KR102167370B1 - Silicone Resin and Method of Preparing the Same - Google Patents

Abstract

The present invention relates to a silicone resin and a method of manufacturing the same, and more specifically, the physical property limits of organic resins (acrylic-epoxy) in materials for displays and semiconductors that require high specifications (heat resistance/light resistance, hardness and high temperature and high humidity) Adhesion in the state) while maintaining high hardness even at low temperature curing, it is advantageous for reducing process cost and protecting the device from scratches in subsequent processes after film formation, and maintaining high adhesion to the substrate even in high temperature and high humidity environments. Thus, a silicone resin useful for manufacturing a protective film of a display and a semiconductor device, and a manufacturing method thereof are provided.

Description

Silicone resin and method of preparing the same {Silicone Resin and Method of Preparing the Same}

The present invention relates to a silicone resin and a method of manufacturing the same.

Currently, in the case of passivation materials for displays and semiconductors, the development of liquid material materials of a coating method, which is advantageous in terms of process, is being actively made, avoiding the deposition method of inorganic (SiN _x ).

These liquid materials can be largely divided into an acrylic-epoxy-based organic insulating film and a silicon-acrylic organic-inorganic hybrid insulating film having an organopolysiloxane structure.

In the case of organic insulating film composition, patterns are formed by UV exposure and alkali development, or have advantages in terms of adhesion to the substrate, dielectric constant, and chemical resistance, but there are disadvantages in terms of light/heat resistance, transmittance, and hardness. Development of complementary silicon-based materials is being actively conducted.

The main object of the present invention is to provide a silicone resin having excellent heat/light resistance and hardness compared to an acrylic-epoxy based organic resin, and a method of manufacturing the same.

The present invention also provides a silicone resin that has excellent adhesion in a high-temperature, high-humidity state compared to an acrylic-epoxy-based organic resin, and has low-temperature curing properties, thereby reducing process costs and a method of manufacturing the same.

The present invention also provides a silicone resin composition containing the silicone resin and a cured product using the same.

In order to achieve the above object, an embodiment of the present invention is one or more compounds selected from compounds represented by the following formulas 1 to 3 and at least one compound selected from compounds represented by the following formulas 4 to 6 It is a condensation reactant and provides a silicone resin having a weight average molecular weight of 1,000 to 100,000 g/mol.

<Formula 1>

R _{1 (n)} SiX _(4-n)

<Formula 2>

R _{2 (n)} SiX _(4-n)

<Formula 3>

SiX ₄

<Formula 4>

R _{1 (n)} MeX _(4-n)

<Formula 5>

R _{2 (n)} MeX _(4-n)

<Formula 6>

MeX ₄

In Formulas 1 to 6, R ₁ is each independently an organic group having 2 to 10 carbon atoms or a mercapto group having at least one unsaturated bond; R ₂ is each independently a hydroxy group, a hydrogen atom, a fluorine atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group, X Is a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group, Me is a metal, and n is an integer of 1 to 3.

In a preferred embodiment of the present invention, each of R ₁ is independently selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acrylic group, an acryloxy group, and a mercapto group. I can.

In a preferred embodiment of the present invention, Me may be characterized in that it is selected from the group consisting of zirconium, titanium, manganese and tungsten.

Another embodiment of the present invention is a condensation reaction of at least one compound selected from compounds represented by the following formulas 1 to 3 and at least one compound selected from compounds represented by the following formulas 4 to 6 to have a weight average molecular weight of 1,000 It provides a method for producing a silicone resin, characterized in that to prepare a silicone resin of 100,000g / mol.

<Formula 1>

R _{1 (n)} SiX _(4-n)

<Formula 2>

R _{2 (n)} SiX _(4-n)

<Formula 3>

SiX ₄

<Formula 4>

R _{1 (n)} MeX _(4-n)

<Formula 5>

R _{2 (n)} MeX _(4-n)

<Formula 6>

MeX ₄

In Formulas 1 to 6, R ₁ is each independently an organic group having 2 to 10 carbon atoms or a mercapto group having at least one unsaturated bond; R ₂ is each independently a hydroxy group, a hydrogen atom, a fluorine atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group, X Is a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group, Me is a metal, and n is an integer of 1 to 3.

In another preferred embodiment of the present invention, each of R ₁ is independently selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acrylic group, an acryloxy group, and a mercapto group. I can.

In another preferred embodiment of the present invention, Me may be characterized in that it is selected from the group consisting of zirconium, titanium, manganese and tungsten.

In another preferred embodiment of the present invention, the silicone resin contains at least one compound selected from compounds represented by Formulas 1 to 3 and at least one compound selected from compounds represented by Formulas 4 to 6, 100:1 to 100 It can be prepared by condensation at a molar ratio of.

In another preferred embodiment of the present invention, the condensation may be performed at room temperature to 150° C. for 1 to 48 hours.

Another embodiment of the present invention provides a silicone resin composition comprising 1 to 70% by weight of the silicone resin and a cured product formed of the silicone resin composition.

In another preferred embodiment of the present invention, the silicone resin composition may be cured at 100 to 300°C.

Another embodiment of the present invention provides a silicone resin comprising a repeating unit represented by the following Chemical Formula 7 and having a weight average molecular weight of 1,000 to 100,000 g/mol.

