KR20140144530A - Polyimide resin precursor composition, dry film, and circuit board - Google Patents

Abstract

The present invention relates to a polyimide resin precursor composition, a dry film, and a circuit board including a cured product of the same. More specifically, according to the present invention, a step for providing adhesive force to a final product can be skipped. Therefore, productivity and efficiency of producing the polyimide resin using the polyimide resin precursor composition can be increased. The polyimide resin precursor composition is used for providing the polyimide film that has excellent mechanical properties without compromising appearance of the polyimide resin, and has increased adhesiveness of the surface.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyimide resin precursor composition, a dry film and a circuit board,

The present invention relates to a polyimide resin precursor composition, a dry film, and a circuit board. More particularly, the present invention relates to a polyimide resin precursor composition, To a precursor composition, a dry film and a circuit board of a polyimide resin in which surface adhesion is remarkably improved while ensuring excellent mechanical properties without deterioration of characteristics.

Recently, weight reduction and miniaturization of products have been emphasized in the field of display, and glass substrates which are currently used are heavy, fragile and difficult to be continuously processed. Therefore, plastic substrates having advantages of light, To mobile phones, notebook computers, PDAs, and the like.

Particularly, the polyimide (PI) resin has advantages that it is easy to synthesize, can form a thin film and does not need a crosslinking agent for curing. Therefore, it has recently become a lightweight and refinement of electronic products, And a lot of research is going on to use PI for a flexible plastic display board having light and flexible properties.

A polyimide (PI) film produced by film-forming the polyimide resin is generally prepared by solution polymerization of an aromatic dianhydride and an aromatic diamine or aromatic diisocyanate to prepare a polyamic acid derivative, Refers to a high heat-resistant resin which is prepared by dehydrating and cyclizing cyclic rings.

In order to use the polyimide resin on a circuit board, a semiconductor substrate, or a flexible display substrate, the polyimide resin must have excellent adhesion to a silicon wafer or glass in addition to physical properties such as heat oxidation, heat resistance, radiation resistance, low temperature characteristics and chemical resistance.

Generally, an adhesion promoting agent such as a silane compound is used to improve the adhesion between a polyimide film and glass. In the case where the adhesion promoting agent is applied to glass to improve the adhesion, foreign matter is generated due to application of the adhesion promoting agent, It may not be smoothly formed, and it may be economically disadvantageous to perform the coating step after coating once more.

When the adhesion promoter is directly added to the polyamic acid, the problem caused by the application can be minimized, but the amino group of the silane compound may be precipitated as a carboxylic acid and a salt of the polyamic acid to generate foreign substances on the substrate.

Accordingly, it is possible to omit the step for adhering the final product, thereby improving the productivity and the efficiency of the process. Further, the polyimide resin with remarkably improved surface adhesion can be obtained while securing excellent mechanical properties without deteriorating the appearance characteristics of the polyimide resin It is necessary to develop precursor compositions, dry films and circuit boards.

The present invention can improve the productivity and process efficiency by omitting the steps for adhesion of the final product, and can provide a polyimide resin with remarkably improved surface adhesion while securing excellent mechanical properties without deteriorating the appearance characteristics of the polyimide resin to be produced. To provide a resin precursor composition.

The present invention also provides a dry film containing a cured product of the polyimide resin precursor composition.

 The present invention also provides a circuit board comprising the dry film.

The present invention relates to a tetracarboxylic dianhydride represented by the following formula (1): A diamine represented by the following formula (2); And an adhesion promoting agent comprising a compound of the following general formula (3) or (4).

[Chemical Formula 1]

(2)

NH ₂ - X ₂ - NH ₂

(3)

[Chemical Formula 4]

Wherein X ₁ is a divalent organic group and X ₂ is a divalent organic group; and A is a tetravalent organic group in the general formulas (3) and (4), R is a divalent organic group having 1 to 5 carbon atoms Alkyl group, and n is an integer of 1 to 5.

The present invention also provides a dry film comprising a cured product of the polyimide resin precursor composition.

The present invention also provides a circuit board comprising the dry film.

According to the present invention, it is possible to omit the steps for adhering the final product, thereby improving the productivity and the efficiency of the process, and it is possible to secure the excellent mechanical properties without deteriorating the appearance characteristics of the polyimide resin to be produced, A polyimide resin precursor composition, a dry film, and a circuit board may be provided.

