KR20160120865A - Polyimide resin having vinyl group and photosensitive resin composition comprising same - Google Patents

Abstract

The present invention relates to a polyimide resin having a vinyl group, and to a photosensitive resin composition comprising the same. More particularly, the photosensitive resin composition has a lower free volume by mutually cross-linking polyimides by using a polyimide resin having a vinyl group, thereby preventing diffusion of copper ions. Also, the photosensitive composition can be cured at a low temperature.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyimide resin having a vinyl group and a photosensitive resin composition containing the polyimide resin. [0002]

The present invention relates to a polyimide resin having a vinyl group and a photosensitive resin composition containing the same, and more particularly, to a polyimide resin having a vinyl group by cross-linking the polyimide with each other to lower the free volume of the resin, To a photosensitive resin composition comprising a polyimide having a vinyl group capable of preventing diffusion of copper ions as well as being capable of low-temperature curing.

Resins typified by polyimide and polybenzoxazole have excellent heat resistance and electrical insulation, and thus are used as surface protective films for semiconductor devices, interlayer insulating films, insulating layers of organic electroluminescent devices, and the like.

In recent years, due to the miniaturization of semiconductor devices, a high resolution of several mu m level is required for a surface protective film, an interlayer insulating film and the like, and a positive photosensitive polyimide resin composition and a positive photosensitive polybenzoxazole resin composition are widely used.

Conventionally used resins for an interlayer insulating film include polyamic acid (PAA) which is a polyimide precursor and polyhydroxyl amide (PHA) which is a precursor of polybenzoxazole to a substrate such as a silicon wafer After forming a film by spin coating, a pattern is formed through a series of exposure and development processes, and then the film is cured at a high temperature of about 300 ° C or higher for a certain period of time to form an insulating film.

However, recently, in order to improve the productivity of semiconductor production, it is aimed to shorten the temperature rise time. Especially, as the chip is thinned by the highly integrated semiconductor production, a low curing temperature of the mounting materials is required.

A naphthoquinonediazide sulfonic acid ester compound has been widely used as a photosensitizer for use in a conventionally used positive photosensitive resin composition. Thus, a naphthoquinonediazide sulfonic acid ester compound has been widely used, and therefore, an alkali soluble resin and a naphthoquinonediazide sulfonic acid ester compound of phenol A positive photosensitive resin composition containing a positive photosensitive resin composition or a heat resistant resin precursor such as a novolac resin or a polyimide precursor, a quinone diazide compound, an alkoxymethyl group-containing compound and a solvent has been proposed. However, such a method has difficulty in obtaining a high-resolution photosensitive resin composition. Particularly, low-temperature curing at 200 ° C or less is not easy, and the mechanical properties of the film deteriorate at low temperature curing. Also, conventional photosensitive materials have a problem in that diffusion of copper ions can not be directly prevented.

In order to solve the above problems, it is an object of the present invention to provide a positive photosensitive resin composition which can prevent diffusion of copper ions and can be cured at low temperature by using a polyimide resin having a vinyl group.

In order to achieve the above object,

Claims [1] A polyimide resin represented by the following formula (1):

[Chemical Formula 1]

In this formula,

X is a tetravalent organic group containing a vinyl group;

R ₁ is a divalent organic group containing a vinyl group;

n is an integer of 10 to 1000;

The present invention also provides a polyimide resin represented by the following general formula (2)

(2)

In this formula,

X is a tetravalent organic group including a vinyl group;

X ₁ is a tetravalent organic group;

R ₁ is a divalent organic group containing a vinyl group;

R is an organic group containing an aromatic ring compound or an inorganic group not containing an aromatic ring compound;

K and L are each independently an integer of 0 to 4, provided that K and L may be the same or different, and K + L must be 1 or more;

a and b are each independently an integer of 10 to 1000;

D is hydrogen, a methyl group or a vinyl group.

The present invention also

a) a polyimide resin having a vinyl group represented by the above formula (1) or (2);

b) Photosensitizer;

c) a crosslinking agent;

d) thermal initiators; And

e) Solvent

And a polyimide having a vinyl group.

