KR20130113635A - Photosensitive resin composition comprising organopolysiloxane - Google Patents

Abstract

PURPOSE: A photosensitive resin composition is provided to form a uniform and stable coated film when coated on a substrate, to generate no stain such as resin stain and cumulus stain, and to facilitate the pattern formation. CONSTITUTION: A photosensitive resin composition comprises a) an organic siloxane polymer including a siloxane unit having at least one functional group selected from the group consisting of oxetane, epoxy, hydroxy and thiol; b) an acrylate compound having at least one ethylenic unsaturated double bond; c) a polymer or an oligomer including at least one epoxy (however, it is different from a) organic siloxane polymer); and D) an acid generator.

Description

Photosensitive resin composition containing an organosiloxane polymer {PHOTOSENSITIVE RESIN COMPOSITION COMPRISING ORGANOPOLYSILOXANE}

The present invention relates to a photosensitive resin composition comprising an organosiloxane polymer. Specifically, the present invention can form a uniform and stable coating film when applied on the substrate, there is no spot, easy to develop the pattern, and photosensitive characteristics such as adhesion, heat resistance, light transmittance, resolution with the substrate The present invention relates to a photosensitive resin composition comprising an organosiloxane polymer which is excellent in film rate, can be thermally cured at a particularly low temperature, and is suitable for forming a thin film having excellent hardness after such low temperature curing.

A protective film is formed on a device such as a touch panel device (TPD), a liquid crystal display (LCD), a charge coupled device (CCD), or a CMOS (Complementary Metal-Oxide Semiconductor) sensor to protect an internal device. It is.

The apparatus undergoes various processes such as high temperature, light irradiation, sputtering for electrode formation during its manufacturing process. therefore, The protective film is also required to have high heat resistance and light resistance and not to cause deterioration such as coloring, yellowing, and whitening over a long period of time. In addition, when the protective film is coated on the substrate, the coating film is formed on a uniform and stable surface without staining such as resin stains, agglomeration stains, and other components having a poor heat resistance. The curing should be able to be completed within and outside the curing time. In particular, the protective film should have a light transmittance of 95% or more in the 400-800nm wavelength range, in order to ensure excellent light transmittance, 5B or more adhesive force is required, and a hardness of 6H or more pencil hardness tester to secure scratch resistance .

In particular, there has been a problem that the hardness of the coating film is poor after low temperature curing.

International Patent Publication WO 2007/001039 discloses a curable organosiloxane polymer resin composition and an optical component comprising a cured product thereof having a light transmittance of 80% or more in a cured state, and as an effect thereof, excellent transmittance and transmittance upon exposure to high temperature Although a small reduction of and good adhesion are described, the composition still has the problem of curing at 150 ° C. for at least 15 minutes and not having sufficient hardness.

[Patent Document] International Publication No. WO 2007/001039

Accordingly, the problem of the present invention is that it can form a uniform and stable coating film when applied on the substrate, there is no spot and easy pattern development, and the photosensitive properties such as adhesion, heat resistance, light transmittance, resolution with the substrate It is to provide a photosensitive resin composition comprising an organosiloxane polymer which is excellent in film ratio and particularly suitable for forming a thin film having excellent hardness after curing at low temperature.

As a technical means for achieving the above object, the present invention is a) an organosiloxane polymer comprising a siloxane unit having at least one functional group selected from the group consisting of an oxetane group, an epoxy group, a hydroxy group and a thiol group; b) an acrylate compound having at least one ethylenically unsaturated double bond; c) a polymer or oligomer comprising at least one epoxy group, wherein the polymer differs from the a) organosiloxane polymer; And d) provides a photosensitive resin composition comprising an acid generator.

The composition according to the present invention forms a uniform and stable coating film upon application on a substrate, does not cause stains such as resin stains, aggregates, and the like, and easily forms a pattern. Moreover, the thin film obtained after low temperature curing in a range of 150 ° C. or lower has a resolution. Is high, has a light transmittance of 95% or more in the wavelength range of 400 to 800 nm, adhesion to the substrate is 5B or more, and particularly hardness is 6H or more.

The basic shape and properties of siloxane polymers are determined by how many or few networks there are between the silicon and oxygen atoms. In other words, if a relatively low number of organic groups bonded to one Si atom is in the range of 1 to 1.5, the network can be regarded as a solid siloxane polymer in a three-dimensionally high density crosslinked form (crosslinked with a large number of Si-O). If two or more organic groups are bonded, the siloxane polymer is in the form of liquid or elastomer.

Units constituting the siloxane polymer may be divided into the following four types, as shown in Table 1, depending on the number of oxygen atoms bonded to one silicon atom.

[Table 1]

The siloxane unit in which the Si atom in the siloxane polymer is connected to one oxygen atom is called a monofunctional unit, and the siloxane unit in which the Si atom is connected to two oxygen atoms is called a difunctional unit (D type). The siloxane unit connected with the two oxygen atoms is called a trifunctional unit (T type), and the siloxane unit with the Si atom connected with the four oxygen atoms is called a tetrafunctional unit (Q type).

Compounds in which any two siloxane units are connected among the four types of siloxane units are called siloxane dimers (disiloxanes), and compounds in which three siloxane units are linked are called siloxane trimers (trisiloxanes), and a plurality of siloxane units The case of forming a network is called siloxane polymer (polysiloxane).

In the silicon polymerization, a reactor is a hydroxy group (Si-OH) bonded to a silicon atom, and these silanols are condensation-polymerized as a monomer to synthesize a siloxane polymer. Therefore, the synthesis of the siloxane polymer can be largely divided into two stages: synthesis of the silanol monomer and synthesis of the siloxane polymer through condensation polymerization thereof.

Chlorosilane is generally used for the synthesis of the silanol monomer, but in some cases, an alkoxysilane such as methoxysilane or ethoxysilane may be used.