<Formula 7>

는 화학식 8로 표시되며, n은 10 이하이다.In Formula 7, R ₁ is an organic group or a mercapto group having 2 to 10 carbon atoms each independently having at least one unsaturated bond; R ₂ is each independently a hydroxy group, a hydrogen atom, a fluorine atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group, Me Is a metal,

Is represented by Chemical Formula 8, and n is 10 or less.

<Formula 8>

In another preferred embodiment of the present invention, each of R ₁ is independently selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acrylic group, a mercapto group, and an acryloxy group. I can.

In another preferred embodiment of the present invention, Me may be characterized in that it is selected from the group consisting of zirconium, titanium, manganese and tungsten.

The silicone resin according to the present invention overcomes the physical property limitations (heat/light resistance characteristics, hardness, adhesion in high temperature and high humidity conditions) of organic resins (acrylic-epoxy based) used as materials for displays and semiconductors, thereby reducing process cost and film After formation, it is advantageous for device protection from scratches in subsequent processes, and high adhesion to the substrate can be maintained even in a high-temperature, high-humidity environment, so that it can be usefully used for manufacturing a protective film of displays and semiconductor devices.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by an expert skilled in the art to which the present invention belongs. In general, the nomenclature used in this specification is well known and commonly used in the art.

Throughout the specification of the present application, when a certain part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

In one aspect, the present invention is a condensation reaction product of at least one compound selected from compounds represented by the following formulas 1 to 3 and at least one compound selected from compounds represented by the following formulas 4 to 6, and a weight average molecular weight of 1,000 To 100,000 g/mol.

<Formula 1>

R _{1 (n)} SiX _(4-n)

<Formula 2>

R _{2 (n)} SiX _(4-n)

<Formula 3>

SiX ₄

<Formula 4>

R _{1 (n)} MeX _(4-n)

<Formula 5>

R _{2 (n)} MeX _(4-n)

<Formula 6>

MeX ₄

In Formulas 1 to 6, R ₁ is each independently an organic group having 2 to 10 carbon atoms or a mercapto group having at least one unsaturated bond; R ₂ is each independently a hydroxy group, a hydrogen atom, a fluorine atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group, X Is a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group, Me is a metal, and n is an integer of 1 to 3.

In another aspect, the present invention is a condensation reaction of at least one compound selected from the compounds represented by the following formulas 1 to 3 and at least one compound selected from the compounds represented by the following formulas 4 to 6 to have a weight average molecular weight of 1,000 to It relates to a method for producing a silicone resin, characterized in that to prepare a silicone resin of 100,000 g / mol.

<Formula 1>

R _{1 (n)} SiX _(4-n)

<Formula 2>

R _{2 (n)} SiX _(4-n)

<Formula 3>

SiX ₄

<Formula 4>

R _{1 (n)} MeX _(4-n)

<Formula 5>

R _{2 (n)} MeX _(4-n)

<Formula 6>

MeX ₄

In Formulas 1 to 6, R ₁ is each independently an organic group having 2 to 10 carbon atoms or a mercapto group having at least one unsaturated bond; R ₂ is each independently a hydroxy group, a hydrogen atom, a fluorine atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group, X Is a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group, Me is a metal, and n is an integer of 1 to 3.

In another aspect, the present invention relates to a silicone resin composition comprising 1 to 70% by weight of the silicone resin and a cured product formed of the silicone resin composition.

In another aspect, the present invention relates to a silicone resin comprising a repeating unit represented by the following Chemical Formula 7 and having a weight average molecular weight of 1,000 to 100,000 g/mol.

<Formula 7>

는 화학식 8로 표시되며, n은 10 이하이다.In Formula 7, R ₁ is an organic group or a mercapto group having 2 to 10 carbon atoms each independently having at least one unsaturated bond; R ₂ is each independently a hydroxy group, a hydrogen atom, a fluorine atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group, Me Is a metal,

Is represented by Chemical Formula 8, and n is 10 or less.

<Formula 8>

In Formulas 1 to 7 described above, the organic group may be selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acrylic group, and an acryloxy group.

In addition, in Formulas 1 to 7, R ₁ is selected from the group consisting of a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acrylic group, an acryloxy group, and a mercapto group by radical reaction with an additive. It is preferable in terms of crosslinking formation.

In addition, in Chemical Formulas 1 to 7, Me is preferably a metal selected from the group consisting of zirconium, titanium, manganese and tungsten in terms of reactivity.

The silicone resin according to the present invention contains -OH groups other than the functional groups represented by R ₁ and R ₂ in the polymer chain, and thus has self-condensation when heat is applied, and due to these properties, in the case of a composition containing the silicone resin, It has a low-temperature curing property that cures at a low temperature (100 ~ 150°C).

In addition, when the silicone resin has a weight average molecular weight of 1,000 to 100,000 g/mol, and the weight average molecular weight is less than 1,000 g/mol, the flatness or developability of the coating film may decrease, and when it exceeds 100,000 g/mol, Hardness may decrease or a problem of gelation may occur.

In particular, in Formula 7, n represents the average value of the degree of polymerization, and n is 10 or less, preferably 1 to 8.

The silicone resin is prepared by condensing at least one compound selected from compounds represented by Formulas 1 to 3 and at least one compound selected from compounds represented by Formulas 4 to 6, represented by Formulas 1 to 3 When condensed with at least one compound selected from the compounds represented by Formulas 4 to 6 than when condensed with only the compound to be used, the adhesion properties with the coating substrate can be improved by improving the hardness and adhesion in high temperature and high humidity conditions. have.

