KR102232349B1 - Negative-type photosensitive resin composition having high thermoresistance and hardened overcoat layer prepared therefrom - Google Patents

Abstract

The present invention relates to a highly heat-resistant negative photosensitive resin composition and a cured film prepared therefrom, comprising: (a) (a-1) an organosiloxane polymer comprising a siloxane unit having a (meth)acrylate group; (a-2) an organosiloxane polymer containing a siloxane unit having a phenyl group; And (b) a cured film prepared from the photosensitive resin composition of the present invention that contains a photopolymerization initiator and does not contain an acrylate-based compound having an ethylenically unsaturated double bond, has excellent heat resistance under high-temperature curing conditions, and is thus smooth by suppressing the occurrence of cracks. Since a film can be implemented and does not show a decrease in light transmittance due to yellowing, it can be usefully used as a protective film of electronic components.

Description

High heat resistance negative photosensitive resin composition and cured film prepared therefrom {NEGATIVE-TYPE PHOTOSENSITIVE RESIN COMPOSITION HAVING HIGH THERMORESISTANCE AND HARDENED OVERCOAT LAYER PREPARED THEREFROM}

The present invention has excellent heat resistance under high-temperature curing conditions, thereby suppressing the occurrence of cracks, thereby enabling a flat film to be implemented, not exhibiting a decrease in light transmittance due to yellowing, etc., and capable of realizing high resolution, a protective film, an insulating film, and a semiconductor device or a display device. It relates to a negative photosensitive resin composition useful for manufacturing an optical waveguide and the like. Further, the present invention relates to a cured film formed using the composition and an electronic component including the cured film.

In order to implement the negative photosensitive resin composition used in the manufacture of protective films, insulating films, and optical waveguides of various display devices such as liquid crystal display devices and organic light emitting devices, a photopolymerization initiator and a monomer having a photocurable unsaturated double bond are used as composition additives. Has been. However, these additives have a carbon structure with poor heat resistance, and in particular, they volatilize as fumes at high temperatures, causing large film shrinkage, causing cracks, and carbonization at high temperatures to reduce the light transmittance of the thin film. Therefore, most photosensitive resin compositions including these additives have a problem in that it is difficult to implement excellent heat resistance and photosensitivity properties.

On the other hand, in recent years, various studies have been made on the use of a siloxane polymer having excellent flatness, heat resistance, refractive index, and transmittance as a photosensitive resin in such a resin composition for a protective film.

For example, Korean Patent No. 10-0963111 (Patent Publication No. 10-2008-0055989) uses a siloxane polymer containing a styrene group to provide a siloxane structure with improved flatness and improved adhesion and elongation with the underlying metal wiring. A photosensitive resin composition capable of forming a resin film is disclosed, and Korean Patent No. 10-1121936 (Patent Publication No. 10-2010-0009536) contains a siloxane into which a metal element is introduced, and thus conventional photosensitive polyimide- Compared to the containing composition, a photosensitive composition having excellent planarization, good mechanical properties, and reduced shrinkage after heat curing is disclosed.

However, the composition disclosed in Korean Patent No. 10-0963111 has an unsatisfactory resolution, and the composition disclosed in Korean Patent No. 10-1121936 has a limitation in realization of a low dielectric constant due to the use of siloxane into which a metal element is introduced. .

Domestic Patent No. 10-0963111 Domestic Patent No. 10-1121936

Accordingly, the object of the present invention is to use a siloxane polymer having excellent photosensitivity and heat resistance, and at the same time, by excluding monomers having ethylenically unsaturated double bonds that reduce heat resistance, it has excellent heat resistance under high-temperature curing conditions, thereby suppressing the occurrence of cracks. To provide a highly heat-resistant negative-type photosensitive resin composition capable of implementing a film, not showing a decrease in light transmittance due to yellowing, etc., and implementing a high resolution, and a cured film prepared therefrom.