The present invention also provides a cured product of a photosensitive resin composition comprising a polyimide having a vinyl group prepared by curing a photosensitive resin composition comprising the polyimide having a vinyl group.

The present invention also provides a method for forming a pattern of a substrate using an insulating film for a semiconductor passivation film or a redistribution line (RDL), an OLED substrate, and a photosensitive resin composition containing the cured product of the photosensitive resin composition comprising the vinyl group .

The photosensitive resin composition comprising the vinyl group-containing polyimide according to the present invention can be produced by using a polyimide resin having a vinyl group, that is, a polyimide resin having completed the cyclization, at a low curing temperature for removing the solvent, The curing can be carried out at a temperature. The curing reaction can effectively increase the degree of crosslinking by the radicals by reacting the double bond of the vinyl group contained in the main chain of the thermal initiator and the polyimide resin to lower the free volume of the resin. As a result, Can be used to produce a firm film that can prevent diffusion of ions.

1 shows the results of evaluating the degree of copper diffusion using the composition of the example of the present invention and the composition of the comparative example.

The photosensitive resin composition comprising a polyimide having a vinyl group according to the present invention is a photosensitive resin composition comprising: a) a polyimide resin having a vinyl group; b) Photosensitizer; c) a crosslinking agent; d) a thermal initiator; And e) a solvent.

The components will be described below.

a) a polyimide resin having a vinyl group

The polyimide resin having a vinyl group that can be used in the present invention is characterized by being represented by the following formula (1) or (2), and each independently has a weight average molecular weight (Mw) in terms of polystyrene of 3,000 to 100,000.

[Chemical Formula 1]

(2)

In the above formula (1) or (2)

X is a tetravalent organic group including a vinyl group;

X ₁ is a tetravalent organic group;

R ₁ is a divalent organic group containing a vinyl group;

R is an organic group containing an aromatic ring compound or an inorganic group not containing an aromatic ring compound;

K and L are each independently an integer of 0 to 4, provided that K and L may be the same or different, and K + L must be 1 or more;

n is an integer from 10 to 1000;

a and b are each independently an integer of 10 to 1000;

D is hydrogen, a methyl group or a vinyl group.

Preferably, X may be selected from the group consisting of the following formulas (3) to (5): (* in the following structures is a linking site in the formula)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

Preferably, R < ₁ > is a structure represented by the following formula (6) or (7)

[Chemical Formula 6]

(7)

Preferably, X ₁ may be selected from the group consisting of Formulas 3 to 5 and Formulas 8 to 9. (* in the following structures is a connecting site in the formula)

[Chemical Formula 8]

[Chemical Formula 9]

Preferably, the R may be selected from the group consisting of structures represented by the following formulas (10) to (15). (In the following structures, * is a linking site in the formula)

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

More preferably, the molar ratio of a and b in the above formula (2) is preferably 0.05: 0.95 to 0.95: 0.05. In this case, the effect of preventing diffusion of copper ions is better.

The polyimide resin may also be capped at the end by an end capping agent. Wherein the end capping agent is at least one member selected from the group consisting of monoamine, acid anhydride, acid chloride and monocarboxylic acid containing at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, sulfonic acid group, thiol group, vinyl group, ethynyl group and allyl group Preferably, the end capping agent is contained in an amount of 5 to 50 mol% based on the total amine component (100 mol%) in the polyimide resin.

The polyimide resin having a vinyl group can be synthesized by a conventional method known in the art using the specific monomers of the present invention and is preferably a solvent such as N-methyl-2-pyrrolidone or γ- Can be synthesized by condensing a specific diamine compound and a dianhydride compound in a butyrolactone to synthesize a polyimide precursor and continuously dehydrating it to proceed an imide cyclization reaction.