In the present specification, the carbon ring group includes both an alicyclic ring group and an aromatic ring group, and also includes a hetero ring thereof. Means a functional group containing 1 to 3 hetero atoms selected from the group consisting of N, O, S, P and Si.

In the present specification, the "C4 to C20 condensed polycyclic carbon ring group" means a group in which two or more carbon rings are condensed with each other.

In the present specification, the term "C6 to C30 non-condensed polycyclic carbon ring group linked by a linker" means a linkage of two or more carbon rings by a linker. The linker may be a single bond, -O-, -CO-, -S-, -SO2-, -C (CH3) 2-, -C (CF3) 2-, -CONH-, -COO-, - -O (CH2) n2O-, -OCO (CH2) n3OCO-, and the like.

Unless otherwise defined herein, the meaning of "substituted" is a substituent selected from the group consisting of halogen, a C1 to C15 haloalkyl group, a nitro group, a cyano group, a C1 to C15 alkoxy group, and a C1 to C10 lower alkylamino group Substituted "

Hereinafter, a polyimide resin precursor composition, a dry film and a circuit board according to a specific embodiment of the present invention will be described in more detail.

According to one embodiment of the invention, tetracarboxylic dianhydride represented by the following formula (1): A diamine represented by the following formula (2); And an adhesion promoting agent comprising a compound of the following general formula (3) or (4): < EMI ID = 1.0 >

[Chemical Formula 1]

(2)

NH ₂ - X ₂ - NH ₂

(3)

[Chemical Formula 4]

Wherein X ₁ is a divalent organic group and X ₂ is a divalent organic group; and A is a tetravalent organic group in the general formulas (3) and (4), R is a divalent organic group having 1 to 5 carbon atoms Alkyl group, and n is an integer of 1 to 5.

In order to improve the adhesiveness of the conventional high-temperature-resistant polyimide film to glass, an adhesion promoting agent such as a silane compound is coated on the glass and the film is formed. However, in the conventional adhesion promoting agent, foreign matters are generated due to application of the adhesion promoting agent, There is a limit in that the coating process is required and the economical efficiency in the process is poor. In addition, even when the conventional adhesion promoter is directly added to the polyimide resin precursor, the limit of the amino group of the adhesion promoter to be precipitated by the carboxylic acid and salt of the polyamic acid is also generated.

The inventors of the present invention have conducted studies to prepare high-adhesion polyimide while solving the above-mentioned limitations, and have found that if a polyimide resin precursor composition containing an adhesion promoting agent having a specific structure is imidized, And the surface adhesion of the polyimide resin can be improved because the adhesion promoter can be strongly bonded to the surface of glass or metal. Thus, the present invention has been completed.

In particular, the polyimide resin precursor composition according to one embodiment of the present invention can introduce a specific functional group into the polyimide resin itself including the adhesion promoter of the above formula (3) or (4) The step for the addition can be omitted, the productivity and the efficiency of the process can be increased, and the excellent mechanical properties and surface adhesion can be improved without deteriorating the appearance characteristics of the polyimide resin to be produced.

More specifically, the polyimide resin precursor composition is obtained by reacting a tetracarboxylic dianhydride and a diamine to form a polyamic acid repeating unit, and bonding the adhesion promoter of the specific structure to the terminal of the polyamic acid repeating unit, A polyimide resin containing a repeating unit represented by the general formula (6) or (7) can be provided. The polyimide resin can exhibit strong adhesion to the surface of the substrate because the alkoxysilane (Si-OR) portion can undergo condensation reaction with the glass or metal surface in the form of Si-O-surface.

The tetracarboxylic dianhydride contained in the polyimide resin precursor composition is a compound represented by the formula (1), and the polyimide resin precursor composition may include at least one tetracarboxylic dianhydride. That is, the tetracarboxylic dianhydride may include a dianhydride compound in which X ₁ in the formula (1) is different from that of the tetracarboxylic dianhydride.

In Formula 1, X ₁ represents a substituted or unsubstituted C4 to C20 carbon ring group; A substituted or unsubstituted C4 to C20 condensed polycyclic carbon ring group; And a C6 to C30 non-condensed polycyclic carbon ring group linked by a substituted or unsubstituted linker.