Specifically, the silicone resin prepared as described above is difficult to specify by the structural formula, but one or more compounds selected from compounds represented by Formulas 1 to 3 and at least one compound selected from compounds represented by Formulas 4 to 6 are random It can be made of a polymer represented by the following formula (7) irregularly arranged in shape.

<Formula 7>

및 n은 전술한 바와 같다. In Formula 7, R ₁ , R ₂ , Me,

And n is as described above.

The silicone resin is prepared by condensing at least one compound selected from compounds represented by Formulas 1 to 3 and at least one compound selected from compounds represented by Formulas 4 to 6 at a molar ratio of 100:1 to 100 And condensation is preferably carried out in a molar ratio of 100:10 to 80.

If, when preparing a silicone resin, at least one compound selected from the compounds represented by Formulas 1 to 3 and at least one compound selected from the compounds represented by Formulas 4 to 6 are outside the above content range, other than silicone It may be difficult to form a polymer due to the strong reactivity of other metal alkoxides, or it may be difficult to expect an increase in hardness due to the addition of metal alkoxides or improvement in adhesion at high temperature and high humidity.

Meanwhile, the condensation of at least one compound selected from the compounds represented by Formulas 1 to 3 and the condensation of at least one compound selected from the compounds represented by Formulas 4 to 6 may be performed at room temperature to 150°C for 1 to 48 hours. And, preferably, it can be performed at 40 to 80° C. for 1 to 12 hours.

If the condensation reaction is performed at room temperature or less than 1 hour, the reaction does not proceed, and when it exceeds 150° C. or 48 hours, supercondensation proceeds and gelation may occur due to polymer formation.

In addition, in the present invention, the reaction product (at least one compound selected from compounds represented by Formulas 1 to 3 and at least one compound selected from compounds represented by Formulas 4 to 6) itself as a solvent is used as a reaction embodiment. Although preferred, it is also possible to use other reaction solvents. In this case, the reaction solvent is not particularly limited as long as it is a solvent and content that does not inhibit the reaction, and examples thereof include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate.

The silicone resin composition according to the present invention comprises the above-described silicone resin, and thus has excellent heat/light resistance, hardness and low temperature (100 ~ 150°C) curing properties compared to conventional thermosetting and photocurable organic compositions including acrylic-epoxy resins. There is an advantage that it is excellent and it is possible to reduce process cost. At this time, when the silicone resin is included in an amount of less than 1% by weight with respect to the entire composition, the effect of the addition of the silicone resin is insignificant, and when it exceeds 70% by weight, storage stability may be deteriorated due to curing characteristics. .

In addition, the silicone resin composition of the present invention may optionally contain an additive and a solvent according to an arbitrary purpose in addition to the above-described silicone resin. As the additive, as long as it is commonly used in the field to which the present invention belongs, it may be used without particular limitation, and specifically, a surfactant, a leveling agent, an adhesion increasing agent, a silane coupling agent, a chelating agent, a curing accelerator, etc. I can.

The additive may be included in an amount of 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the silicone resin. When the content of the additive is less than 5 parts by weight, properties such as adhesion or smoothness are insignificant, and when it exceeds 50 parts by weight, it is difficult to implement the properties of the original composition.

In addition, the silicone resin composition of the present invention includes a solvent, and in the case of the solvent, 100 to 1,000 parts by weight, preferably 150 to 700 parts by weight, is preferable based on 100 parts by weight of the silicone resin. Specific examples of the solvent include alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol alkyl ether acetates such as propylene glycol butyl ether acetate, but are not limited thereto.

The present invention is a step of coating the above-described silicone resin composition to prepare a cured product such as a protective film (overcoat) for an optical device and an insulating film for semiconductors, a pre bake (PRB) step of evaporating a solvent, and exposure (Exposure) Step, develop step, and finally post bake (PSB) step of curing the coating.

In the case of the coating, it may be performed by a method such as spin coating, bar coating, or dipping, and it is preferable to change the condition according to the desired thickness.

In the case of the pre-baking (PRB) step, it is preferably selected according to the boiling point of the solvent used, 50 to 150°C, preferably 80 to 130°C, and the time is 10 to 200 seconds, preferably 30 to 150 seconds. desirable. If applied for less than 50° C. for less than 30 seconds, the solvent is not completely dried, which may affect physical properties, and when applied for more than 150° C. for more than 200 seconds, coating properties may deteriorate due to rapid drying of the solvent contained in the composition.

In the case of the exposure step, it means exposure by ultraviolet rays, and the exposure amount is preferably 10 to 1000 mJ/cm ² (igh line), preferably 30 to 500 mJ/cm ² (igh line). If the exposure amount is less than 10mJ/cm ² (igh line), there is a risk that the coating film may be washed out during the development stage because radical curing by exposure does not occur completely, and if it exceeds 1000 mJ/cm ² (igh line), the pattern The properties are poor, and adhesion may decrease due to over-hardening.