In order to achieve the above object, the present invention,

(a) (a-1) an organosiloxane polymer containing a siloxane unit having a (meth)acrylate group; (a-2) an organosiloxane polymer containing a siloxane unit having a phenyl group; And (b) a photopolymerization initiator, and does not contain an acrylate compound having an ethylenically unsaturated double bond.

The present invention also provides a cured film prepared from the photosensitive resin composition.

The photosensitive resin composition of the present invention not only enables high resolution implementation, such as implementing the same fine pattern even at a low exposure amount of about 1/10 compared to the composition disclosed in the Korean Patent No. 10-0963111, but also the domestic patent No. 10-1121936. It can exhibit a relatively low dielectric constant compared to the composition disclosed in the issue, and has excellent heat resistance under high-temperature curing conditions, thereby suppressing the occurrence of cracks, thereby enabling a flat film to be realized, and does not show a decrease in light transmittance due to yellowing, etc., therefore, a semiconductor device or a display device It can be usefully used in the manufacture of a protective film, an insulating film, and an optical waveguide.

The present invention uses a siloxane polymer containing a (meth)acrylate group having excellent photosensitivity and a siloxane polymer having a phenyl group having excellent heat resistance, but retains photosensitivity by excluding compounds having ethylenically unsaturated double bonds that reduce heat resistance. A stable photosensitive resin composition that does not generate cracks or yellowing at high temperatures has been developed.

Hereinafter, the constituent components of the present invention will be described in detail.

(a) organosiloxane polymer

The composition of the present invention comprises (a-1) an organosiloxane polymer comprising a siloxane unit having a (meth)acrylate group and (a-2) an organosiloxane polymer comprising a siloxane unit having a phenyl group. At this time, in terms of the film residual ratio, the photosensitive resin composition contains (a-1) an organosiloxane polymer and (a-2) an organosiloxane polymer in the range of 1:99 to 70:30, preferably in the range of 3:97 to 65:35, and further Preferably, it may be included in a weight ratio in the range of 5:95 to 55:45.

The (a-1) organosiloxane polymer includes at least one siloxane unit selected from Formulas 1 and 2 below, and the (a-2) organosiloxane polymer includes at least one siloxane unit selected from Formulas 3 and 4 below. do:

In the above formula, A is each independently a single bond, a C ₁ -C ₉ alkylene group, a C ₃ -C ₁₄ cycloalkylene group, a C ₆ -C ₁₄ arylene group, a C ₇ -C ₁₄ alkylarylene group or a C ₇ -C ₁₄ It is an arylalkylene group, and X is each independently a (meth)acrylate group.

In the above formula, B is each independently the same as the definition for A in Formula 1 or Formula 2, and Y is each independently a phenyl group, _one selected from the group consisting of halogen, hydroxy, nitro, and C 1 -C _{4 alkyl} It may have more than one substituent.

In addition, (a-1) an organosiloxane polymer, (a-2) an organosiloxane polymer, or both, are at least one siloxane unit selected from the group consisting of the following formulas 5 to 7 (however, the siloxane units of formulas 1 to 4 and May further include:

In the above formula, R is each independently a hydrogen atom, a C ₁ -C ₉ alkyl group, a C ₃ -C ₁₄ cycloalkyl group, a C ₆ -C ₁₄ aryl group, a C ₇ -C ₁₄ alkylaryl group or a C ₇ -C ₁₄ arylalkyl group to be.

It is preferable that the (a-1) organosiloxane polymer, (a-2) the organosiloxane polymer, or both further include a siloxane unit represented by the above formula (7). In particular, the (a-2) organosiloxane polymer is a mixture of one or more organosiloxane polymers containing a siloxane unit of Formula 7 and one or more organosiloxane polymers not containing a siloxane unit of Formula 7. It is more preferable in

The weight average molecular weight of each of the (a-1) organosiloxane polymer and (a-2) the organosiloxane polymer may be 1,000 to 500,000, preferably 1,000 to 100,000, and more preferably 2,000 to 50,000. When the weight average molecular weight of the organosiloxane polymer is 1,000 or more, cracks do not occur on the surface during curing, and a desirable thickness of the cured film may be realized. In addition, when the weight average molecular weight is 500,000 or less, it is possible to improve surface flatness by maintaining the viscosity required for coating.