Alternatively, X ₁ may be one quaternary organic group selected from the group consisting of the following formulas (21) to (35).

[Chemical Formula 21]

[Chemical Formula 22]

In Formula 22, Y ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} OCO-, and wherein n1, n2 and n3 is an integer from 1 to _{10, - -COO-, - (CH 2} ) n1

 (23)

Y ₂ and Y ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 - _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} OCO-, wherein n1, n2, and n3 is an integer of 1 to 10,

≪ EMI ID =

In the above formula (24), Y ₄ , Y ₅ And Y ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} a OCO-, wherein n1, n2 and n3 is 1 to 10 - -CONH-, -COO-, - (CH 2) n1 Lt; / RTI &

(25)

(26)

(27)

In the above formulas 26 and 27, * denotes a bonding point,

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

The diamine contained in the polyimide resin precursor composition is a compound represented by Formula 2, and the polyimide resin precursor composition may include one or more diamines. That is, the diamine may include a mixture of diamines in which X ₂ in Formula ₂ is different.

X ₂ in Formula 2 is a substituted or unsubstituted C 1 to C 20 alkylene group, a substituted or unsubstituted C 5 to C 40 arylene group, a substituted or unsubstituted C 3 to C 40 heteroarylene group, a substituted or unsubstituted C 5 to C 40 cyclo An alkylene group, and a substituted or unsubstituted C5 to C40 heterocycloalkylene group.

Alternatively, X ₂ in the formula (2) may be one divalent organic group selected from the group consisting of the following formulas (40) to (48).

(40)

(41)

Y ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n1} -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 and O-, or COO (CH _{2) n3} OCO-, wherein n1 , n2 and n3 are each an integer of 1 to 10,

(42)

In Formula 42, L ₂ and L ₃ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- or - a OCO (CH _{2) n3} OCO-, and wherein n1, n2 and n3 is an integer from 1 to 10,

(43)

In the above formula (43), L ₄ , L ₅ And L ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{-CONH-, -COO-, - (CH 2} ) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- , or -OCO (CH _{2) n3} OCO -, n1, n2 and n3 are each an integer of 1 to 10,

 (44)

[Chemical Formula 45]

(46)

In the above formulas (44), (45) and (46), * denotes a bonding point,

(47)

Wherein R ₁ is alkylene or arylene having 2 to 8 carbon atoms, R ₂ is alkylene having 2 to 8 carbon atoms, a and b are each 0 or 1, c is an integer of 1 to 21 ,

(48)

In Formula _{48, R 11, R 12,} R 13 and R ₁₄ may be the same or different from each other, are each an aryl group of the alkyl group or having 6 to 10 carbon atoms having 1 to 5, R ₁₅ and R ₁₆ are each C 1 M is an integer of 1 or more, and n is an integer of 0 or more.

The tetracarboxylic dianhydride and the diamine of the polyimide resin precursor composition each include a case where the above compounds are individually contained and a case where a reaction product between the above compounds is included.

That is, the polyimide resin precursor composition may include a reaction product of the tetracarboxylic dianhydride of Formula 1 and the diamine of Formula 2.

The reactant between the tetracarboxylic dianhydride and the diamine may form a polyamic acid repeating unit containing a repeating unit represented by the following formula (5), and the polyamic acid repeating unit may be imidized to provide a polyimide resin . The polyimide film has excellent mechanical properties, has excellent flexibility, can be in a stable form without breaking, and has a low coefficient of thermal expansion (CTE), which is excellent in thermal stability.

[Chemical Formula 5]

In Formula 5, X ₁ is a _divalent organic group and X ₂ is a divalent organic group. The above-mentioned specific functional groups in Formulas 1 and 2 can be applied to X ₁ and X ₂ in Formula 5.

Meanwhile, the adhesion promoter contained in the polyimide resin precursor composition may include the compound represented by the above formula (3) or (4).

The compound of formula (3) or (4) can be prepared by reacting tetracarboxylic dianhydride and monoaminotrialkoxysilane. The alkoxysilane (Si-OR) . ≪ / RTI > The silanol group can be condensed with a glass or metal surface in the form of Si-O-surface to increase the adhesion to the substrate surface. The compound of formula (3) or (4) does not contain an amino group, It is possible to minimize the generation of salt precipitated by reaction with an acid. That is, the adhesion promoter can minimize precipitation of salt even when mixed with a polyimide resin precursor solution containing a polyamic acid, so that it is possible to omit an additional purification step and to remarkably improve adhesion to a glass or metal surface have.