For chlorosilanes

As shown in the following reaction formula, since the Si-Cl bond has a very high reactivity with water, Cl is rapidly hydrolyzed to form silanol, and the synthesized silanol is condensed to form siloxane.

Hydrolysis:

≡SiCl + H ₂ O → ≡Si-OH + HCl

Condensation reaction:

≡Si-OH + OH-Si≡ → ≡Si-O-Si≡ + H ₂ O

For alkoxysilanes

As shown in the following scheme, the Si-OR bond is hydrolyzed with water to form alcohol and silanol, and the silanol is then condensed with residual alkoxysilane or other silanol to form siloxane.

Hydrolysis ：

≡Si-OR + H ₂ O → ≡Si-OH + ROH

Condensation reaction:

≡Si-OH + ≡Si-OH → ≡Si-O-Si≡ + H ₂ O

≡Si-OH + ≡Si-OR → ≡Si-O-Si≡ + ROH

Mono-, di-, tri- and tetra-functional siloxane units in the siloxane polymer can be obtained by hydrolysis and condensation reactions from chlorosilanes or alkoxysilanes in this manner. For example, the bifunctional siloxane unit is formed by condensation reaction after producing silanediol through hydrolysis of dichlorodimethylsilane or dimethoxydimethylsilane.

Hereinafter, the structural component of this invention is demonstrated concretely.

a) Organosiloxane  polymer

The organosiloxane polymer of the present invention includes siloxane units having at least one functional group selected from the group consisting of oxetane group, epoxy group, hydroxy group and thiol group. Preferably, the siloxane units are one or more selected from the following general formulas (1) and (2).

[Formula 1]

(2)

In the above Formulas 1 and 2,

Each A is 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 Alkyl arylene group or C ₇ -C ₁₄ Arylalkylene group, preferably C ₁ -C ₉ Alkylene group or C ₃ -C ₁₄ A cycloalkylene group, more preferably C ₁ -C ₅ Alkylene group or C ₃ -C ₁₀ cycloalkylene group, still more preferably C ₁ -C ₅ An alkylene group,

Y is each independently —OH, —Z, —OZ or —SH, Z is — (CH ₂ ) nQ (n is an integer of 0 to 5), and Q is an epoxy group or an oxetane group.

In the organosiloxane polymer of the present invention, the molar ratio of the siloxane units having at least one functional group selected from the group consisting of oxetane group, epoxy group, hydroxy group and thiol groups to the total polymerized units forming the organosiloxane polymer is 0.01 to 0.90, more preferably. Preferably 0.03 to 0.85, even more preferably 0.05 to 0.80. When the molar ratio of the siloxane units having one or more functional groups is 0.01 or more, the ratio of functional molecules participating in the crosslinking at the time of thermal curing is increased, so that the crosslinkability is increased, so that high hardness can be realized at low temperature, and when the storage is 0.90 or less, Stability and heat resistance may be excellent, and hardness degradation due to microcavities formed in the thin film may be improved.

The organosiloxane polymer according to the present invention may further include one or more siloxane units selected from the group consisting of the following Chemical Formulas 3 to 5 as polymerized units.

(3)

[Formula 4]

[Chemical Formula 5]

In Formulas 3 to 5, each R is independently a hydrogen atom, C ₁ -C ₉ Alkyl group, C ₃ -C ₁₄ A cycloalkyl group, a C ₆ -C ₁₄ Aryl group, C ₇ -C ₁₄ Alkylaryl groups or C ₇ -C ₁₄ Arylalkyl group, preferably a hydrogen atom, C ₁ -C ₉ Alkyl group or C ₆ -C ₁₄ Aryl group, more preferably a C ₁ -C ₅ alkyl group or a C ₆ -C ₁₀ It is an aryl group, More preferably, it is a methyl group or a phenyl group.

The organosiloxane polymer of the present invention has a weight average molecular weight of 1,000 to 500,000, more preferably 1,500 to 100,000, even more preferably 2,000 to 50,000. When the weight average molecular weight of the organosiloxane polymer of the present invention is 1,000 or more, the shrinkage rate is reduced, so that cracks do not occur on the coated surface during the curing process, the thickness of the thin film is easily realized, heat resistance and surface hardness are excellent, and etching is performed by a developer. Therefore, the thin film thickness at the time of application can be prevented from decreasing after development. In addition, when the weight average molecular weight is 500,000 or less, the viscosity does not increase any more to maintain the flowability, thereby improving the surface planarity, and uniform lamination of the polymer during the coating and curing process It can solve the problem of thin film density and poor hardness due to the empty microcavity inside the film, improve light transmittance, and especially improve the solubility in the developer so that high resolution pattern can be realized after the photocuring and developing process. It is possible.

On the other hand, when the organosiloxane polymer of the present invention includes a tetrafunctional siloxane unit as the polymer unit, the crosslinking tendency of the polymer is increased and the film density becomes dense, thereby improving the hardness after heat curing. The molar ratio of the tetrafunctional siloxane units to the total polymerized units forming the organosiloxane polymer is from 0.01 to 0.90, more preferably from 0.05 to 0.50, even more preferably from 0.10 to 0.30. Within this range, the storage stability and light transmittance are excellent.

b) one or more Ethylenic  With unsaturated double bonds Acrylate series  compound

An acrylate compound having at least one ethylenically unsaturated double bond as a composition component of the composition of the present invention improves the hardness, sensitivity, and residual film ratio of the thin film surface obtained from the composition.

The present invention may use an acrylate compound containing at least one reactive ethylenic double bond, more preferably two or more reactive ethylenic double bonds as the acrylate compound having an ethylenically unsaturated double bond, specific examples, ethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tree Monoester of (meth) acrylate and succinic acid, pentaerythritol tetra (meth) acrylate, dipentaerythritol Other (meth) acrylate, dipentaerythritol hexa (meth) acrylate, monoester of dipentaerythritol penta (meth) acrylate and succinic acid, caprolactone modified dipentaerythritol hexa (meth) acrylate, penta Erythritol triacrylate hexamethylene diisocyanate (reactant of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, bisphenol A epoxy One or more selected from the group consisting of acrylate and ethylene glycol monomethyl ether acrylate may be used, but is not limited thereto.