(b) photopolymerization initiator

The photopolymerization initiator used in the present invention acts to initiate polymerization of a compound having a (meth)acrylate group by wavelengths such as visible light, ultraviolet light, and far ultraviolet light.

Such a photoinitiator may be any photoinitiator known in the art, and acetophenone-based compound, biimidazole-based compound, triazine-based compound, onium salt-based compound, benzoin-based compound, benzophenone-based compound, diketone-based compound, α -One or more selected from the group consisting of diketone compounds, polynuclear quinone compounds, thioxanthone compounds, diazo compounds, imide sulfonate compounds, oxime compounds, carbazole compounds, and sulfonium borate compounds It is desirable. Among them, Korean Patent Application Publication No. 2004-0007700, same as 2005-0084149, same as 2008-0083650, same as 2008-0080208, same as 2007-0044062, same as 2007-0091110, same as 2007 -0044753, same as 2009-0009991, same as 2009-0093933, same as 2010-0097658, same as 2011-0059525, international publication WO 10/102502, same as WO 10/133077 An oxime compound is preferable, and commercial items such as OXE-01, OXE-02 (manufactured by Ciba), and N-1919 (manufactured by Adeka) are preferable in terms of high sensitivity and resolution. In addition, the photoinitiator may be used alone or in combination of two or more as needed.

The photopolymerization initiator is used in an amount of 0.1 to 20 parts by weight, preferably 3 to 17 parts by weight, based on 100 parts by weight of the organosiloxane polymer (based on solid content). If the content of the polymerization initiator is within the above range, curing by exposure is sufficiently performed to easily obtain a pattern of the organic insulating film, and there is an advantage that the organic insulating film is sufficiently in close contact with the lower layer.

Hereinafter, (c) a silane-based coupling agent, (d) a surfactant, and (e) a solvent that can be used in the present invention will be described.

(c) Silane coupling agent

The silane-based coupling agent used in the present invention is added to improve the adhesion between the formed cured film and the substrate. As the silane-based coupling agent, a functional silane compound having a reactive substituent is used. Examples include a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.

Specific examples of the silane-based coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -At least one selected from glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane may be used. Preferably, γ-glycidoxypropyltriethoxysilane and/or γ-glycidoxypropyltrimethoxysilane having an epoxy group may be used in view of the residual film rate and adhesion to the substrate. In addition, the silane-based coupling agent may be used alone or in combination of two or more as needed.

The silane-based coupling agent of the present invention is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the organosiloxane polymer (based on solid content). When the content of the silane-based coupling agent is 0.1 parts by weight or more, adhesion to the substrate is improved, and when the content is 20 parts by weight or less, thermal stability at high temperature is improved, and staining after development can be prevented.

(d) surfactant

The photosensitive resin composition according to the present invention contains a surfactant to improve coating performance. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and other surfactants.

As a surfactant, for example, FZ2122 (Dow Corning Toray Co., Ltd.), BM-1000, BM-1100 (manufactured by BM CHEMIE), Megapack F142D, F172, F173, F183 (Dai Nippon Ink Chemical Co., Ltd.) Shiki Corporation), Florade FC-135, copper FC-170 C, copper FC-430, copper FC-431 (manufactured by Sumitomo 3M Limited), Suffron S-112, B S-113, B S-131, East S-141, East S-145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (Asahi Glass Co., Ltd. Manufacture), Ftop EF301, 303, 352 (manufactured by Shin-Akida Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC- Fluorine-based and silicone-based surfactants such as 190 (manufactured by Toray Silicone Co., Ltd.); Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, and polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether , Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), or (meth)acrylic acid-based copolymer Polyflow No.57,95 (manufactured by Kyoeisha Yuji Chemical Co., Ltd.) alone or two types These can be used in parallel.