Further, the tetracarboxylic dianhydride-derived portion of the compound of Formula 3 or 4 may be easily bonded or compatibilized with an organic compound, and may be combined with a reactant of diamine and dianhydride of a polyimide resin precursor solution . Accordingly, the compound of Formula 3 or 4 can be uniformly mixed with the polyimide resin precursor solution through the portion derived from the tetracarboxylic dianhydride.

Therefore, the adhesion promoter containing the compound of Formula 3 or 4 including the moieties having the above characteristics is uniformly mixed in the polyimide resin precursor solution to significantly improve the adhesion between the polyimide film and the glass or metal surface .

In the above formulas (3) and (4), A may be a tetravalent organic group, and the type of the tetravalent organic group to be used is not limited, but may be a substituted or unsubstituted C4 to C20 carbon ring group; A substituted or unsubstituted C4 to C20 condensed polycyclic carbon ring group; And a C6 to C30 non-condensed polycyclic carbon ring group linked by a substituted or unsubstituted linker; May be a tetravalent organic group selected from the group consisting of

Alternatively, A may be a single tetravalent organic group selected from the group consisting of the following formulas (21) to (35).

The polyimide resin precursor composition may contain 0.1 to 20 moles of the adhesion promoter per 100 moles of the sum of the tetracarboxylic dianhydride and diamine. If the content of the adhesion promoter is too small, the adhesion between the polyimide film and the glass or metal surface may not be sufficiently improved.

The polyimide resin precursor composition may further include an organic solvent for the purpose of dissolving the components of the polyimide resin precursor composition and imparting a viscosity suitable for application of the composition. The organic solvent may be used without limitation as long as it is known to be usable in the polyimide resin precursor composition.

Ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Glycol ethers (cellosolve) such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Acetic acid esters such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate and dipropylene glycol monomethyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol and carbitol; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; And amides such as dimethylacetamide (DMAc) and dimethylformamide (DMF). These solvents may be used alone or as a mixture of two or more thereof.

The organic solvent may be one which is easy to dissolve the tetracarboxylic dianhydride, diamine, adhesion promoter or optionally further additives, and is particularly preferably a solvent which can be easily dried during the coating process. The content of the organic solvent may be 100 to 1000 parts by weight based on 100 parts by weight of the tetracarboxylic dianhydride and diamine solid in the polyimide resin precursor composition. If the content of the organic solvent is too low, the viscosity of the composition may become excessively high and the coating property may be deteriorated. If the content is too high, the composition may not be dried easily, .

The polyimide resin precursor composition may further comprise a heat crosslinking agent, a curing accelerator, a phosphorus flame retardant, a defoaming agent, a leveling agent, an antigelling agent or a mixture thereof. Such additives can be used without limitation as long as they are known to be usable in the polyimide resin precursor composition. The additives can be used in appropriate amounts in consideration of the physical properties of the polyimide resin precursor composition or films obtained therefrom.

On the other hand, a dry film containing a cured product of the polyimide resin precursor composition may be provided.

As described above, when a polyimide resin precursor composition to which an adhesion promoter containing the compound of Formula 3 or 4 is added to tetracarboxylic dianhydride and a diamine compound is used, excellent mechanical properties, flexibility, and thermal stability can be obtained A dry film having improved adhesion to a glass or metal surface can be provided.

Specifically, the dry film refers to a film obtained by drying the polyimide resin precursor composition, or a film obtained by photo-curing or thermosetting the polyimide resin precursor composition.

The dry film can be produced by applying a polyimide resin precursor composition on a support by a known method and then drying it. It is preferable that the support can peel the polyimide resin precursor composition layer, and the light transmittance and the surface smoothness are good.

Specific examples of the support include polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, alkyl (meth) acrylates, poly (meth) acrylate copolymers, polyvinyl chloride, poly Various plastic films such as polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride-vinyl acetate copolymer, polytetrafluoroethylene, and polytrifluoroethylene Glass substrates. A composite material composed of two or more of these materials may also be used, and the thickness of the support is preferably 5 to 150 mu m.