The monomer of the diamine compound usable in the present invention may be a compound represented by the following formula (16) or (17), and may further include a compound selected from the group consisting of the following formulas (18) to (23)

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

The monomer of the dianhydride compound may be a compound selected from the group consisting of the following formulas (24) to (26), and may further include a compound represented by the following formula (27) or (28)

≪ EMI ID =

(25)

(26)

(27)

(28)

b) Photosensitizer

The photosensitive resin composition of the present invention basically includes a photosensitive agent as a positive photosensitive resin composition. The photosensitive agent is not particularly limited as long as it is a photosensitive agent conventionally used in a photosensitive resin composition, preferably a quinone diazide compound, more preferably May be synthesized by esterification of a phenol compound with naphthoquinone diazide sulfonic acid.

In the present invention, examples of the naphthoquinonediazide sulfonyl group of the naphthoquinone diazide sulfonic acid include a 5-naphthoquinonediazide sulfonyl group or a 4-naphthoquinone diazide sulfonyl group, But is not limited thereto.

In the present invention, it is preferable to select the 4-naphthoquinone diazide sulfonyl ester compound or the 5-naphthoquinone diazide sulfonyl ester compound according to the wavelength to be exposed, and for example, A naphthoquinone diallyl sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group or a 5-naphthoquinone diazide sulfonyl group is used in combination, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5- A toquinonediazide sulfonyl ester compound may be used in combination.

The photosensitive agent is preferably used in an amount of 1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the polyimide resin having the vinyl group.

c) Crosslinking agent

The crosslinking agent usable in the present invention has a function of forming a crosslinking structure with the polyimide resin, and may be a crosslinking agent containing an alkoxymethyl group. Generally, the alkoxymethyl group undergoes crosslinking at about 150 ° C. To increase the crosslinking density, a compound having two or more alkoxymethyl groups is preferable, and in order to further improve the chemical resistance by increasing the crosslinking density, four or more alkoxymethyl groups Branched compounds are more preferable. It is particularly preferable to have at least one compound having six or more alkoxymethyl groups from the viewpoint of reducing uneven pattern size after curing.

The crosslinking agent is preferably used in an amount of 1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyimide resin having the vinyl group. When the content is less than 1 part by weight, a film having high chemical resistance can not be obtained. When the content is more than 30 parts by weight, storage stability is deteriorated.

d) Thermal initiator

The thermal initiator that can be used in the present invention is preferably a peroxide or an azo compound and a compound which is initiated at a temperature of 100 ° C or higher. For example, the peroxide is dicumyl peroxide, di -tert- butyl peroxide may be, the azobis compound, having a structure of, R "R'N = NR a CH _3, (CH _{3) 2} CH or C ₆ H ₅ (CH ₃ CH).

The thermal initiator is preferably used in an amount of 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the polyimide resin.

e) Solvent

The solvent that can be used in the present invention functions to prevent the flatness and unevenness of the coating of the polyimide photosensitive resin composition and to form a uniform pattern profile.

The solvent is selected from the group consisting of N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, Glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, and combinations thereof, and may be used in an amount sufficient to balance the total composition weight have. Preferably, it is preferred that the solids content of the entire composition is comprised between 5 and 50% by weight.

The composition of the present invention can also be added to various additives such as an end capping agent, a metal corrosion inhibitor, a silane compound and other positive photosensitive resin compositions, depending on the intended use of the material Various additives may be further included.

The terminal capping agent usable in the present invention is used for capping the terminal of the resin having the structure represented by the formula (1) as the main component. The terminal of the resin is preferably a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, The dissolution rate of the resin in an aqueous alkali solution can be adjusted to a desired range by sealing with a capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid, or the like having a functional group such as a hydroxyl group,

The content of the end capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid and the like is preferably 5 to 50 mol% relative to the total amine component.

The metal corrosion inhibitor which can be used in the present invention can be used for preventing the diffusion of metal ions in the insulating layer to be protected. Examples of the metal corrosion inhibitor include a lysole-based compound, a purine-based compound and a sulfonic acid- Particularly, benzotriazole (BTA) compounds are suitable.

The metal corrosion inhibitor may be used in an amount of 0.1 to 10 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total composition. Within the above range, the effect of preventing metal film corrosion, the heat resistance and the chemical resistance of the film can be satisfied at the same time.

The silane compound usable in the present invention is used for improving the adhesion with the base substrate and includes, for example, N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenyl Aminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, N-phenylaminobutyltrimethoxysilane, N-phenylaminobutyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and combinations thereof. However, the present invention is not limited thereto.