The surfactant is preferably used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the organosiloxane polymer (based on solid content), and more preferably 0.001 to 1 part by weight. When the content of the surfactant is 0.001 parts by weight or more, coating properties are improved, no cracks are generated on the coated surface, and when the content is 5 parts by weight or less, it is advantageous in terms of price.

(e) solvent

The photosensitive resin composition according to the present invention may include a solvent, particularly an organic solvent, so that the solid content is 20 to 90% by weight, preferably 20 to 50% by weight, based on the total weight of the composition. The solid content refers to a composition component excluding a solvent in the resin composition of the present invention.

Specific examples of the solvent include propylene glycol methyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, propylene glycol methyl ether, ethylacetoacetate, ethylacetolactate, ethylcellulose-acetate, gamma-butyrolactone , 2-methoxyethyl acetate, ethyl-beta-ethoxypropionate, normal propyl acetate, normal butyl acetate, and mixtures thereof, preferably propylene glycol methyl ether acetate, 4-hydroxy-4- At least one selected from methyl-2-pentanone, propylene glycol methyl ether, and ethylacetoacetate may be used.

In addition to the above components, the composition of the present invention may further include additional components commonly used in thermosetting resin compositions and photosensitive resin compositions, if necessary.

In addition, the present invention provides a cured film prepared from the photosensitive resin composition.

The cured film may be prepared by a method known in the art, for example, by applying the photosensitive resin composition on a substrate and then curing it. More specifically, in the curing, the photosensitive resin composition applied on the substrate is pre-cured at, for example, 60 to 130°C to remove the solvent, and then exposed using a photomask having a desired pattern, and a developer (e.g., tetra By developing with methyl ammonium hydroxide solution (TMAH)), a pattern can be formed on the coating layer. Thereafter, if necessary, the patterned coating layer may be post-bake at 180 to 350° C. for 10 minutes to 5 hours to prepare a desired cured film. The exposure may be performed at an exposure amount of 10 to 200 mJ/cm 2 in a wavelength range of 200 to 450 nm. According to the method of the present invention, a desired pattern can be easily formed in terms of a process.

The cured film of the present invention prepared as described above has excellent physical properties such as having a light transmittance of 95% or more in a wavelength range of 400 to 800 nm, and does not generate cracks even at a high temperature of 250 to 300°C, and can be usefully used as a protective film of electronic components. . Accordingly, the present invention provides an electronic component including the cured film as a protective film.

Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

The weight average molecular weight described in the following preparation examples is a polystyrene conversion value measured by gel permeation chromatography (GPC).

Preparation Example 1: Preparation of organosiloxane polymer ([A-1])

After filling 153g of distilled water into a 3-neck round bottom flask with a cooling jacket equipped with a condenser, 15g of acetic acid was mixed, and the temperature was raised to about 5℃ by stirring at a speed of about 300 rpm using a stirrer while adjusting the jacket temperature with a 3℃ refrigerant. Lowered it.

In the flask, 303 g of a mixture in which 3-[(methacryloxy)propyl]trimethoxysilane:tetramethoxysilane (TMOS) was mixed at a molar ratio of 75:25, respectively, was taken and a rate of 2.0 g/min was carried out through a metering pump. Was put into. The reaction temperature was maintained at less than 10°C, and polymerization was performed using hydrolysis and condensation polymerization for 3 hours. After polymerization was completed, the mixture was allowed to stand for 30 minutes, after which propylene glycol methyl ether acetate (PGMEA) was added to dissolve the organosiloxane polymer, followed by stirring for 30 minutes. Then, after removing methyl alcohol and water in the reaction product through atmospheric distillation, 153 g of distilled water was added and stirred for 1 hour to remove residual acetic acid and alcohol, and water was removed through low-temperature vacuum distillation to obtain a product. Aged at °C for 72 hours to prepare an organosiloxane polymer [A-1]. Through GPC analysis, it was confirmed that this compound is a siloxane compound having a weight average molecular weight of about 4,500.