In the case of the developing step, it means development by an alkali developer, and the developer is not limited to one. The developing time is generally 1 second to 10 minutes, preferably 20 seconds to 5 minutes. If it is less than 1 second, it is difficult to form an appropriate pattern because the uncured powder is not washed away. If it exceeds 10 minutes, the pattern is lost or only the developer is used in excess, but does not affect the pattern characteristics.

In addition, in the case of the post-baking (PSB) step, the curing time is 100 to 300°C, the curing time is 1 to 3 hours, preferably 100 to 250°C, and the curing time is 30 minutes to 2 hours. When the curing condition is less than 100°C for less than 30 minutes, it is not completely cured, which is disadvantageous in terms of hardness and adhesion, and when the curing condition exceeds 300°C for 3 hours, cracks or decrease in transmittance may occur.

Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited to the following examples.

< Example 1>

1-1: Preparation of silicone resin

In a reaction vessel equipped with a cooling tube and a stirrer, with respect to 100 parts by weight of propylene glycol monomethyl ether acetate as a solvent, vinyl triethoxy silane (in Formula 1, R ₁ is a vinyl group, X is ethoxy, and n is 1 Im) After mixing 5 parts by weight (0.2 mol) and 60 parts by weight (0.8 mol) of tetraethoxy silane (in Chemical Formula 3, X is ethoxy) at room temperature, 5 parts by weight of 0.01N HCl is gradually dropped thereinto The hydrolysis reaction proceeded for 1 hour. 55 parts by weight (0.5 mol) of zirconium (IV) butoxide (in Chemical Formula 6, Me is zirconium and X is butoxy) was gradually dropped over 30 minutes, and then heated to 70° C. and reacted for 5 hours. Proceeded. Thereafter, the reaction was cooled to room temperature and stabilized for 10 hours, and then 80 parts by weight of propylene glycol monomethyl ether acetate was added thereto. Afterwards, a silicone resin having a solid content of 39% by weight by vacuum evaporation at 60° C. to remove adducts such as water and alcohol generated during the reaction (in Formula 7, R ₁ is a vinyl group, R ₂ is a hydroxy group, and Me is Zirconium, n is 1) 178g was obtained. The weight average molecular weight of the silicone resin thus obtained was 4,725 g/mol.

At this time, the above and below molecular weights were determined by gel permeation chromatography (GPC) (Waters E2695) to determine the weight average molecular weight in terms of polystyrene. The polymer to be measured was dissolved in tetrahydrofuran to a concentration of 1% by weight, and 20 µl was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and the flow rate was 1 mL/min, and the analysis was performed at 40°C. As for the column, 2 Plgel mixed D and 1 Plgel guard column were connected in series. As a detector, it was measured using a Waters 2414 RI Detector.

1-2: Preparation of silicone resin composition

With respect to 100 parts by weight of the silicone resin obtained in Example 1-1, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 10 parts by weight of 3-glycidyloxypropyltriethoxy silane (silane coupling agent) as an additive, and 50 g of a thermosetting silicone resin composition having a solid content of 16.8% by weight was prepared by mixing 0.5 parts by weight of a silicone-based surfactant (BYK, B-302) (diluted by 2.5%).

1-3: Insulation film formation

On the glass surface, the thermosetting silicone resin composition obtained in Example 1-2 was spin-coated at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm. The glass on which the coating film was formed was subjected to a pre-baking step at 100° C. for 90 seconds on a hot plate, and then a post bake step at 150° C. for 30 minutes in a convection oven to form an insulating film.

< Example 2>

2-1: Preparation of silicone resin

A silicone resin was prepared in the same manner as in Example 1-1, but instead of vinyltriethoxy silane, 3-glycidyloxypropyltrimethoxy silane (in Formula 2, R ₂ is an epoxy group (3-glycidyloxypropyl). Group), X is methoxy, and n is 1) 5 parts by weight (0.2 mol) of a silicone resin (in Chemical Formula 7, R ₁ is a vinyl group, R ₂ is an epoxy group (3-glycidyloxy)) Propyl group), Me is zirconium, n is 1) 185 g was obtained. The weight average molecular weight of the silicone resin thus obtained was 5,018 g/mol.

2-2: Preparation of silicone resin composition

With respect to 100 parts by weight of the silicone resin obtained in Example 2-1, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 10 parts by weight of 3-glycidyloxypropyltrimethoxy silane (silane coupling agent) as an additive, and 50 g of a thermosetting silicone resin composition having a solid content of 17.1 wt% was prepared by mixing 0.5 parts by weight of a silicone-based surfactant (BYK, B-302) (diluted by 2.5%).

2-3: insulating film formation

On the glass surface, the thermosetting silicone resin composition obtained in Example 2-2 was spin-coated at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm. The glass on which the coating film was formed was subjected to a pre-baking step at 100° C. for 90 seconds on a hot plate, and then a post bake step at 150° C. for 30 minutes in a convection oven to form an insulating film.

< Example 3>

3-1: Preparation of silicone resin

A silicone resin was prepared in the same manner as in Example 1-1, but instead of 0.5 mol of zirconium (IV) butoxide, zirconium (IV) acetate hydroxide (in formula 4, R ₁ is an acetate group, and X is a hydroxy group, n is 1) 5 parts by weight (0.5 mol) were added to obtain 168 g of a silicone resin (in Chemical Formula 7, R ₁ is acetate, R ₂ is hydroxy, and Me is zirconium). The weight average molecular weight of the silicone resin thus obtained was 5,210 g/mol.