The content of the silane compound is preferably 0.01 part by weight to 15 parts by weight based on 100 parts by weight of the total composition. When the amount is within the above range, sufficient effect can be obtained as an adhesive while maintaining the heat resistance of the positive photosensitive resin composition have.

The photosensitive resin composition comprising a polyimide having a vinyl group according to the present invention can be produced by using a polyimide resin which has been subjected to the cyclization to obtain a low curing temperature for removing the used solvent, preferably a temperature of 200 DEG C or lower, The curing can be carried out at a temperature of 150 to 200 DEG C and the degree of crosslinking by radicals can be effectively increased by reacting the double bond of the vinyl group contained in the main chain of the thermal initiator and the polyimide resin during curing, , And consequently can be used to produce a firm film that can prevent the diffusion of copper ions.

The present invention provides a cured product of a photosensitive resin composition comprising a polyimide having a vinyl group prepared by curing a photosensitive resin composition comprising the polyimide having a vinyl group.

The present invention also provides a method for forming a pattern of a substrate using an insulating film for a semiconductor passivation film or a redistribution line (RDL), an OLED substrate, and a photosensitive resin composition containing the cured product of the photosensitive resin composition comprising the vinyl group .

The method for forming a pattern on a substrate of the present invention is characterized in that the photosensitive resin composition is used in a method for forming a pattern of a substrate using a photosensitive resin composition. In the present invention, the substrate may be a semiconductor substrate or an OLED substrate.

As a specific example, a method of forming a pattern of a substrate using the above photosensitive resin composition is as follows.

First, the polyimide photosensitive resin composition of the present invention is applied to the substrate surface by a spraying method, a roll-coating method, a spin coating method, or the like, and the solvent is removed by pre-baking to form a coating film. At this time, it is preferable that the prebaking is performed at a temperature of 80 to 130 ° C for 1 to 15 minutes.

Then, a visible ray, an ultraviolet ray, a far ultraviolet ray, an electron ray, an X-ray and the like are irradiated to the formed coating film according to a previously prepared pattern, and after performing post exposure bake (PEB) and front exposure (Flood Exposure) Thereby forming a predetermined pattern by removing unnecessary portions.

An alkaline aqueous solution is preferably used as the developing solution, and specific examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, and sodium carbonate; Primary amines such as ethylamine and n-propylamine; Secondary amines such as diethylamine and n-propylamine; Tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; Alcohol amines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; Or an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. At this time, the developer is used by dissolving the alkaline compound in a concentration of 0.1 to 10% by weight, and a proper amount of a water-soluble organic solvent such as methanol, ethanol and the like and a surfactant may be added.

After developing with the developer as described above, it is cleaned with ultrapure water for 30 to 90 seconds to remove unnecessary portions and dried to form a pattern. The pattern is heated to 130 to 250 ° C, more preferably 150 to 250 ° C by a heating device such as an oven, And then heat-treated at a temperature of 200 ° C for 30 to 90 minutes to obtain a final pattern.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

Synthesis Example 1 : Synthesis of Polymers

15 g (0.04 mol) of the diamine monomer of formula (16) was dissolved in 100 g of solvent GBL under a dry nitrogen stream. 10.03 g (0.04 mol) of the dianhydride monomer of the formula (23) was added thereto, and the mixture was reacted at room temperature for 6 hours with stirring. Thereafter, 30 g of toluene was further added thereto, and a Dean-stack was installed. The temperature was raised to 160 ° C., and the mixture was stirred for 12 hours to conduct a dehydration reaction. Thereafter, the reaction solvent was cooled to room temperature, and the solution was poured into 3 L of methanol. After filtration, a polymer solid precipitate was obtained, which was washed three times with an excess amount of methanol and dried in a vacuum drier at 80 ° C for 48 hours.

The average molecular weight of the polymer obtained by GPC NMP column was measured and the relative imidization rate was calculated by FT-IR.