Preparation Example 2: Preparation of organosiloxane polymer ([A-2])

0.07 g of 0.1N hydrochloric acid (0.0019 mol) and 40.57 g of water (2.25 mol) were added to the reaction flask, followed by stirring. Here, a mixed solution containing 92.45 g of phenyltrimethoxysilane (0.383 mol, Aldrich) and 34.29 g of methyltrimethoxysilane (0.192 mol, Aldrich) was added and stirred at room temperature for 1 hour. Then, after the reaction flask was equipped with a condenser and a Dean-Stark trap, distillation was performed at 105° C. for 2 hours, and the reaction was carried out at 100° C. for 3 hours. 6 g of propylene glycol methyl ether acetate (PGMEA) was added to the reaction product, the reaction product was cooled, and the acid remaining in the reaction product was removed through an ion exchange column. The reactant was put into a reactor, and water and alcohol were removed under reduced pressure at a temperature of 45° C. to synthesize an organosiloxane polymer [A-2]. Through GPC analysis, it was confirmed that this compound is a siloxane compound having a weight average molecular weight of about 14,000.

Preparation Example 3: Preparation of organosiloxane polymer ([A-3])

In a round bottom flask equipped with a thermometer inside, 764 g of a mixture of phenyltrimethoxysilane: methyltrimethoxysilane: tetramethoxysilane in a molar ratio of 25:50:25, respectively, was added, and then 134g of distilled water and 12g of acetic acid. Was put in. After installing the flask in a heating jacket, the flask was stirred at room temperature using a stirrer at a speed of about 400 rpm and stirred for about 20 minutes until the solution became transparent.

The transparent flask was heated for 1 hour to perform forced reflux, and then 455 g of propylene glycol methyl ether acetate (PGMEA) was added, followed by distillation under atmospheric pressure while heating again to remove acetic acid and low molecular weight unreacted substances. When the thermometer installed inside the flask reached 100° C., heating was stopped, and 455 g of propylene glycol methyl ether acetate (PGMEA) was re-introduced to lower the temperature of the reaction product, followed by stirring for 1 minute to mix the reaction product.

The heating jacket was removed, the flask was cooled to room temperature while stirring, and then aged for 60 minutes to synthesize an organosiloxane polymer [A-3]. Through GPC analysis, it was confirmed that this compound is a siloxane compound having a weight average molecular weight of about 7,800.

Preparation Example 4: Preparation of organosiloxane polymer ([A-4])

After filling 200g of distilled water into a cooling jacketed 3-neck round bottom flask equipped with a condenser, 15g of acetic acid was mixed, and the temperature was raised to about 5℃ by stirring at a speed of about 300 rpm using a stirrer while adjusting the jacket temperature with a 3℃ refrigerant. Lowered it.

In the flask, 3-[(methacryloxy)propyl]trimethoxysilane: phenyltrimethoxysilane: methyltrimethoxysilane: tetramethoxysilane was mixed in a molar ratio of 20:30:30:20, respectively 368 g was taken and added at a rate of 2.0 g/min through a metering pump. The reaction temperature was maintained at less than 10°C, and polymerization was performed using hydrolysis and condensation polymerization for 5 hours. After completion of the polymerization, the mixture was allowed to stand for 1 hour, after which propylene glycol methyl ether acetate (PGMEA) was added to dissolve the organosiloxane polymer, followed by stirring for 30 minutes. Subsequently, after removing methyl alcohol and water in the reaction product through atmospheric distillation, 200 g of distilled water was added and stirred for 4 hours to remove residual acetic acid and alcohol, and water was removed through low-temperature vacuum distillation to obtain a product. Aged at °C for 72 hours to prepare an organosiloxane polymer [A-4]. Through GPC analysis, it was confirmed that this compound is a siloxane compound having a weight average molecular weight of about 2,800.