3-2: Preparation of silicone resin composition

With respect to 100 parts by weight of the silicone resin obtained in Example 3-1, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 10 parts by weight of 3-glycidyloxypropyltrimethoxy silane (silane coupling agent) as an additive, and 0.5 parts by weight of a silicone-based surfactant (BYK, B-302) (2.5% diluted) was mixed to prepare 50 g of a thermosetting silicone resin composition having a solid content of 17.4% by weight.

3-3: Insulation film formation

On the glass surface, the thermosetting silicone resin composition obtained in Example 3-2 was spin-coated at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm. The glass on which the coating film was formed was subjected to a pre-baking step at 100° C. for 90 seconds on a hot plate, and then a post bake step at 150° C. for 30 minutes in a convection oven to form an insulating film.

< Comparative example 1>

1-1: Preparation of acrylic-epoxy resin

2.5 parts by weight of 2-2'azobis isobutyronitrile were dissolved in 100 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 5 parts by weight of styrene, 7.5 parts by weight of methacrylic acid, 27.5 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added, followed by nitrogen substitution, followed by stirring. The reaction was heated to 80° C. and reacted for 6 hours to obtain 355 g of an acrylic-epoxy resin having a solid content of 39% by weight. The weight average molecular weight of the acrylic-epoxy resin thus obtained was 7,500 g/mol.

1-2: Preparation of acrylic-epoxy resin composition

With respect to 100 parts by weight of the acrylic-epoxy resin obtained in Comparative Example 1-2, 10 parts by weight of a urethane-based curable compound (UA-510I, Gongyeongsa) and 10 parts by weight of an epoxy curable compound (E-103A, Arakawa) were mixed, and the solid content was 23%. 300 g of acrylic-epoxy resin compositions were obtained.

1 -3: insulating film formation

On the glass surface, the acrylic-epoxy resin composition obtained in Comparative Example 1-2 was spin-coated at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm. The glass on which the coating film was formed was subjected to a pre-baking step at 100° C. for 90 seconds on a hot plate, and then a post bake step at 150° C. for 30 minutes in a convection oven to form an insulating film.

< Comparative example 2>

An acrylic-epoxy resin composition was prepared in the same manner as in Comparative Example 1, but with respect to 100 parts by weight of the acrylic-epoxy resin, 20 parts by weight of a urethane-based curable compound (UA-510I, Gongyeongsa) and an epoxy curable compound (E-103A, Arakawa ) 20 parts by weight of an acrylic-epoxy resin composition having a solid content of 25% After obtaining 320 g, an insulating film was formed in the same manner as in Example 1.

< Comparative example 3>

A silicone resin composition was prepared in the same manner as in Example 1, but when the silicone resin was prepared, the reaction was carried out except for zirconium (IV) butoxide to proceed with the silicone resin (in Formula 7, R ₁ is a vinyl group, and R ₂ is a hydroxy group. And n is 1) 150 g was obtained. The weight average molecular weight of the silicone resin thus obtained was 5,000 g/mol. With respect to 100 parts by weight of the obtained silicone resin, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 10 parts by weight of 3-glycidyloxypropyltrimethoxy silane (silane coupling agent) as an additive, and a silicone-based surfactant ( BYK, B-302) (2.5% diluted) 0.5 parts by weight were mixed to obtain 50 g of a silicone resin composition having a solid content of 17.4% by weight, and an insulating film was formed in the same manner as in Example 1.

< Comparative example 4>

A silicone resin composition was prepared in the same manner as in Example 1, but when preparing the silicone resin, instead of 0.5 mol of zirconium (IV) butoxide, 165 parts by weight (1.5 mol) of zirconium (IV) butoxide was added to the silicone resin (Chemical Formula 7). In, R ₁ is a vinyl group, R ₂ is a hydroxy group, Me is zirconium, and n is 1), but the physical properties of the thermosetting composition were not measured due to the gelation of the prepared silicone resin.

Each of the thermosetting compositions of Examples 1 to 3 and Comparative Examples 1 to 3 was evaluated by measuring physical properties, and the results are shown in Tables 1 to 5.

(1) Measurement of pencil hardness change by curing temperature

The compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were spin-coated on glass at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm, and then prebaked at 100° C. for 90 seconds on a hot plate, and convection Cured in an oven at 150℃, 180℃, 200℃ and 230℃ for 20 minutes, respectively. The hardness of the cured film was measured by pencil hardness, and the physical properties were measured by applying a load of 9.8N using a test machine and pencil conforming to the JIS-D5400 standard, and are shown in Table 1.

(2) Measurement of transmittance by exposure to high temperature/ultraviolet rays

The compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were spin-coated on glass at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm, and then prebaked at 100° C. for 90 seconds on a hot plate, and convection It was cured in an oven at 200℃ for 20 minutes. The transmittance change after exposure to ultraviolet light (60J) on the cured film and the transmittance change after exposure to high temperature (240°C, 90 minutes) were measured using a UV/Vis Spectrometer to measure the transmittance (%) at a wavelength of 400 nm and shown in Table 1. Indicated.

(3) Measurement of color change due to exposure to high temperature/ultraviolet rays

As shown in (2), the color change of the film exposed to high temperature and ultraviolet rays was measured using a color difference meter (CM-3500d, Konica Minolta Co.), and is shown in Table 2.

