the reaction solution was diluted, and while cooling the outside, 145.2 g of acetic anhydride and 62.2 g of pyridine were added at 25 ° C. over 10 minutes, and then at 20 ° C. The imidization reaction was performed by stirring overnight. The obtained imide resin solution was deposited in a 3 liter container containing 1.5 liters of methanol over 2 minutes using a disperser. The precipitate was collected using a filter paper (No. 3 Advantech) and washed with a small amount of methanol. After this operation was repeated three times, the filtrated product was vacuum dried (25 ° C., 15 hours) to obtain 85.5 g of a photosensitive polyimidesiloxane resin.

  After dissolving 30 g of the above-described photosensitive polyimidesiloxane resin in 45 g of NMP, 5.25 g of Aerosil (average particle size: about 0.02 μm), 12 g of talc (average particle size: 1.5 μm), 1-hydroxy-cyclohexyl phenyl ketone 6 .92 g, 6.92 g of 2-benzyl-1,2-dimethylamino-1- (4-morpholinophenyl) butane-1 was added and stirred. This mixture was kneaded with three rolls to obtain a photosensitive resin composition solution. The resulting photosensitive resin composition solution was completely defoamed with a defoaming apparatus and subjected to the same evaluation as in Examples 1-11. The evaluation results are shown in Table 6.

  The obtained cured film was poor in solvent resistance, and the wetting index on the surface of the cured coating film was very low. Furthermore, it was insoluble in the dilute alkaline aqueous solution of the developer during development.

(Comparative Example 3)
After introducing air into the reaction vessel, polycarbonate diol (manufactured by Daicel Chemical Industries, trade name: Plaxel CD205PL, number average molecular weight: 500) 196.8 g (0.394 mol), 2,2-bis (hydroxymethyl) butane Acid 58.3 (0.394 mol) g, diethylene glycol 37.6 g (0.353 mol), 1,4-cyclohexanedimethanol monoacrylate 148.1 (0.748 mol) g, p-methoxyphenol 0.55 g, dibutyltin 0.55 g of dilaurate and 110.2 g of methyl ethyl ketone were charged, and the temperature was raised to 65 ° C. with uniform stirring under an air stream. 305.9 g (1.457 mol) of trimethylhexamethylene diisocyanate was charged into the dropping vessel and dropped into the reaction vessel over 3 hours with uniform stirring at 65 ° C. After the completion of dropping, the dropping container was washed with 76.5 g of methyl ethyl ketone, and the washed solution was put into the reaction container as it was. Further, the mixture was kept warm for 2 hours with uniform stirring, then heated to 75 ° C. and stirred uniformly for 5 hours. Next, 9.3 g of methanol was added to the reaction vessel, and uniform stirring was performed at 60 ° C. for 30 minutes. Thereafter, 56.4 g of methyl ethyl ketone was added to obtain a transparent resin solution. This resin solution had a solid concentration of 75% by weight and a viscosity of 20 poise at 23 ° C.

  To 50 g of the resin solution, 0.25 g of 2,2-dimethoxy-2-phenylacetone was added and stirred. This mixture was kneaded with three rolls to obtain a photosensitive resin composition solution. The resulting photosensitive resin composition solution was completely defoamed with a defoaming apparatus and subjected to the same evaluation as in Examples 1-11. The evaluation results are shown in Table 6.

  The cured film obtained had poor solvent resistance and solder heat resistance, and the copper circuit was discolored black after the insulation reliability test.