The composition of the organosiloxane polymer prepared in Preparation Examples 1 to 4 is shown in Table 1 below.

division Organosiloxane polymer
Content of polymerization unit (mol%) Weight average
Molecular Weight T_methacrylate T_methyl T_phenyl TMOS Production Example 1 [A-1] 75 25 4,500 Production Example 2 [A-2] 80 20 14,000 Production Example 3 [A-3] 50 25 25 7,800 Production Example 4 [A-4] 20 30 30 20 2,800

Example 1

(a) 40 parts by weight of organosiloxane polymer [A-1] synthesized in Preparation Examples 1 and 2 (based on solid content) and 60 parts by weight of organosiloxane polymer [A-2] (based on solid content), (b) photopolymerization 3.3 parts by weight of initiator N-1919 (manufactured by Adeka), (c) 0.3 parts by weight of silane coupling agent GPTMS (γ-glycidoxypropyltrimethoxysilane, manufactured by Aldrich), and (d) FZ2122 as a fluorine-based surfactant ( Dow Corning Toray Corporation) 0.16 parts by weight and (e) propylene glycol methyl ether acetate as an organic solvent were mixed so that the solid content was 25% by weight based on the total weight of the composition to prepare a liquid photosensitive resin composition.

Example 2

As the component (a), 40 parts by weight of the organosiloxane polymer [A-1] synthesized in Preparation Examples 1 and 3 (based on the solid content) and 60 parts by weight of the organosiloxane polymer [A-3] (based on the solid content), respectively, Except for using, it was prepared in the same manner as in Example 1.

Example 3

As the component (a), 5 parts by weight of the organosiloxane polymer [A-1] synthesized in Preparation Examples 1 to 3 (based on the solid content), 10 parts by weight of the organosiloxane polymer [A-2] (based on the solid content), And the organosiloxane polymer [A-3] 85 parts by weight (based on solid content), and was prepared in the same manner as in Example 1 above.

Example 4

As the component (a), 15 parts by weight of the organosiloxane polymer [A-1] synthesized in Preparation Examples 1 to 3 (based on the solid content), 10 parts by weight of the organosiloxane polymer [A-2] (based on the solid content), And the organosiloxane polymer [A-3] was prepared in the same manner as in Example 1, except that 75 parts by weight (based on solid content) were used.

Example 5

As the component (a), 40 parts by weight of the organosiloxane polymer [A-1] synthesized in Preparation Examples 1 to 3 (based on the solid content), 10 parts by weight of the organosiloxane polymer [A-2] (based on the solid content), And the organosiloxane polymer [A-3] was prepared in the same manner as in Example 1, except that 50 parts by weight (based on solid content) were used.

Comparative Example 1

As the component (a), it was prepared in the same manner as in Example 1, except that only 100 parts by weight (based on solid content) of the organosiloxane polymer [A-1] synthesized in Preparation Example 1 was used.

Comparative Example 2

As the component (a), it was prepared in the same manner as in Example 1, except that only 100 parts by weight (based on solid content) of the organosiloxane polymer [A-2] synthesized in Preparation Example 2 was used.

Comparative Example 3

As the component (a), it was prepared in the same manner as in Example 1, except that only 100 parts by weight (based on solid content) of the organosiloxane polymer [A-3] synthesized in Preparation Example 3 was used.

Comparative Example 4

As the component (a), it was prepared in the same manner as in Example 1, except that only 100 parts by weight (based on solid content) of the organosiloxane polymer [A-4] synthesized in Preparation Example 4 was used.