In the present invention, (meth) acryl and (meth) acrylate refer to acryl and / or methacrylate and acrylate and / or methacrylate, respectively.

In addition, the content of the acrylate compound having at least one ethylenically unsaturated double bond is 1 to 80 parts by weight based on 100 parts by weight (based on the solid content) of the organosiloxane polymer to maintain the light transmittance of the thin film and to maintain adhesion and surface It is preferable because it can improve smoothness and maintain workability.

c) a polymer comprising at least one epoxy group or Oligomer

The composition of the present invention comprises a polymer or oligomer comprising at least one epoxy group as an auxiliary curing agent for increasing the internal density of the thin film formed through the thermal curing process and at the same time improving the adhesion to the substrate.

Specific examples of the polymer or oligomer containing one or more epoxy groups of the present invention include a compound including a unit represented by the following formula (6), and commercially available products thereof include GHP03 (Glycidyl methacrylate Homopolymer, Miwon) comprising a unit represented by the formula (7) Company).

[Formula 6]

In Formula 6,

R ² represents a hydrogen atom or a straight or branched C ₁ -C ₅ alkyl group, preferably a straight or branched C ₁ -C ₅ alkyl group,

R ³ represents a hydrogen atom or a C ₁ -C ₂ alkyl group, preferably a hydrogen atom,

m represents the integer of 1-10, Preferably 1-5.

[Formula 7]

It is preferable that the polymer or oligomer containing one or more epoxy groups is 1-50 weight part with respect to 100 weight part of said organosiloxane polymers. When the content is 1 part by weight or more, the adhesiveness with the substrate is excellent, the crosslinkability is increased during thermal curing, the thin film density becomes dense, the hardness is improved after thermal curing, and the epoxy compound that does not undergo the ring opening reaction when the content is 50 parts by weight or less. The fall of the thin film density and hardness which exist after this thermosetting can be prevented.

The molecular weight of the polymer or oligomer containing at least one epoxy group is not particularly limited as long as the object of the present invention can be achieved, but is preferably lower than the organosiloxane polymer. Specifically, the weight average molecular weight is preferably 100 to 30,000, more preferably the weight average molecular weight 1,000 to 10,000. When the weight average molecular weight is 100 or more, the adhesion to the substrate is excellent, and the crosslinkability is increased during thermal curing, and the hardness of the thin film is excellent. When the viscosity is 30,000 or less, the viscosity of the present component is appropriate to prevent excessive degradation of the flowability of the composition. As a result, the flatness is excellent, whereby the thickness of the thin film can be made uniform, making it suitable for flattening of steps.

d) acid Generator

The acid generator used in the present invention is a thermal latent acid generator in which acid is generated by heat. Such acid generator is not particularly limited as long as it can promote the ring-opening reaction of the compound having an epoxy group or an oxetane group.

As the acid generator, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, fluoroalkylsulfonic acids such as camphor sulfonic acid, trifluoromethanesulfonic acid and perfluorobutanesulfonic acid, methanesulfonic acid and ethanesulfonic acid Preference is given to generating alkylsulfonic acids such as propanesulfonic acid and butanesulfonic acid. Such acids efficiently promote the ring-opening reaction of the compound having an epoxy or oxetane group and can prevent the ring-opening from being lowered even if the curing temperature is lowered.

Among the acid generators that generate these acids, compounds in the form of salts such as onium salts or in the form of covalent bonds such as imide sulfonates are preferred. Specifically, iodonium and sulfonium salts are preferable as onium salts, for example, diaryl iodonium salts such as diphenyl iodonium salts, alkylaryl iodonium salts such as t-butylphenyl iodonium salts, and dialkyls. Iodonium salts, trialkylsulfonium salts such as trimethylsulfonium salts, dialkylmonoarylsulfonium salts such as dimethylphenylsulfonium salts, and diarylmonoalkylsulfonium salts such as diphenylmethylsulfonium salts. They have a decomposition initiation temperature of 100 to 120 ° C. and effectively act on ring opening and crosslinking reaction of the ring compound at 150 ° C. or lower. As the acid generator of the imide sulfonate series, naphthalimide sulfonate or the like is preferable. Commercially available products of such thermal acid generators that can be used in the present invention include TAG-2678 (imide sulfonate series, manufactured by King Industries).

The acid generator used in the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight based on 100 parts by weight of the organosiloxane polymer. When the content of the acid generator is 0.01 parts by weight or more, crosslinking proceeds sufficiently to improve the surface hardness of the thin film, adhesion to the substrate, acid resistance, alkali resistance, solvent resistance and flatness, and dissolution in the composition when the content is 20 parts by weight or less. It is easy to maintain, storage stability is maintained, and is advantageous in terms of product cost.

e) Light curing Initiator

The composition of the present invention may further comprise a photopolymerization initiator. The photopolymerization initiator has a function of initiating polymerization by wavelengths of visible light, ultraviolet light, far ultraviolet light and the like.

Such a photopolymerization initiator may be any photopolymerization initiator known in the art, and may include acetophenone compounds, biimidazole compounds, triazine compounds, onium salt compounds, benzoin compounds, benzophenone compounds, diketone compounds, α At least one member selected from the group consisting of diketone compounds, polynuclear quinone compounds, thioxanthone compounds, diazo compounds, imidesulfonate compounds, oxime compounds, carbazole compounds, and sulfonium borate compounds It is preferable. Among them, Republic of Korea Patent Publication No. 2004-0007700, Republic of Korea Patent Publication No. 2005-0084149, Republic of Korea Patent Publication No. 2008-0083650, Republic of Korea Patent Publication No. 2008-0080208, Republic of Korea Patent Publication No. 2007-0044062 Republic of Korea Patent Publication No. 2007-0091110, Republic of Korea Patent Publication No. 2007-0044753, Republic of Korea Patent Publication No. 2009-0009991, Republic of Korea Patent Publication No. 2009-0093933, Republic of Korea Patent Publication No. 2010-0097658 The oxime compounds described in Korean Patent Application Laid-Open No. 2011-0059525, International Publication No. WO 10/102502, and International Publication No. WO 10/133077 are preferred, and OXE-01 and OXE-02 (Ciba Corporation). Product) and a commercial item, such as N-1919 (made by ADEKA Corporation), are preferable at the point of high sensitivity and resolution.