(4) Measurement of high temperature and high humidity adhesion and chemical resistance

The compositions obtained in Example 1 and Comparative Example 1 were spin-coated on glass at 450 rpm for 12 seconds to form a coating film, and then pre-baked at 100°C for 90 seconds on a hot plate, and then cured at 150°C for 30 minutes in a convection oven. Made it. The cured film was exposed to 100% RH at 120° C. for 6 hours, and then the adhesion was observed (Table 3), and chemical substances (n-methyl-2-pyrrolidone (NMP), 5% HCl) at 40° C. for 30 minutes And 5% Tetramethyl ammonium hydroxide (TMAH) to measure the change in the film thickness (Table 4) In this case, the measurement was repeated three times.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Pencil hardness
(Hardness by temperature)


Hardening
(150℃ for 20 minutes) 3H 3H 3H 1H HB 3H Hardening
(180℃ for 20 minutes) 6H 5H 5H 2H H 5H Hardening
(200℃ for 20 minutes) 7H 6H 6H 3H 3H Not measurable
(Cracking) Hardening
(230℃ for 20 minutes) 7H 7H 6H 5H 4H Not measurable
(Cracking) Transmittance
(%, 400nm)


Hardening
(200℃ for 20 minutes) 99.79 99.89 99.81 98.82 98.51 Not measurable
(Cracking) UV exposure
(60J) 99.34 99.31 99.22 82.82 90.74 Not measurable
(Cracking) High temperature exposure
(240℃ for 90 minutes) 99.29 99.25 99.10 77.50 68.21 Not measurable
(Cracking)

As shown in Table 1, it can be seen that the silicone resin compositions of Examples 1 to 3 are cured at a lower temperature than the acrylic-epoxy compositions of Comparative Examples 1 and 2, and the pencil hardness is also the silicone resin of Examples 1 to 3 It was confirmed that the composition was superior to the acrylic-epoxy compositions of Comparative Examples 1 and 2 even at a low temperature.

In addition, it was found that the transmittance of the silicone resin compositions of Examples 1 and 2 did not change compared to the acrylic-epoxy compositions of Comparative Examples 1 and 2 as well as the transmittance according to UV and high temperature exposure.

On the other hand, in Comparative Example 3, cracks were generated in the cured film at a curing temperature of 200°C or higher, whereas in Examples 1 to 3, cracks were not generated and thus crack resistance was also excellent.

division L a b YI Example 1

Hardening
(200℃ for 20 minutes) 97.42 -0.02 0.17 0.12 UV exposure
(60J) 97.38 -0.03 0.24 0.23 High temperature exposure
(240℃ for 90 minutes) 97.20 -0.06 0.25 0.24 Example 2

Hardening
(200℃ for 20 minutes) 97.45 -0.03 0.19 0.15 UV exposure
(60J) 97.40 -0.03 0.23 0.21 High temperature exposure
(240℃ for 90 minutes) 97.25 -0.05 0.25 0.27 Example 3

Hardening
(200℃ for 20 minutes) 97.40 -0.03 0.20 0.14 UV exposure
(60J) 97.29 -0.04 0.23 0.19 High temperature exposure
(240℃ for 90 minutes) 97.18 -0.06 0.27 0.26 Comparative Example 1

Hardening
(200℃ for 20 minutes) 96.98 -0.03 0.25 0.25 UV exposure
(60J) 96.84 -0.36 1.50 2.10 High temperature exposure
(240℃ for 90 minutes) 95.61 -0.90 5.78 8.53 Comparative Example 2

Hardening
(200℃ for 20 minutes) 96.81 -0.05 0.29 0.33 UV exposure
(60J) 95.91 -0.40 2.10 3.01 High temperature exposure
(240℃ for 90 minutes) 95.34 -0.98 7.85 10.21 Comparative Example 3

Hardening
(200℃ for 20 minutes) Not measurable
(Cracking) Not measurable
(Cracking) Not measurable
(Cracking) Not measurable
(Cracking) UV exposure
(60J) Not measurable
(Cracking) Not measurable
(Cracking) Not measurable
(Cracking) Not measurable
(Cracking) High temperature exposure
(240℃ for 90 minutes) Not measurable
(Cracking) Not measurable
(Cracking) Not measurable
(Cracking) Not measurable
(Cracking)

As shown in Table 2, it was found that there was no color change of the silicone resin compositions of Examples 1 to 3 compared to the acrylic-epoxy compositions of Comparative Examples 1 and 2 as well as the color change according to UV and high temperature exposure.

division Example 1 Comparative Example 1 High temperature and high humidity adhesion
(120℃, 100%RH)
Optical microscope
image
(×200 magnification)

Presence or absence of peeling No peeling No peeling

As shown in Table 3, in the case of adhesion to the substrate at high temperature/high humidity, both Example 1 and Comparative Example 1 showed excellent adhesion to the substrate without peeling.

division

Thickness(㎛) NMP 5% HCl 5% TMAH Before After Variation Before After Variation Before After Variation Example 1

2.177 2.182 0.580%


2.139 2.141 1.002%


2.215 2.172 -1.292%


2.104 2.108 2.453 2.508 2.231 2.205 2.241 2.270 2.175 2.186 2.175 2.159 Average 2.174 2.187 2.256 2.278 2.207 2.179 Comparative Example 1

2.447 2.461 1.321%


2.432 2.447 0.828%


2.371 2.386 0.516%


2.388 2.456 2.399 2.427 2.293 2.296 2.431 2.446 2.415 2.430 2.307 2.326 Average 2.422 2.454 2.415 2.435 2.324 2.336

As shown in Table 4, in the case of the chemical resistance properties of Example 1 and Comparative Example 1, as the change in thickness was found to be within the range of -5 to +5, the chemical resistance of Example 1 and Comparative Example 1 It was found that the characteristics were also good.