Comparative Example 5

As the component (a), 10 parts by weight of the organosiloxane polymer [A-1] synthesized in Preparation Examples 1 and 3 (based on the solid content) and 60 parts by weight of the organosiloxane polymer [A-3] (based on the solid content), respectively, Use; It was prepared in the same manner as in Example 1, except that 30 parts by weight of an acrylate-based compound M-520 (manufactured by Toagosei) having an ethylenically unsaturated double bond was additionally used.

Comparative Example 6

As the component (a), 10 parts by weight of the organosiloxane polymer [A-1] synthesized in Preparation Examples 1 and 3 (based on the solid content) and 70 parts by weight of the organosiloxane polymer [A-3] (based on the solid content), respectively, Use; It was prepared in the same manner as in Example 1, except that 20 parts by weight of an acrylate-based compound M-520 (manufactured by Toagosei) having an ethylenically unsaturated double bond was additionally used.

Comparative Example 7

As the component (a), 20 parts by weight of the organosiloxane polymer [A-1] synthesized in Preparation Examples 1 and 3 (based on the solid content) and 50 parts by weight of the organosiloxane polymer [A-3] (based on the solid content), respectively, Use; It was prepared in the same manner as in Example 1, except that 30 parts by weight of an acrylate-based compound M-520 (manufactured by Toagosei) having an ethylenically unsaturated double bond was additionally used.

The composition (parts by weight) of the resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 7 are shown in Table 2 below, and crack resistance (250° C. and 300° C.) and light transmittance of the cured film prepared from each of them. Was measured and the results are shown in Table 3 below.

division Organosiloxane polymer Ethylene unsaturated double bond acrylate compound Light polymerization
Initiator Silane coupling agent Surfactants menstruum [A-1] [A-2] [A-3] [A-4] Example 1 40 60 3.3 0.3 0.16 25% by weight of solid content Example 2 40 60 Example 3 5 10 85 Example 4 15 10 75 Example 5 40 10 50 Comparative Example 1 100 Comparative Example 2 100 Comparative Example 3 100 Comparative Example 4 100 Comparative Example 5 10 60 30 Comparative Example 6 10 70 20 Comparative Example 7 20 50 30

1. 250℃ crack resistance evaluation

After rotating the photosensitive resin composition onto a glass substrate, pre-baking for 90 seconds on an on-plate maintained at 100°C to form a dry coating film with a thickness of 1.5 μm, and an aligner that emits a wavelength of 200 nm to 450 nm on the composition film. Trade name MA6) was exposed through a pattern mask to be about 30 mJ/cm 2 based on 365 nm, and developed through a spray nozzle at 25° C. with a developer consisting of a 2.38% tetramethylammonium hydroxide aqueous solution. The obtained exposed film was heated in a convection oven at 250° C. for 30 minutes, taken out, cooled to room temperature, and then observed for cracks by observing the surface. A good level was judged as OK, and if it was bad, it was judged as NG.

2. 300℃ crack resistance evaluation

Produced in the same manner as in the 250° C. crack resistance evaluation, but after heating at 300° C. for 30 minutes in a convection oven, taken out, cooled to room temperature, and observed for cracks by observing the surface. A good level was judged as OK, and if it was bad, it was judged as NG.

3. Light transmittance evaluation

The composition was spin-coated on an organic substrate, and a cured film having a thickness of about 1.5 μm was formed through the same process as in the above 300° C. crack resistance evaluation. At this time, it was heated in a convection oven at 300° C. for 30 minutes and then taken out, and the light transmittance in the wavelength range of 400 nm to 800 nm was evaluated through ultraviolet/visible spectrum measurement. If it was 90% or more, it was judged to be excellent, and if it was 95% or more, it was judged to be very excellent. When measurement was impossible, it was evaluated as NG.