The method of applying the polyimide resin precursor composition is not particularly limited and may be, for example, spraying, roll coating, spin coating, slit coating, extrusion coating, curtain coating, die coating, wire bar coating, Knife coating method and the like can be used. The drying of the polyimide resin precursor composition is preferably carried out at 60 to 100 캜 for 30 seconds to 15 minutes although it depends on the kind of each constituent component and the type of organic solvent and the content ratio.

The film thickness of the dry film after drying and curing is 5 to 95 탆, more preferably 10 to 50 탆. If the film thickness of the dry film is 5 m or less, the insulating property is not good, and if it exceeds 95 m, the resolution may be lowered.

According to another embodiment of the present invention, there can be provided a polyimide resin comprising a repeating unit represented by the following general formula (6) or (7).

[Chemical Formula 6]

(7)

Wherein Y is a residue derived from the diamine, Z is a residue derived from the tetracarboxylic dianhydride, A is a tetravalent organic group, R is an alkyl group having 1 to 5 carbon atoms N is an integer of 1 to 5, and m is an integer of 1 or more. In the above formulas (6) and (7), A and R are as defined above.

The repeating unit represented by the above formula (6) or (7) can be prepared by reacting the polyimide resin precursor composition with the tetracarboxylic dianhydride represented by the formula (1), the diamine represented by the formula (2) And the details of the above-mentioned compounds are as described above.

The polyimide resin containing the repeating units of the above formula (6) or (7) can be in a stable form without breaking due to excellent mechanical properties and flexibility, and has a low coefficient of thermal expansion (CTE) have. In addition, the polyimide resin exhibits strong adhesion to the surface of the substrate without the step of coating the surface of the substrate with an additional adhesion promoter by strong condensation reaction of the alkoxysilane (Si-OR) portion bonded to the end of the polyamic acid repeating unit with the glass or metal surface And productivity and process efficiency can be improved.

According to another embodiment of the present invention, a dry film containing a polyimide resin containing the repeating units of the above formula (6) or (7) may be provided.

As described above, the polyimide resin containing the repeating unit represented by the above formula (6) or (7) is a polyimide resin having excellent mechanical properties and improved adhesion to glass or metal surfaces. The dry film containing the same also has excellent mechanical properties, It is possible to provide a dry film having improved adhesion to the substrate surface while exhibiting flexibility, thermal stability, and the like.

The dry film comprising the cured product of the polyimide resin precursor composition or the dry film comprising the polyimide resin containing the repeating unit of the above formula (6) or (7) can be used as a protective film for a circuit substrate, a base film of a circuit substrate, It can be suitably used for a flexible circuit board or a flexible display substrate which can be used for an insulating layer, an interlayer insulating film of a semiconductor, a solder resist, a flexible circuit board, or a flexible display substrate,

According to another embodiment of the present invention, a circuit board including the dry film may be provided.

The circuit board may include a multilayered printed circuit board, a flexible circuit board, or a flexible circuit board. As described above, the dry film can be used as a protective film for a circuit board, a base film of a circuit board, an insulating layer of a circuit board, an interlayer insulating film of a semiconductor, a solder resist, or the like on a circuit board.

The dry film included in the circuit board is meant to include a dry film or a workpiece of a dry film, for example, a workpiece or a photoreaction product laminated on a certain substrate.

Claims (12)

Tetracarboxylic dianhydride represented by the following formula (1);
A diamine represented by the following formula (2); And
A polyimide resin precursor composition comprising: an adhesion promoting agent comprising a compound of the following formula (3) or (4):
[Chemical Formula 1]

(2)
NH ₂ - X ₂ - NH ₂
(3)

[Chemical Formula 4]

In Formula 1, X ₁ is a divalent organic group,
In Formula 2, X ₂ is a divalent organic group,
In the above formulas (3) and (4), A is a tetravalent organic group,
R is an alkyl group having 1 to 5 carbon atoms,
n is an integer of 1 to 5;
The method according to claim 1,
X _{1 in} Formula ₁ and A in Formula 3 are substituted or unsubstituted C4 to C20 carbon ring groups; A substituted or unsubstituted C4 to C20 condensed polycyclic carbon ring group; And a C6 to C30 non-condensed polycyclic carbon ring group linked by a substituted or unsubstituted linker.
The method according to claim 1,
Wherein X _{1 in} Formula ₁ and A in Formula 3 are one quaternary organic group selected from the group consisting of the following Formulas 21 to 35, respectively:
[Chemical Formula 21]