Synthesis Examples 2 to 14 : Synthesis of Polymers

Polymers were synthesized and analyzed in the same manner as in Synthesis Example 1 except that diamines and dianhydrides were different according to the composition shown in Table 1 below.

Diamine Dianhydride GBL
(g) Molecular Weight
(GPC) Imidization rate
(%) The mol input
(g) The mol input
(g) The mol input
(g) The mol input
(g) One 16 0.04 15 24 0.04 10.03 100 16000 17 0.092 10 24 0.092 22.87 131 12000 96 16 0.027 10 18 0.027 5.83 24 0.054 13.38 117 18000 97 16 0.027 10 19 0.027 9.87 24 0.054 13.38 133 13500 98 16 0.027 10 20 0.027 6.96 24 0.054 13.38 124 16000 95 16 0.027 10 21 0.027 7.56 24 0.054 13.38 134 17000 95 16 0.027 10 22 0.027 10.25 24 0.054 13.38 135 16000 96 17 0.046 5 18 0.046 9.96 24 0.092 22.87 151 16000 97 17 0.046 5 19 16.87 24 0.092 22.87 179 18000 98 17 0.046 5 20 11.9 24 0.092 22.87 159 20000 97 17 0.046 5 21 12.92 24 0.092 22.87 163 19000 96 17 0.046 5 22 17.53 24 0.092 22.87 181.63 18000 98 17 0.039 15 24 0.02 4.89 25 0.02 6.12 101.3 21000 98 17 0.039 15 24 0.02 4.89 26 0.02 5.8 103 21000 98

Comparative Synthesis Example 1 : Synthesis of Polymers

15 g (0.041 mol) of the formula 18 diamine monomer was dissolved in 129 g of solvent GBL under a dry nitrogen stream. 12.70 g (0.041 mol) of the dianhydride monomer of the formula (25) was added thereto and reacted with stirring at room temperature for 6 hours. The reaction mixture was cooled to room temperature, and the solution was poured into 3 L of methanol. The precipitate of the polymer solid was collected by filtration, washed three times with excess methanol, and dried in a vacuum dryer at 80 ° C for 48 hours to obtain polyamic acid.

Example 1 : Preparation and Evaluation of Photosensitive Resin Composition

0.6 g of crosslinking agent MX-270 (oxidizing chemical, Japan) and 0.2 g of DCP (dicumyl peroxide, Aldrich) were dissolved in 15 g of a solvent PGMEA to 1.2 g of a photosensitizer DON-DIP1 from Toyo Kasei (Japan), 6 g of the polymer of Synthesis Example 1 Thereby obtaining a positive photosensitive resin composition.

Examples 2 to 16 and Comparative Example 1 : Preparation and Evaluation of Photosensitive Resin Composition

According to the composition shown in the following Table 2, a photosensitive resin was prepared by using each of the polymers of Synthesis Examples 2 to 14 and Comparative Synthesis Example 1 in the same manner as in Example 1 above. In addition, Example 15 and Example 16 were added to confirm the effect of the film residual ratio on the presence or absence of the metal corrosion inhibitor. In Table 2 below, BTA means Benzotriazole.

Composition Polymer additive Exposure
energy
(mJ) definition
(탆) film
Residual film ratio
(%) Example 1 Synthesis Example 1 500 3 90 Example 2 Synthesis Example 2 400 3 95 Example 3 Synthesis Example 3 500 3 95 Example 4 Synthesis Example 4 600 3 95 Example 5 Synthesis Example 5 500 3 95 Example 6 Synthesis Example 6 500 3 90 Example 7 Synthesis Example 7 500 3 90 Example 8 Synthesis Example 8 500 3 90 Example 9 Synthesis Example 9 500 3 92 Example 10 Synthesis Example 10 600 3 92 Example 11 Synthesis Example 11 600 3 93 Example 12 Synthesis Example 12 600 3 94 Example 13 Synthesis Example 13 600 3 94 Example 14 Synthesis Example 14 400 3 98 Example 15 Synthesis Example 1 BTA 1% 500 3 98 Example 16 Synthesis Example 1 BTA 5% 500 3 98 Comparative Example 1 Comparative Synthesis Example 1 400 3 0