(Comparative Example 4)
62.5 g of resin solution obtained in Comparative Example 3 (solid content 50 g), 30 g of 2,2′-bis (4-methacryloxypentaethoxyphenyl) propane, methacrylic acid / methyl methacrylate / butyl acrylate = 22/71 / 16 (weight ratio) copolymer dissolved in methyl cellosolve / toluene = 6/4 (weight ratio) solution to a solid content of 40% by weight (solid content: 65 g), benzophenone 5 g, 0.1 g of N, N′-tetraethyl-4,4′-diaminobenzophenone, blocked isocyanate compound (manufactured by Asahi Kasei Chemicals Corporation, trade name Duranate TPA-B80E, solid content 80% by weight) 18.75 g (solid content 15 g) ), Phosphoric ester-based flame retardant (trade name CR-747, manufactured by Daihachi Chemical Industry Co., Ltd.) 40 g and acetone 85 g were added and stirred. It was. This mixture was kneaded with three rolls to obtain a photosensitive resin composition solution. The resulting photosensitive resin composition solution was completely defoamed with a defoaming apparatus and subjected to the same evaluation as in Examples 1-11. The evaluation results are shown in Table 6.

  The resistance value after the insulation reliability test was 10 9 or less, the surface of the coating film became sticky due to the bleed-out of the flame retardant, migration occurred, and the copper circuit turned black.

(Comparative Example 5)
40.68 g of ethyl diglycol acetate, 22.20 g (0.1 mol) of isophorone diisocyanate, and 8.88 g (0.06 mol) of 2,2-bis (hydroxymethyl) butanoic acid are put into a reaction vessel, and the mixture is stirred under a nitrogen stream. The temperature was raised to 0 ° C. and uniform stirring was performed for 3 hours. Next, 9.60 g (0.05 mol) of trimellitic anhydride was added, the temperature was raised to 160 ° C., and the mixture was heated to reflux for 4 hours to carry out an imidization reaction. Next, 7.10 g (0.05 mol) of glycidyl methacrylate was added, and stirred uniformly at 100 ° C. for 5 hours to obtain an imide-urethane acrylate. Further, 6.84 g (0.045 mol) of tetrahydrophthalic anhydride was charged and stirred uniformly at 100 ° C. for 5 hours. The resulting resin solution had a solid content concentration of 56% by weight and a number average molecular weight of 5,500 in terms of polyethylene glycol.

  133.93 g of the above resin solution (solid content: 75 g), 25 g of cresol novolac type epoxy resin (trade name EOCN-104S, manufactured by Nippon Kayaku Co., Ltd.), 10 g of dipentaerythritol hexaacrylate, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one (5 g) and N, N-dimethylbenzylamine (1 g) were added and stirred. This mixture was kneaded with three rolls to obtain a photosensitive resin composition solution. The resulting photosensitive resin composition solution was completely defoamed with a defoaming apparatus and subjected to the same evaluation as in Examples 1-11. The evaluation results are shown in Table 6.

  The obtained cured film was poor in flexibility, and in the bendability test, a crack was generated by one folding. Furthermore, the amount of warping of the test piece after curing showed a value of 20 mm or more.

(Comparative Example 6)
A reaction vessel was charged with 58.8 g (0.20 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 30 g (0.40 mol) of 3-aminopropanol, and 200 g of dimethylacetamide under a nitrogen atmosphere. And stirred uniformly at 100 ° C. for 1 hour. Next, 50 g of toluene was added, the temperature was raised to 180 ° C., and the mixture was heated to reflux for 4 hours to remove water generated by imidization azeotropically with toluene. The reaction solution was poured into 2 liters of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 43.16 g of hydroxyl-terminated imide oligomer powder.

  In a reaction vessel, polycarbonate diol (Kuraray Co., Ltd., trade name Kuraray polyol C-2015 29.94 g (0.015 mol), 2,2-bis (hydroxymethyl) propionic acid 1.01 g (0.0075 mol), 4 , 4'-diphenylmethane diisocyanate (8.53 g, 0.034 mol) and isophorone (13.7 g) were charged and stirred uniformly in a nitrogen atmosphere for 1.5 hours at 80 ° C. Subsequently, the synthesized hydroxyl-terminated imide oligomer (6.13 g) ( 0.015 mol) and 31.9 g of isophorone were added and stirred uniformly for 1.5 hours at 80 ° C. The polyimide resin solution thus obtained (number average molecular weight was 26000 in terms of polyethylene glycol). The solid concentration was 50% by weight, and the solution viscosity was 600 poise at 23 ° C.