The photopolymerization initiator is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight (based on the solid content) of the organosiloxane polymer. When the content is 0.5 parts by weight or more, the degree of curing of the thin film, the sensitivity and the linearity of the pattern is excellent, and when the content is 10 parts by weight or less, the degree of curing of the thin film is not excessive, so that excellent resolution can be realized, and a residual film is generated in portions other than the formed pattern. The problem of being easy to do can be prevented.

f) Silane system Coupling agent

The composition of the present invention may further include a silane coupling agent to improve the adhesion between the cured film and the substrate. As such a silane coupling agent, the functional silane compound which has a reactive functional group can be used. As said reactive functional group, a carboxyl group, methacryloyl group, an isocyanate group, an epoxy group, etc. are mentioned, for example. Such silane coupling agents are well known per se in the art.

Specific examples include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycidoxypropyltrimethoxy One or more selected from silane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane may be used, but is not limited thereto. Preferably, in terms of the remaining film ratio and the adhesion between the substrate, γ-glycidoxypropyltriethoxysilane and / or γ-glycidoxypropyltrimethoxysilane having an epoxy group can be used.

The silane coupling agent of the present invention is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the organosiloxane polymer. When the content of the silane coupling agent is 0.01 parts by weight or more, when the adhesiveness to the substrate is improved and 10 parts by weight or less, the thermal stability is improved at high temperatures, it is possible to prevent the phenomenon that the stain occurs after development.

g) surfactants

The composition of the present invention may further include a surfactant as needed to improve the coating performance of the composition.

Such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and other surfactants. For example, FZ2122 (Dow Corning Toray Co., Ltd.), BM-1000, BM-1100 (manufactured by BM CHEMIE Co., Ltd.), Mega Pack F142 D, Copper F172, Copper F173, Copper F183 (manufactured by Dai Nippon Ink Chemical Co., Ltd.) , Florad FC-135, Copper FC-170 C, Copper FC-430, Copper FC-431 (manufactured by Sumitomo 3M Limited), Supron S-112, Copper S-113, Copper S-131, Copper S-141 S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF301, copper 303, copper 352 (manufactured by New Kasei Co., Ltd.), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (Toray Silicon Fluorine-based and silicone-based surfactants such as manufactured by Co., Ltd.); Polyoxyethylene aryl ethers such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, 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 copolymer polyflow No. 57,95 (manufactured by Kyoeisha Chemical Co., Ltd.) alone or two kinds. The above may be used in parallel, but is not limited thereto.

These surfactants are preferably used 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight (based on the solid content) of the organosiloxane polymer. When the content of the surfactant is 0.05 parts by weight or more, the applicability is improved and cracks do not occur on the coated surface, and when it is 10 parts by weight or less, it is advantageous in terms of price.

h) organic solvents

The composition of the present invention comprises an organic solvent such that the solids content is 10 to 50% by weight, based on the total weight of the composition. The said solid content means the composition component except the organic solvent in the resin composition of this invention.

The organic solvent of the present invention is not particularly limited as long as it can dissolve each component and is chemically stable. Examples of the organic solvent include propylene glycol methyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, propylene glycol methyl ether, ethyl aceto acetate, ethyl acetolactate, ethyl cellsolve-acetate, gamma-butyro One or more selected from lactone, 2-methoxyethyl acetate, ethyl-beta-ethoxypropionate, normal propyl acetate and normal butyl acetate can be used, and preferably, propylene glycol methyl ether acetate, 4-hydroxy- One or more types selected from 4-methyl-2-pentanone, propylene glycol methyl ether and ethyl acetoacetate can be used.

The composition of the present invention may further include, in addition to the above components a) to h), additional components usually used in the thermosetting resin composition and the photosensitive resin composition as necessary.

The composition of the present invention can be applied to a substrate in accordance with conventional methods known in the art to form a cured film, the coating method may be a spray method, a roll coating method, a rotary coating method and the like.

The cured film formed by the composition of the present invention is free from spots and has excellent photosensitive properties such as pattern developability, surface hardness, adhesiveness with a substrate, heat resistance, light transmittance, and resolution, and a residual film rate. (TPD), a liquid crystal display (LCD), a charge coupled device (CCD), or a semiconductor sensor such as a CMOS sensor, etc., is useful as a cured film.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Comparative Preparation Examples, Examples and Comparative Examples. In the following example, a weight average molecular weight is the polystyrene conversion value measured by gel permeation chromatography (GPC).

Manufacturing example  One: Organosiloxane  polymer( PL Preparation of

633 g of distilled water was charged into a three-neck round bottom flask equipped with a condenser, and then 30 g of acetic acid was mixed. The temperature was adjusted to a jacket of 3 ° C. with a coolant of 3 ° C. Lowered the temperature.

To the flask, 154 g of a mixture of γ-glycidoxypropyltrimethoxysilane: methyltrimethoxysilane: phenyltrimethoxysilane: tetramethoxysilane was mixed in a molar ratio of 2: 2: 4: 2, respectively, and a metering pump Was added at a rate of 1.3 g / min.