division Crack resistance
(250℃) Crack resistance
(300℃) Light transmittance (%)
(400~800nm) Example 1 OK OK 98.341 Example 2 OK OK 97.963 Example 3 OK OK 97.736 Example 4 OK OK 98.595 Example 5 OK OK 97.84 Comparative Example 1 OK NG NG Comparative Example 2 OK NG NG Comparative Example 3 OK NG NG Comparative Example 4 OK NG NG Comparative Example 5 OK OK 88.71 Comparative Example 6 OK OK 82.578 Comparative Example 7 OK OK 83.42

As can be seen from the results of Table 3, the resin compositions prepared in Examples 1 to 5 used a siloxane polymer containing a (meth)acrylate group having excellent photosensitivity and a siloxane polymer having a phenyl group having excellent heat resistance, but the heat resistance Excluding the compound having an ethylenically unsaturated double bond to reduce the exhibited excellent crack resistance at 250 ℃ and 300 ℃ was also excellent light transmittance. On the other hand, Comparative Examples 1 to 7 in which only one of a siloxane polymer containing a (meth)acrylate group and a siloxane polymer having a phenyl group are used, or both siloxane polymers are used but a compound having an ethylenically unsaturated double bond is also used. The resin composition prepared in showed poor crack resistance or low light transmittance at a high temperature of 300°C.

Claims (6)

(a) (a-1) an organosiloxane polymer containing a siloxane unit having a (meth)acrylate group; (a-2) an organosiloxane polymer containing a siloxane unit having a phenyl group; And (b) a photopolymerization initiator, and does not contain an acrylate compound having an ethylenically unsaturated double bond,
The (a-2) organosiloxane polymer is a photosensitive resin composition comprising a mixture of at least one organosiloxane polymer containing a siloxane unit of the following formula (7) and at least one organosiloxane polymer not containing a siloxane unit of the following formula (7):
[Formula 7]

. The method of claim 1, wherein the (a-1) organosiloxane polymer comprises at least one siloxane unit selected from Formulas 1 and 2 below, and the (a-2) organosiloxane polymer is 1 selected from Formulas 3 and 4 below. A photosensitive resin composition comprising more than one type of siloxane unit:
[Formula 1]

[Formula 2]

In the above formula, A is each independently a single bond, C ₁ -C ₉ Alkylene group, C ₃ -C ₁₄ Cycloalkylene group, C ₆ -C ₁₄ Arylene group, C ₇ -C ₁₄ Alkylarylene group or C ₇ -C ₁₄ It is an arylalkylene group, and X is each independently a (meth)acrylate group.
[Formula 3]

[Formula 4]

In the above formula, B is each independently a single bond, a C ₁ -C ₉ alkylene group, a C ₃ -C ₁₄ cycloalkylene group, a C ₆ -C ₁₄ arylene group, a C ₇ -C ₁₄ alkylarylene group or a C ₇ -C ₁₄ It is an arylalkylene group, and Y is each independently a phenyl group, and may have one or more substituents selected from the group consisting of _{halogen, hydroxy, nitro, and C 1} -C _{4 alkyl.} The method of claim 2, wherein the (a-1) organosiloxane polymer further comprises at least one siloxane unit selected from the group consisting of the following formulas 5 to 7 (however, different from the siloxane units of formulas 1 to 4) and,
Photosensitive, characterized in that the (a-2) organosiloxane polymer further comprises at least one siloxane unit selected from the group consisting of the following formulas 5 and 6 (however, different from the siloxane units of the formulas 1 to 4) Resin composition:
[Formula 5]

[Formula 6]

In the above formula, R is each independently a hydrogen atom, a C ₁ -C ₉ alkyl group, a C ₃ -C ₁₄ cycloalkyl group, a C ₆ -C ₁₄ aryl group, a C ₇ -C ₁₄ alkylaryl group or a C ₇ -C ₁₄ arylalkyl group to be. The photosensitive resin composition according to claim 3, wherein the (a-1) organosiloxane polymer further comprises a siloxane unit represented by the formula (7). delete The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises the (a-1) organosiloxane polymer and the (a-2) organosiloxane polymer in a weight ratio of 1:99 to 70:30. .