  200 g of the above polyimide resin solution (solid content is 100 g), 10 g of epoxy resin (manufactured by Daicel Chemical Industries, Ltd., trade name Epolide PB3600), 20 g of a blocked isocyanate compound (trade name Burnock D-550, manufactured by Dainippon Ink & Chemicals, Inc.) , 0.8 g of amine compound (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name Curezol 2E4MZ), 10 g of filler 1 (manufactured by Nippon Aerosil Co., Ltd., trade name Aerosil 130), filler 2 (manufactured by Nippon Aerosil Co., Ltd., trade name Aerosil 50) ) 5 g was added and stirred. This mixture was kneaded with three rolls to obtain a polyimide resin composition solution. The obtained polyimide resin composition solution was subjected to the same evaluation as in Examples 1 to 11 by completely defoaming bubbles in the solution with a defoaming apparatus. The evaluation results are shown in Table 6.

  The resulting polyimide resin composition did not exhibit photosensitivity and was insoluble in the dilute alkaline aqueous solution of the developer during development.

※１：新中村化学工業株式会社製、商品名ＮＫエステル ＢＰＥ−５００（エトキシ化ビスフェノールＡジメタクリレート、ＥＯ＝１０）
※２：日本化薬株式会社製、商品名ＫＡＹＡＲＡＤ ＺＡＲ−１４０１Ｈ（多塩基酸無水物変性エポキシアクリレート樹脂）
※３：チバスペシャルティケミカルズ製、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）ブタノン−１
※４：ジャパンエポキシレジン株式会社製、ビスフェノールＡ型エポキシ樹脂
※５：旭化成ケミカルズ株式会社製、商品名デュラネートＴＰＡ−Ｂ８０Ｅ（ヘキサメチレンジイソシアネート系ブロックイソシアネート化合物）
※６：日本アエロジル株式会社製、超微粒子状無水シリカ

* 1: Shin-Nakamura Chemical Co., Ltd., trade name: NK ester BPE-500 (ethoxylated bisphenol A dimethacrylate, EO = 10)
* 2: Product name KAYARAD ZAR-1401H (polybasic acid anhydride-modified epoxy acrylate resin) manufactured by Nippon Kayaku Co.
* 3: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 manufactured by Ciba Specialty Chemicals
* 4: Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin * 5: Asahi Kasei Chemicals Co., Ltd., trade name Duranate TPA-B80E (hexamethylene diisocyanate block isocyanate compound)
* 6: Nippon Aerosil Co., Ltd., ultrafine anhydrous silica

Schematic diagram measuring the amount of warping of the film

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyimide film which laminated the photosensitive resin composition 2 Warpage amount 3 Smooth stand

Claims (14)

(A) The main chain has an etherimide skeleton having an ether bond derived from a tetracarboxylic dianhydride having at least one ether bond in the molecule , a polycarbonate skeleton, and a urethane bond, and at least a side chain has a developing group. , A polyimide resin having a photosensitive group at the end of the main chain, (B) a photosensitive compound other than (A) having at least one photosensitive group in the molecule, (C) a photopolymerization initiator, and (D) thermosetting. A photosensitive resin composition comprising at least a compound.   The developing group of the (A) polyimide resin is a carboxyl group, and the photosensitive group of the (A) polyimide resin and (B) the photosensitive compound is a (meth) acryloyl group. Photosensitive resin composition. The (A) polyimide resin is at least (a1) a hydroxyl-terminated etherimide oligomer represented by the following general formula (1), (a2) a polycarbonate diol represented by the following general formula (2), (a3) the following general formula ( 3) dihydroxycarboxylic acid compound (a4) (compound having an isocyanate group and at least one (meth) acryloyl group in the molecule represented by the following general formula (4)) and / or (the following general formula (5) ), A compound having a hydroxyl group and at least one (meth) acryloyl group), and (a5) a diisocyanate compound represented by the following general formula (6). Item 3. The photosensitive resin composition according to Item 1 or 2.