The polymerization was carried out using hydrolysis and condensation polymerization for 3 hours while maintaining the reaction temperature below 10 ℃. After the completion of the polymerization, the mixture was allowed to stand for 30 minutes, after which propylene glycol methyl ether acetate (PGMEA) was added to dissolve the organosiloxane, and then allowed to stand for 30 minutes. Subsequently, the methyl alcohol and water in the reaction product were removed through atmospheric distillation, 633 g of distilled water was added and stirred for 1 hour to remove residual acetic acid and alcohol. After aging at 72 DEG C, organosiloxane polymer PL-011 was obtained. The organosiloxane polymer obtained had a viscosity of 41.5 cP and a yield of 85.1% as measured by a Brookfield viscometer.

Manufacturing example  2: Organosiloxane  polymer( PL -012) Preparation

Production Example 1, except that 151 g of a mixture of? -glycidoxypropyltrimethoxysilane: dimethyldimethoxysilane: methyltrimethoxysilane: phenyltrimethoxysilane was mixed in a molar ratio of 2: 2: 2: 4, respectively An organosiloxane polymer PL-012 was prepared in the same manner as in the following. The obtained organosiloxane polymer had a viscosity of 39.4 cP and a yield of 87.2% as measured by a Brookfield viscometer.

Manufacturing example  3: Organosiloxane  polymer( PL -013)

Production Example 1 except that 154 g of a mixture of? -glycidoxypropyltrimethoxysilane: methyltrimethoxysilane: phenyltrimethoxysilane: tetramethoxysilane was used in a molar ratio of 2: 2: 4: 2, respectively In the same manner as in the product to obtain a product, it was aged for 115 hours at 60 ℃ to prepare an organosiloxane polymer PL-013. The organosiloxane polymer obtained had a viscosity of 47.2 cP and a yield of 83.4% as measured by a Brookfield viscometer.

Manufacturing example  4 : Organosiloxane  polymer( PL (014)

γ-hydroxypropyltrimethoxysilane: methyltrimethoxysilane: phenyltrimethoxysilane: tetramethoxysilane, except that 154 g of a mixture of 2: 2: 4: 2 was used. The procedure was carried out in the same manner to obtain a product, which was aged at 40 ° C. for 64 hours to prepare organosiloxane polymer PL-014. The organosiloxane polymer obtained had a viscosity of 37.9 cP and an yield of 86.0% as measured by a Brookfield viscometer.

Manufacturing example  5: Organosiloxane  polymer( PL -015)

γ-hydroxypropyltrimethoxysilane: dimethyldimethoxysilane: methyltrimethoxysilane: phenyltrimethoxysilane was used in Preparation Example 1 except that 151 g of a mixture of 2: 2: 2: 4 was used. The same procedure was followed to obtain a product, which was aged at 40 ° C. for 77 hours to prepare organosiloxane polymer PL-015. The organosiloxane polymer obtained had a viscosity of 34.2 cP and a yield of 88.7% as measured by a Brookfield viscometer.

Manufacturing example  6: Organosiloxane  polymer( PL -016)

γ-hydroxypropyltrimethoxysilane: methyltrimethoxysilane: phenyltrimethoxysilane: tetramethoxysilane, except that 154 g of a mixture of 2: 2: 4: 2 was used, respectively. The same procedure was followed to obtain a product, which was aged at 60 ° C. for 120 hours to prepare organosiloxane polymer PL-016. The organosiloxane polymer obtained had a viscosity of 48.4 cP and a yield of 81.4% as measured by a Brookfield viscometer.

Manufacturing example  7: Organosiloxane  polymer( PL Preparation of

Preparation Example 1 except that 154 g of a mixture of gamma -mercaptopropyltrimethoxymethylsilane: methyltrimethoxysilane: phenyltrimethoxysilane: tetramethoxysilane was mixed in a molar ratio of 2: 2: 4: 2, respectively. In the same manner as in the product to obtain a product, which was aged for 55 hours at 40 ℃ to prepare an organosiloxane polymer PL-017. The obtained organosiloxane polymer had a viscosity of 38.7 cP and a yield of 82.9% as measured by a Brookfield viscometer.

Manufacturing example  8: Organosiloxane  polymer( PL -018)

Preparation Example 1 except that 151 g of a mixture of gamma -mercaptopropyltrimethoxymethylsilane: dimethyldimethoxysilane: methyltrimethoxysilane and phenyltrimethoxysilane was mixed in a molar ratio of 2: 2: 2: 4, respectively. In the same manner as in the product to obtain a product, it was aged for 70 hours at 40 ℃ to prepare an organosiloxane polymer PL-018. The organosiloxane polymer obtained had a viscosity of 35.8 cP and a yield of 89.6% as measured by a Brookfield viscometer.

Manufacturing example  9: Organosiloxane  polymer( PL -019)

Production Example 1 except that 154 g of a mixture of gamma -mercaptopropyltrimethoxymethylsilane: methyltrimethoxysilane: phenyltrimethoxysilane: tetramethoxysilane was mixed in a molar ratio of 2: 2: 4: 2, respectively. In the same manner as in the product to obtain a product, it was aged for 113 hours at 60 ℃ to prepare an organosiloxane polymer PL-019. The organosiloxane polymer obtained had a viscosity of 51.1 cP and a yield of 80.8% as measured by a Brookfield viscometer.

Manufacturing example  10: Organosiloxane  polymer( PL -020)

(3-oxetanylmethoxypropyl) trimethoxysilane: methyltrimethoxysilane: phenyltrimethoxysilane: tetramethoxysilane except that 154 g of a mixture of 2: 2: 4: 2 was used. Organizing in the same manner as in Preparation Example 1 to obtain a product, which was aged for 62 hours at 40 ℃ to prepare an organosiloxane polymer PL-020. The organosiloxane polymer obtained had a viscosity of 40.2 cP and an yield of 81.6% by the Brookfield viscometer.