Test Example 1

The photosensitive resin composition solutions of Examples 1 to 16 and Comparative Example 1 were spin-coated on a silicon wafer using TEL ACT8 track, and then baked at 120 DEG C for 3 minutes to obtain a film having a thickness of 5 mu m. After exposure using a MA-6 mask aligner with a broadband wavelength and a mask with a pattern of 1 to 10 mu m L / S pattern, a 2.38 wt% aqueous solution of TMAH was applied for 60 seconds to obtain a desired size pattern. The obtained patterned film was cured at 200 ° C for 60 minutes, immersed in NMP solvent at 40 ° C for 10 minutes, washed with water to observe the change in thickness of the film, and the results are shown in Table 2 above. However, in the case of Comparative Example 1, since the structure is converted to polyimide at a high temperature of 300 ° C or higher from general PAA (polyamic acid), curing was performed at 300 ° C for 3 hours to obtain a polyimide film from polyamic acid.

As shown in Table 2, the polymers used in the present invention can be cured at a relatively low temperature of 200 ° C, unlike the polymer of Comparative Synthesis Example 1 using polyamic acid, which has been used previously, I could make it.

Test Example 2

In order to confirm whether the polyimide polymers of Synthesis Examples 1 to 14 and Comparative Synthesis Example 1 could serve as a copper diffusion preventing film, a metal wafer of Ti (100 nm) / Cu (300 nm) CVD was deposited on a silicon wafer, To 16 were applied, dried and cured at 200 ° C in the same manner as in Test Example 1, and then heated again in an oven at 180 ° C for 10 days. Then, copper diffusion lengths Respectively. The results are shown in Fig. 1 and Table 3 below.

In the case of the photosensitive resin composition solution of Comparative Example 1, comparative evaluation was carried out in the same manner as above except that the curing was carried out at 300 ° C for 3 hours. The results are shown in FIG. 1 and Table 3.

Composition Polymer additive Copper layer
thickness
(nm) Copper
Spreading distance
(nm) Example 1 Synthesis Example 1 405 5 Example 2 Synthesis Example 2 412 12 Example 3 Synthesis Example 3 413 13 Example 4 Synthesis Example 4 407 7 Example 5 Synthesis Example 5 405 5 Example 6 Synthesis Example 6 401 One Example 7 Synthesis Example 7 402 2 Example 8 Synthesis Example 8 405 5 Example 9 Synthesis Example 9 405 5 Example 10 Synthesis Example 10 408 8 Example 11 Synthesis Example 11 405 5 Example 12 Synthesis Example 12 403 3 Example 13 Synthesis Example 13 405 5 Example 14 Synthesis Example 14 406 6 Example 15 Synthesis Example 1 BTA 1% 401 One Example 16 Synthesis Example 1 BTA 5% 402 2 Comparative Example 1 Comparative Synthesis Example 1 650 250

As shown in Table 3 and FIG. 1, in the composition of Comparative Example 1, unlike copper diffusion of about 250 nm in the polyimide layer in the copper layer, the compositions according to the present invention cause diffusion of copper It can be seen that it can act as a copper diffusion preventive film.

Claims (24)

1. A polyimide resin represented by the following formula (1)
[Chemical Formula 1]

In this formula,
X is a tetravalent organic group containing a vinyl group;
R ₁ is a divalent organic group containing a vinyl group;
n is an integer of 10 to 1000; The method according to claim 1,
Wherein X is at least one selected from the group consisting of structures represented by the following formulas (3) to (5): < EMI ID =
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above structures,
* Represents the bonding position in the repeating unit of formula (1). The method according to claim 1,
Wherein R < _{1 >} is a structure represented by the following formula (6) or (7)
[Chemical Formula 6]

(7)

In the above structures,
* Represents the bonding position in the repeating unit of formula (1). A polyimide resin represented by the following formula (2)
(2)