(Wherein X represents a tetravalent organic group having at least one ether bond, Y represents a divalent organic group, and a plurality of R _{1 s} independently represent a divalent organic group. P represents It is an integer from 0 to 20.)

(In the formula, plural R _{2 s} each independently represent a divalent organic group. Q is an integer of 1 to 20.)

(In the formula, R ₃ represents at least a trivalent organic group.)

(In the formula, R ₄ represents a divalent organic group, R ₅ represents hydrogen or an alkyl group, and m is an integer of 1 to 3.)

(Wherein R ₆ represents a divalent organic group, R ₇ represents hydrogen or an alkyl group, and n is an integer of 1 to 3)

(Wherein R ₈ is a divalent organic group.) The (a1) hydroxyl group-terminated etherimide oligomer is at least represented by the following general formula (7) or the following general formula (8), a tetracarboxylic dianhydride having at least one ether bond in the molecule, and the following general formula 4. The photosensitive resin composition according to claim 3, which is obtained by reacting an amino alcohol represented by the formula (9).

(In the formula, R ₉ represents a divalent organic group.)

(In the formula, R ₁₀ is a divalent organic group.)   The (a1) hydroxyl group-terminated etherimide oligomer is in a molar ratio (number of moles of tetracarboxylic dianhydride having at least one ether bond in the molecule / number of moles of amino alcohol) = 0.25 to 0.75. The photosensitive resin composition according to claim 4, which is reacted within the range of The photosensitive resin composition according to claim 4, wherein the (a1) hydroxyl-terminated etherimide oligomer is obtained by further reacting with a diamino compound represented by the following general formula (10).

(In the formula, R ₁₁ is a divalent organic group.)   The (a1) hydroxyl-terminated etherimide oligomer is in a molar ratio of (number of moles of tetracarboxylic dianhydride having at least one ether bond in the molecule) / (number of moles of amino alcohol + number of moles of diamino compound). The photosensitive resin composition according to claim 6, which is obtained by reacting within a range of = 0.25 to 1.0.   The (A) polyimide resin has (a1) the number of moles of hydroxyl-terminated etherimide oligomer (a1), (a2) the number of moles of polycarbonate diol (a2), and (a3) the number of moles of dihydroxycarboxylic acid compound (a3). ), (A4) (a compound having an isocyanate group and at least one (meth) acryloyl group in the molecule) and / or (a compound having a hydroxyl group and at least one (meth) acryloyl group in the molecule) ( a4), (a5) [(a1) + (a2) + (a3)] / [(a4) + (a5)] = 0.5-1 when the number of moles of the diisocyanate compound is (a5). 5 and obtained by reacting within the range of [(a1) + (a2)] / (a3) = 0.1 to 5.0. As described in Light resin composition.   The (A) polyimide resin is obtained by further reacting (a6) a compound having an epoxy group and at least one (meth) acryloyl group in the molecule and (a7) a polybasic acid anhydride. Item 9. The photosensitive resin composition according to any one of Items 3 to 8.   The weight ratio of the component (A), the component (B), the component (C), and the component (D) in the photosensitive resin composition is 5 parts by weight with respect to 100 parts by weight of the component (A). The component according to any one of claims 1 to 9, wherein the component (C) is 0.1 to 20 parts by weight, and the component (D) is 0.5 to 100 parts by weight. Photosensitive resin composition.   The photosensitive resin composition solution obtained by melt | dissolving the photosensitive resin composition of any one of Claims 1-10 in the organic solvent.   The photosensitive film obtained by apply | coating the photosensitive resin composition of any one of Claims 1-10 to the base-material surface, and drying.   The insulating film obtained by hardening the photosensitive resin composition of any one of Claims 1-10. The printed wiring board with an insulating film which coat | covered the photosensitive resin composition of any one of Claims 1-10 on the printed wiring board.

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