Manufacturing example  11: Organosiloxane  polymer( PL -021)

γ-glycidoxypropyltrimethoxysilane: γ-glycidoxypropyldimethoxymethylsilane: di (γ-hydroxypropyl) dimethoxysilane: di (γ-mercaptopropyl) dimethoxysilane: methyltrimethoxy The product was obtained by the same method as Preparation Example 1, except that 151 g of a mixture of silane: phenyltrimethoxysilane and tetramethoxysilane was mixed in a molar ratio of 0.5: 0.5: 0.5: 0.5: 2: 4: 2, respectively. It was aged for 81 hours at 40 ° C. to prepare organosiloxane polymer PL-021. The organosiloxane polymer obtained had a viscosity of 37.1 cP and a yield of 87.2% by the Brookfield viscometer.

Manufacturing example  12: Organosiloxane  polymer( PL Preparation of

γ-glycidoxypropyltrimethoxysilane: γ-glycidoxypropyldimethoxymethylsilane: di (γ-hydroxypropyl) dimethoxysilane: di (γ-mercaptopropyl) -dimethoxysilane: dimethyldimethoxy The product was prepared in the same manner as in Production Example 1, except that 151 g of a mixture of silane: methyltrimethoxysilane and phenyltrimethoxysilane, each mixed in a molar ratio of 0.5: 0.5: 0.5: 0.5: 2: 2: 4, was used. It was aged at 40 ° C. for 52 hours to prepare organosiloxane polymer PL-022. The obtained organosiloxane polymer had a viscosity of 39.3 cP and a yield of 83.0% as measured by a Brookfield viscometer.

Manufacturing example  13: Organosiloxane  polymer( PL Preparation of

The product was obtained by the same method as Preparation Example 1, except that 151 g of a mixture of methyltrimethoxysilane and phenyltrimethoxysilane were mixed at a molar ratio of 5: 5, respectively. The siloxane polymer PL-023 was prepared. The obtained organosiloxane polymer had a viscosity of 36.9 cP and a yield of 85.1% as measured by a Brookfield viscometer.

Using the organosiloxane polymer prepared in Preparation Example, the compositions and cured films of the following Examples and Comparative Examples were prepared. Table 2 and Table 3 show the contents of each composition.

Example  One

① 100 parts by weight (based on solids content) of PL-011, an organosiloxane polymer synthesized in Preparation Example 1, ② 50 parts by weight of M-520 (manufactured by Toagosei), an acrylate compound having an ethylenically unsaturated double bond, ③ photopolymerization Initiator N-1919 (manufactured by Adeka) 2.5 parts by weight, ④ 0.85 part by weight of TAG-2678 (imide sulfonite series, manufactured by King Industries, Inc.) as an acid generator, ⑤ GHP03, an oligomer containing one or more epoxy groups (Miwon 8.5 parts by weight, ⑥ silane coupling agent GPTMS (γ-glycidoxypropyltrimethoxysilane, manufactured by Aldrich) 0.3 parts by weight, and ⑦ fluorine-based surfactant FZ2122 (manufactured by Dow Corning) 0.16 parts by weight and ⑧ Propylene glycol methyl ether acetate is mixed as an organic solvent such that the ratio of (① + ② + ③ + ④ + ⑤ + ⑥ + ⑦) / (① + ② + ③ + ④ + ⑤ + ⑥ + ⑦ + ⑧) is 25% by weight. To prepare a composition in liquid form.

The composition was low temperature aged for 12 hours at a temperature of 4 ° C. before rotational application and then filtered using a 1.0 μm filter. The composition obtained by filtration was spun onto a glass or silicon substrate, subjected to prebaking and exposure, and then developed to form a negative pattern, and then the coating layer was post-baked at 150 ° C. for 10 minutes to prepare a cured film. The pattern shape, light transmittance, residual film rate, adhesiveness, thermal stability and surface hardness of the prepared cured film were measured.

Example  2

Except that the organosiloxane polymer PL-012 synthesized in Preparation Example 2 was used, and was the same as in Example 1.

Example  3

It is the same as Example 1 except using the organosiloxane polymer PL-013 synthesize | combined in manufacture example 3.

Example  4

Except for using the organosiloxane polymer PL-014 synthesized in Preparation Example 4 and the same as in Example 1.

Example  5

Except for using the organosiloxane polymer PL-015 synthesized in Preparation Example 5 and the same as in Example 1.

Example  6

It is the same as Example 1 except using the organosiloxane polymer PL-016 synthesize | combined in manufacture example 6.

Example  7

It is the same as Example 1 except using the organosiloxane polymer PL-017 synthesize | combined in manufacture example 7.

Example  8

It is the same as Example 1 except using the organosiloxane polymer PL-018 synthesize | combined in manufacture example 8.

Example  9

It is the same as Example 1 except using the organosiloxane polymer PL-019 synthesize | combined in manufacture example 9.

Example  10

It is the same as Example 1 except using the organosiloxane polymer PL-020 synthesize | combined in manufacture example 10.

Example  11

It is the same as Example 1 except using the organosiloxane polymer PL-021 synthesize | combined in manufacture example 11.

Example  12

It is the same as Example 1 except using the organosiloxane polymer PL-022 synthesize | combined in manufacture example 12.

Comparative Example  One

It is the same as Example 1 except using the organosiloxane polymer PL-023 synthesize | combined in manufacture example 13.

Comparative Example  2

The composition was prepared in the same manner as in Example 1 except that the acid generator TAG-2678 was not included.

Comparative Example  3

A composition was prepared in the same manner as in Example 1, except that GHP03, an oligomer including one or more epoxy groups, was not included.

Comparative Example  4

A composition was prepared in the same manner as in Example 1, except that M-520, an acrylate compound having an ethylenically unsaturated double bond, was not included.

Comparative Example  5

The composition was prepared in the same manner as in Example 4 except that the acid generator TAG-2678 was not included.

Comparative Example  6

A composition was prepared in the same manner as in Example 4, except that GHP03, an oligomer including one or more epoxy groups, was not included.

Comparative Example  7

A composition was prepared in the same manner as in Example 7, except that the acid generator TAG-2678 was not included.

Comparative Example  8

A composition was prepared in the same manner as in Example 7, except that GHP03, an oligomer including one or more epoxy groups, was not included.