[Chemical Formula 22]

In Formula 22, Y ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} OCO-, and wherein n1, n2 and n3 is an integer from 1 to _{10, - -COO-, - (CH 2} ) n1
(23)

Y ₂ and Y ₃ may be the same or different and each represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 - _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} OCO-, wherein n1, n2, and n3 is an integer of 1 to 10,
≪ EMI ID =

In the above formula (24), Y ₄ , Y ₅ And Y ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{a, -O (CH 2) n2 O-} , or -OCO (CH _{2) n3} a OCO-, wherein n1, n2 and n3 is 1 to 10 - -CONH-, -COO-, - (CH 2) n1 Lt; / RTI &
(25)

(26)

(27)

In the above formulas 26 and 27, * denotes a bonding point,
(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

.
The method according to claim 1,
X ₂ in Formula 2 is a substituted or unsubstituted C 1 to C 20 alkylene group, a substituted or unsubstituted C 5 to C 40 arylene group, a substituted or unsubstituted C 3 to C 40 heteroarylene group, a substituted or unsubstituted C 5 to C 40 cyclo An alkylene group, and a substituted or unsubstituted C5 to C40 heterocycloalkylene group.
The method according to claim 1,
Wherein X ₂ in Formula ₂ is one divalent organic group selected from the group consisting of the following Formulas 40 to 48:
(40)

(41)

Y ₁ represents a single bond, -O-, -CO-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -CONH-, _{-COO-, - (CH 2) n1} -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 and O-, or COO (CH _{2) n3} OCO-, wherein n1 , n2 and n3 are each an integer of 1 to 10,
(42)

In Formula 42, L ₂ and L ₃ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C _{(CF 3) 2 -, -CONH-} , -COO-, - (CH 2) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- or - a OCO (CH _{2) n3} OCO-, and wherein n1, n2 and n3 is an integer from 1 to 10,
(43)

In the above formula (43), L ₄ , L ₅ And L ₆ may be the same or different from each other, and respectively a single bond, -O-, -CO-, -S-, -SO 2 -, -C (CH 3) 2 -, -C (CF 3) 2 -, _{-CONH-, -COO-, - (CH 2} ) n1 -, -O (CH 2) n2 O-, -OCH 2 -C (CH 3) 2 -CH 2 O- , or -OCO (CH _{2) n3} OCO -, n1, n2 and n3 are each an integer of 1 to 10,
(44)

[Chemical Formula 45]

(46)

In the above formulas (44), (45) and (46), * denotes a bonding point,
(47)

Wherein R ₁ is alkylene or arylene having 2 to 8 carbon atoms, R ₂ is alkylene having 2 to 8 carbon atoms, a and b are each 0 or 1, c is an integer of 1 to 21 ,
(48)

In Formula _{48, R 11, R 12,} R 13 and R ₁₄ may be the same or different from each other, are each an aryl group of the alkyl group or having 6 to 10 carbon atoms having 1 to 5, R ₁₅ and R ₁₆ are each C 1 M is an integer of 1 or more, and n is an integer of 0 or more.
The method according to claim 1,
Wherein the polyimide resin precursor composition comprises a tetracarboxylic dianhydride of the formula 1 and a reaction product of the diamine of the formula 2.
The method according to claim 1,
And 0.1 to 20 moles of the adhesion promoter, based on 100 moles of the sum of the tetracarboxylic dianhydride and diamine.
A dry film comprising a cured product of the polyimide resin precursor composition of claim 1.
A polyimide resin comprising a repeating unit represented by the following formula (6) or (7):
[Chemical Formula 6]

(7)

Wherein Y is a residue derived from the diamine, Z is a residue derived from the tetracarboxylic dianhydride, R is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 1 to 5 And m is an integer of 1 or more.
A dry film comprising the polyimide resin of claim 9.
11. The method according to claim 8 or 10,
The dry film is used as a protective film for a circuit board, a base film of a circuit board, an insulating layer of a circuit board, an interlayer insulating film of a semiconductor, a solder resist, or a flexible display board.
A circuit board comprising the dry film of claim 8 or 10.