In this formula,
X is a tetravalent organic group including a vinyl group;
X ₁ is a tetravalent organic group;
R ₁ is a divalent organic group containing a vinyl group;
R is an organic group containing an aromatic ring compound or an inorganic group not containing an aromatic ring compound;
K and L are each independently an integer of 0 to 4, provided that K and L may be the same or different, and K + L must be 1 or more;
a and b are each independently an integer of 10 to 1000;
D is hydrogen, a methyl group or a vinyl group. The method of claim 4,
X is selected from the group consisting of structures represented by the following formulas (3) to (5), and X ₁ is selected from the group consisting of structures represented by the following formulas (3) to (5) Polyimide resin:
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 8]

[Chemical Formula 9]

In the above structures,
* Represents the position bonded in the repeating unit of formula (2). The method of claim 4,
Wherein R ₁ is a structure represented by the following formula (6) or (7), and R is selected from the group consisting of structures represented by the following formulas (10) to (15)
[Chemical Formula 6]

(7)

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

[Chemical Formula 15]

In the above structures,
* Represents the position bonded in the repeating unit of formula (2). The method of claim 4,
wherein the molar ratio of a and b is 0.05: 0.95 to 0.95: 0.05. The method according to claim 1 or 4,
Wherein the polyimide resin has a polystyrene reduced weight average molecular weight (Mw) of 3,000 to 100,000. The method according to claim 1 or 4,
Wherein the end of the polyimide resin is capped with an end capping agent. The method of claim 9,
Wherein the terminal capping agent is selected from the group consisting of monoamine, acid anhydride, acid chloride, and monocarboxylic acid containing at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, sulfonic acid group, thiol group, vinyl group, ethynyl group and allyl group And a polyimide resin. The method of claim 9,
Wherein the end capping agent comprises 5 to 50 mol% based on the total amine component (100 mol%) in the polyimide resin. A polyimide precursor is synthesized by condensing a first diamine compound and a dianhydride compound in a solvent to synthesize a polyimide precursor and then dehydrating continuously to proceed an imide cyclization reaction. ≪ / RTI > The method of claim 12,
Wherein the first diamine compound is one of compounds represented by the following general formula (16) or (17): < EMI ID =
[Chemical Formula 16]

[Chemical Formula 17]

The method of claim 12,
Wherein the dianhydride compound is at least one selected from the group consisting of the following Chemical Formulas 24 to 26:
≪ EMI ID =

(25)

(26)

. The method of claim 12,
Wherein the second diamine compound is added in the step of condensing the first diamine compound and the dianhydride compound. 16. The method of claim 15,
Wherein the second diamine compound is any one selected from the group consisting of compounds represented by the following Chemical Formulas 18 to 23:
[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

15. The method of claim 14,
Wherein the dianhydride compound further comprises a compound represented by the following formula (27) or (28) in the condensation step:
(27)

(28)

a) a polyimide resin according to claim 1 or 4;
b) Photosensitizer;
c) a crosslinking agent;
d) a thermal initiator; And
e) solvent;
Wherein the photosensitive resin composition is a photosensitive resin composition. 19. The method of claim 18,
The photosensitive resin composition
a) 100 parts by weight of a polyimide resin;
b) 1 to 50 parts by weight of a photosensitizer based on 100 parts by weight of the resin;
c) 1 to 30 parts by weight of a crosslinking agent based on 100 parts by weight of the resin;
d) 0.5 to 20 parts by weight of a thermal initiator based on 100 parts by weight of the resin; And
e) residual solvent;
Wherein the photosensitive resin composition is a photosensitive resin composition. 19. The method of claim 18,
Wherein the photosensitive resin composition is a positive-working composition. 19. The method of claim 18,
Wherein the photosensitive resin composition further comprises one selected from the group consisting of a metal corrosion inhibitor and a silane compound. (a) applying the photosensitive resin composition according to claim 18 onto a silicon wafer;
(b) baking the applied photosensitive resin composition to form a photosensitive resin film;
(b) exposing the photosensitive resin film to light; And
(c) developing the exposed photoresist film to form a pattern of a desired size;
Wherein the photosensitive resin film pattern is formed on the photosensitive resin film. A semiconductor substrate comprising a photosensitive resin film pattern formed by the method according to claim 22. An OLED substrate comprising a photosensitive resin film pattern formed by the method according to claim 22.

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