Table 2 Examples

Table 3 Comparative Example

In the table, the bifunctional siloxane units are abbreviated as D, the trifunctional siloxane units are abbreviated as T, the tetrafunctional siloxane units are abbreviated as Q, and the acid generator is TAG, at least one ethylenically unsaturated double The acrylate compound which has a bond was abbreviated MM, the siloxane unit derived from tetramethoxysilane was TEOS, and the oligomer containing one or more epoxy groups was abbreviated as EO.

Measurement methods for the physical properties of the cured film prepared in Examples and Comparative Examples are as follows.

One. Developability  evaluation

After spin-coating the photosensitive resin composition on a silicon substrate, prebaking is carried out for 90 seconds on a high temperature plate maintained at 110 ° C. to form a dry film having a thickness of 2.5 μm and an alignmenter having a wavelength of 200 nm to 450 nm in the composition film. It exposed through a pattern mask so that it might be about 30mJ / cm <2> based on 365 nm using brand name MA6), and it developed through the spray nozzle at 25 degreeC with the developing solution which consists of aqueous 2.38% tetramethylammonium hydroxide solution. The obtained exposure film was made into a convection oven at 150 degreeC for 10 minutes. The thermosetting film was obtained by heating. The developability was evaluated through the shape of the developed fine pattern.

The pattern shape evaluated the pattern shape by the following reference | standard by observing the pattern shape formed in the contact hole which has a 10 micrometer line width of a thermosetting film with a scanning microscope.

(Double-circle): A rectangle is favorable and there is no bottom tail.

(Triangle | delta): A rectangle is favorable, but a surface is not smooth or a stainy residual film is formed.

Ⅹ: Rectangle is bad or not resolved.

2. Light transmittance evaluation

The composition was spin-coated on an organic substrate, and a 2.1 mu m cured film was formed through the same process. The light transmittance of 400 nm to 800 nm wavelength was measured and compared through UV / Visible spectrum measurement.

3. Evaluation of adhesion

Using the substrate produced in the evaluation of the light transmittance, a cross-cut test was conducted according to the method described in ASTM D3359, wherein the adhesion was evaluated by the following criteria.

OB: broken into flakes, falling by more than 65%

1B: The edge of the cut and the lattice fall off and the area is greater than 35% and less than 65%

2B: A small area falls off at the intersection of the cut and the area is greater than 15% and less than 35%

3B: A small area falls off at the intersection of the cut and the area is more than 5% and less than 15%

4B: 5% or less of area at intersection of cuts

5B: There is no truncated grid with smooth edges at the ends.

4. Surface Hardness Evaluation

Using the board | substrate produced by the said light transmittance evaluation, the surface hardness of the said cured film was measured by the method of ASTM-D3363. The Mitsubishi Pencil was brought into contact with the board using a Pencil Hardness Tester, and a weight of 500 g was placed on it to scratch the surface of the board at a rate of 50 mm / sec and observe the surface. Measured. Measurement criteria were evaluated based on the appearance of wear, peeling, tearing, scratches of the surface at the level corresponding to the pencil hardness.

5. Heat resistance evaluation

Using the substrate produced in the light transmittance evaluation, the heat resistance of the cured film was evaluated through TGA (Thermo-Gravimetric Analysis) as follows. The measurement conditions were as follows: the temperature was raised from 30 ° C. to 130 ° C. at a rate of 10 ° C. per minute, isothermally heated at 130 ° C. for 5 minutes to remove moisture, and then the temperature was lowered to 30 ° C. The temperature is raised to 150 ° C at a rate of 10 ° C per minute, and isothermally heated for 30 minutes at a temperature of 150 ° C. After the measurement temperature was lowered to 30 ° C, the weight of the cured film lost through isothermal heating was analyzed in%. The smaller the loss, the better the heat resistance.

6. Residual film ratio  evaluation

The thickness of the cured film after development and heat curing (post-baking) for the initial thickness (thickness after prebaking) of the thermal cured film (2.5 mm after pre-baking) using a contact film thickness evaluation equipment (Surface-profiler, trade name ALPHA-STEP IQ) was measured. By evaluation, the residual film rate at 30 mJ / cm 2 was expressed as a percentage.

[Evaluation results]

Table 4 shows the pattern development, the surface hardness, the adhesion, the heat resistance, the light transmittance and the residual film ratio according to the kind of the composition prepared in Examples and Comparative Examples.

[Table 4]

As shown in Table 4, whether the siloxane unit in the organosiloxane polymer has at least one functional group selected from the group consisting of an oxetane group, an epoxy group, a hydroxy group and a thiol group, and an acrylate compound having at least one ethylenically unsaturated double bond. The presence or absence, the presence or absence of a polymer or oligomer containing at least one epoxy group, and the presence or absence of an acid generator affect the physical properties of the coating film. When the composition according to the present invention was used, it was possible to realize a high hardness thin film at the same time as a high resolution pattern. In particular, it was confirmed that the acrylate compound having at least one ethylenically unsaturated double bond essential for pattern formation is effective in forming a high-density thin film structure during photocuring to achieve high hardness.

The composition containing the organosiloxane polymer having the oxetane group, the epoxy group, the hydroxy group or the thiol group of Examples 1 to 12 has a high residual film ratio, all light transmittances higher than 95%, no staining and excellent heat resistance. . Particularly, since the developer contained an epoxy group, an oxetane group, a hydroxyl group, or a thiol group as a soluble component, developability was good and the pattern characteristics were excellent. In particular, the pencil hardness of the coating film which hardened at 150 degreeC for 10 minutes was very excellent as 6H. The epoxy group, oxetane group, hydroxyl group and thiol group all contained non-covalent electron pairs, and crosslinked with the surrounding polymer and additives by the acid generated from the acid generator to improve the degree of curing of the coating film.