In general, acrylic-epoxy-based materials are known to have superior chemical resistance or adhesion to substrates compared to silicone-based materials, but from the above-described results, the silicone resin according to the present invention is based on acrylic-epoxy in terms of chemical resistance or adhesion. It was confirmed that it had the same physical properties as the material of and had excellent other durability (heat resistance/light resistance) and hardness.

< Example 4>

4-1: Preparation of silicone resin

In a reaction vessel equipped with a cooling tube and a stirrer, with respect to 100 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 3-methacryloxypropyltrimethoxy silane (in Formula 1, R ₁ is a methacrylic group, X is methacrylic Time, n is 1) 45 parts by weight (0.35 mol), methyltrimethoxy silane (in Formula 2, R ₂ is a methyl group, X is a methoxy group, n is 1) 4 parts by weight (0.05 mol) And tetraethoxy silane (in Chemical Formula 3, X is an ethoxy group) 60 parts by weight (0.6 mol) were mixed at room temperature, and then 0.01% Acrylic acid 5 parts by weight (alkoxy equivalent) was gradually dropped therein for 1 hour. The hydrolysis reaction proceeded. 55 parts by weight (0.5 mol) of zirconium (IV) acetate (in Chemical Formula 6, Me is zirconium, X is an acetate group) was gradually dropped over 30 minutes, and then heated to 70° C. to proceed for 5 hours. I did. Thereafter, the reaction was cooled to room temperature and stabilized for 10 hours, and then 80 parts by weight of propylene glycol monomethyl ether acetate was added thereto. Afterwards, a silicone resin having a solid content of 39% by weight by vacuum evaporation at 60° C. to remove adducts such as water and alcohol generated during the reaction (in Formula 7, R ₁ is a methacrylic group, R ₂ is a methyl group, and Me Is zirconium, n is 1) 178g was obtained. The weight average molecular weight of the silicone resin thus obtained was 4,300 g/mol.

4-2: Preparation of silicone resin composition

With respect to 100 parts by weight of the silicone resin obtained in Example 4-1, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 1 part by weight of a photoinitiator (OXE-01, Ciba) as an additive, and dipentaerythritol hexaacrylate (DPHA) 25 parts by weight, 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (DIC, RS-72K) (diluted by 3.8%) are mixed to have a solids content of 17% by weight photocurable silicone resin 50 g of the composition was prepared.

4-3: Insulation film formation

On the glass surface, the photocurable silicone resin composition obtained in Example 4-2 was spin-coated at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm. The glass on which the coating film was formed was subjected to a pre-bake step at 100°C for 90 seconds on a hot plate, and then exposed to an exposure amount of 80 mJ/cm ² (igh line), and then with Tetramethyl ammonium hydroxide (TMAH) 2.38% alkaline developer. It developed for 50 seconds. When development was completed, a post bake step was performed at 150° C. for 30 minutes in a convection oven to form an insulating film.

< Example 5>

5-1: Preparation of silicone resin

A silicone resin was prepared in the same manner as in Example 4-1, but instead of 3-methacryloxypropyltrimethoxy silane, 3-mercaptopropyltrimethoxy silane (in Formula 1, R ₁ is a mercapto group, and X is It is a methoxy group, n is 1) 50 parts by weight (0.4 mol) of a silicone resin having a solid content of 40% by weight (in Chemical Formula 7, R ₁ is a mercapto group, R ₂ is a methyl group, and Me is zirconium) , n is 1) 185 g was obtained. The weight average molecular weight of the silicone resin thus obtained was 5,200 g/mol.

5-2: Preparation of silicone resin composition

Based on 100 parts by weight of the silicone resin obtained in Example 5-1, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 1 part by weight of a photoinitiator (OXE-01, Ciba) as an additive, and dipentaerythritol hexaacrylate (DPHA) 25 parts by weight, 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (DIC, RS-72K) (diluted by 3.8%) are mixed to have a solids content of 17% by weight photocurable silicone resin 50 g of the composition was prepared.

5-3: Insulation film formation

On the glass surface, the photocurable silicone resin composition obtained in Example 5-2 was spin-coated at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm. The glass on which the coating film was formed was subjected to a pre-bake step at 100°C for 90 seconds on a hot plate, and then exposed to an exposure amount of 80 mJ/cm ² (igh line), and then with Tetramethyl ammonium hydroxide (TMAH) 2.38% alkaline developer. It developed for 50 seconds. When development was completed, a post bake step was performed at 150° C. for 30 minutes in a convection oven to form an insulating film.