Examples 1, 2, and 3 show that an organosiloxane polymer incorporating an epoxy group is formed with a secondary alcohol by opening an epoxy ring structure by an acid derived from an acid generator, and a non-covalent electron pair of hydroxy is crosslinked through a chain reaction with surrounding hydrogen or the like. As a result of the formation of bonds, the crosslinkability of the coating film was increased, and in particular, Examples 1 and 3, which contain tetrafunctional structures, were more excellent in surface hardness evaluation than Examples 2, which did not contain tetrafunctional groups. .

Examples 4, 5, and 6 exhibited a crosslinking tendency by introducing a hydroxy group into the organosiloxane polymer, and Examples 7, 8 and 9 form a high hardness thin film by introducing a thiol group into the organosiloxane polymer to participate in crosslinking. In Example 10, it was confirmed that the oxetane group having a similar structure to the epoxy group exhibits similar characteristics.

Examples 11 and 12 were applied to the organosiloxane polymer containing all of the epoxy group, hydroxyl group and thiol group to form a coating film exhibiting excellent properties such as high hardness, high resolution, high light transmittance, high adhesiveness.

Comparative Example 1 used an organosiloxane polymer in which methyl and petyl were introduced at 1: 1 with no crosslinking tendency, and since these components had little solubility in a developing solution, not only the pattern was impossible but also no crosslinking was formed. Therefore, although the acid generator and the epoxy oligomer were contained, the hardness of the thin film was poor.

In Comparative Examples 2, 5, and 7, a composition containing no acid generator was used. Thus, the ring-opening reaction of the epoxy did not occur sufficiently under curing conditions of 150 ° C. for 10 minutes, and thus the particles exist in a ring form. The empty space in the coated film was increased, which resulted in a decrease in the density of the coated film, resulting in poor hardness.

In Comparative Examples 3, 6 and 8, the oligomers containing at least one epoxy group were excluded. As a result, not only the thermal crosslinking tendency exerted from the epoxy component was reduced, but also the density of the coating film was greatly worsened, resulting in poor hardness.

In Comparative Example 4, since the crosslinking did not proceed sufficiently during exposure due to the absence of an acrylate compound having an ethylenically unsaturated double bond participating in the optical crosslinking in the exposure step, the pattern formation was poor, and for the developer during subsequent development, It was confirmed that the residual film ratio was very poor because of high solubility, and the hardness was poor because the density of the thin film was not high enough during photocrosslinking. In particular, as a result of analyzing the pattern by SEM, the surface of the thin film was not uniform and defects such as under cut occurred.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (9)

a) an organosiloxane polymer comprising a siloxane unit having at least one functional group selected from the group consisting of an oxetane group, an epoxy group, a hydroxy group and a thiol group;
b) an acrylate compound having at least one ethylenically unsaturated double bond;
c) a polymer or oligomer comprising at least one epoxy group, wherein the polymer differs from the a) organosiloxane polymer; And
d) Photosensitive resin composition containing an acid generator. The photosensitive resin composition of claim 1, wherein the a) organosiloxane polymer comprises at least one siloxane unit selected from Chemical Formulas 1 and 2.
[Formula 1]

(2)

In the above Formulas 1 and 2,
Each A is 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 An arylalkylene group,
Y is each independently —OH, —Z, —OZ or —SH, Z is — (CH ₂ ) nQ (n is an integer of 0 to 5), and Q is an epoxy group or an oxetane group. The photosensitive resin composition of claim 2, wherein the a) organosiloxane polymer further comprises one or more siloxane units selected from the following Chemical Formulas 3 to 5 as polymerized units.
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In Chemical Formulas 3 to 5,
Each R is, independently, a hydrogen atom, C ₁ -C ₉ Alkyl group, C ₃ -C ₁₄ A cycloalkyl group, a C ₆ -C ₁₄ Aryl group, C ₇ -C ₁₄ Alkylaryl groups or C ₇ -C ₁₄ Arylalkyl group. The photosensitive resin composition of claim 3, wherein the molar ratio of the siloxane units of Formula 5 is 0.10 to 0.30 based on the total polymerized units forming the organosiloxane polymer. The method of claim 1, wherein b) the acrylate compound having at least one ethylenically unsaturated double bond is ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acryl Rate, triethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerin tri (meth) acrylic Rate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, monoester of pentaerythritol tri (meth) acrylate and succinic acid, pentaerythritol tetra (meth) acrylate, dipenta Of erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and succinic acid Monoester, caprolactone modified dipentaerythritol hexa (meth) acrylate, pentaerythritol triacrylate hexamethylene diisocyanate (reactant of pentaerythritol triacrylate and hexamethylene diisocyanate), tripentaerythritol hepta ( The photosensitive resin composition which is 1 or more types chosen from the group which consists of a meth) acrylate, a tripentaerythritol octa (meth) acrylate, a bisphenol A epoxy acrylate, and ethylene glycol monomethyl ether acrylate. The photosensitive resin composition of claim 1, wherein the c) polymer or oligomer including at least one epoxy group comprises a unit represented by the following Chemical Formula 6.
[Chemical Formula 6]

In Formula 6,
R ² represents a hydrogen atom or a straight or branched C ₁ -C ₅ alkyl group,
R ³ represents a hydrogen atom or a C ₁ -C ₂ alkyl group,
m represents the integer of 1-10. The photosensitive resin composition according to claim 1, wherein the d) acid generator generates arylsulfonic acid, camphorsulfonic acid, fluoroalkylsulfonic acid or alkylsulfonic acid. According to claim 1, wherein the photosensitive resin composition is a) 1 to 80 parts by weight of acrylate compound having at least one ethylenically unsaturated double bond with respect to 100 parts by weight (based on solids content) of the a) organosiloxane polymer, c 1 to 50 parts by weight of a polymer or oligomer comprising at least one epoxy group, and d) 0.01 to 20 parts by weight of an acid generator. The photosensitive resin composition of Claim 1 which further contains 1 or more types chosen from e) a photoinitiator, f) a silane coupling agent, and g) surfactant.