< Example 6>

6-1: Preparation of silicone resin

A silicone resin was prepared in the same manner as in Example 4-1, but instead of methyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane (in Formula 2, R ₂ is an epoxy group (3-glycidyloxypropyl group). ), X is a methoxy group, n is 1), instead of 0.5 mol of zirconium (IV) acetate, zirconium (IV) butoxide (in Formula 6, X is a butoxy group, Me is zirconium) 53 parts by weight ( 0.5 mol) was added to obtain 188 g of a silicone resin having a solid content of 48.9% by weight (in Chemical Formula 7, R ₁ is a methacrylic group, R ₂ is an epoxy group, Me is zirconium, and n is 1). The weight average molecular weight of the silicone resin thus obtained was 5,250 g/mol.

6-2: Preparation of silicone resin composition

With respect to 100 parts by weight of the silicone resin obtained in Example 6-1, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 1 part by weight of a photoinitiator (OXE-01, Ciba) as an additive, dipentaerythritol hexaacrylate (DPHA) 25 parts by weight, 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (DIC, RS-72K) (diluted by 3.8%) are mixed to have a solids content of 17% by weight photocurable silicone resin 50 g of the composition was prepared.

6-3: Insulation film formation

On the glass surface, the photocurable silicone resin composition obtained in Example 6-2 was spin-coated at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm. The glass on which the coating film was formed was subjected to a pre-bake step at 100°C for 90 seconds on a hot plate, and then exposed to an exposure amount of 80 mJ/cm ² (igh line), and then with a hydroxide Tetramethyl ammonium hydroxide (TMAH) 2.38% alkali developer. It developed for 50 seconds. When development was completed, a post bake step was performed at 150° C. for 30 minutes in a convection oven to form an insulating film.

< Comparative example 5>

5 -1: Preparation of acrylic-epoxy resin

2.5 parts by weight of 2-2'azobis isobutyronitrile were dissolved in 100 parts by weight of diethylene glycol dimethyl ether in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 5 parts by weight of styrene, 7.5 parts by weight of methacrylic acid, 27.5 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added, followed by nitrogen substitution, followed by stirring. The reaction was heated to 80° C. and reacted for 6 hours to obtain 355 g of an acrylic-epoxy resin having a solid content of 39% by weight. The weight average molecular weight of the acrylic-epoxy resin thus obtained was 7,500 g/mol.

5-2: Preparation of acrylic-epoxy resin composition

Based on 100 parts by weight of the acrylic-epoxy resin obtained in Comparative Example 5-1, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 1 part by weight of a photoinitiator (OXE-01, Ciba) as an additive, and dipentaerythritol hexaacrylate ( DPHA) 25 parts by weight, 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (DIC, RS-72K) (diluted by 3.8%) are mixed, and the solid content is 17% by weight acrylic- 50 g of an epoxy resin composition was prepared.

5 -3: insulating film formation

On the glass surface, the acrylic-epoxy resin composition obtained in Comparative Example 5-2 was spin-coated at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm. The glass on which the coating film was formed was subjected to a pre-bake step at 100°C for 90 seconds on a hot plate, and then exposed to an exposure amount of 80 mJ/cm ² (igh line), and then with a hydroxide Tetramethyl ammonium hydroxide (TMAH) 2.38% alkali developer. It developed for 50 seconds. When development was completed, a post bake step was performed at 150° C. for 30 minutes in a convection oven to form an insulating film.

< Comparative example 6>

An acrylic-epoxy resin composition was prepared in the same manner as in Comparative Example 5, but based on 100 parts by weight of the acrylic-epoxy resin, 100 parts by weight of dipentaerythritol hexaacrylate (DPHA) and an epoxy curable compound (E-103A, Arakawa) 20 By adding parts by weight, 320 g of an acrylic-epoxy resin composition having a solid content of 22.5% was obtained, and then an insulating film was formed in the same manner as in Example 4.

< Comparative example 7>

A photocurable silicone resin composition was prepared in the same manner as in Example 4, but when preparing the silicone resin, the reaction was performed except for zirconium (IV) acetate to obtain 150 g of a silicone resin. The weight average molecular weight of the silicone resin thus obtained was 5,200 g/mol. Based on 100 parts by weight of the obtained silicone resin, 150 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 1 part by weight of a photoinitiator (OXE-01, Ciba) as an additive, 25 parts by weight of dipentaerythritol hexaacrylate (DPHA), 3 parts by weight of 3-glycidyloxypropyltrimethoxy silane and 0.3 parts by weight of a fluorine-based surfactant (DIC, RS-72K) (diluted by 3.8%) were mixed to obtain 50 g of an acrylic-epoxy resin composition having a solid content of 17% by weight. , An insulating film was formed in the same manner as in Example 4.

Each of the compositions of Examples 4 to 6 and Comparative Examples 5 to 7 was evaluated by measuring physical properties, and the results are shown in Tables 5 and 6.

(1) Measurement of pencil hardness change by curing temperature

The compositions of Examples 4 to 6 and Comparative Examples 5 to 7 were spin-coated on glass at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm, and then pre-baked (PRB) at 100° C. for 90 seconds on a hot plate. Then, exposure (UV) 80mJ/cm ² (igh line), development 50 seconds (2.38% TMAH), and post-baked (PSB) for 30 minutes at 100°C, 120°C, 140°C and 150°C in a convection oven. The hardness of the cured film was measured by pencil hardness, and the physical properties were measured by applying a load of 9.8N using a pencil and a test machine conforming to the JIS-D5400 standard, and are shown in Table 5.

(2) Measurement of transmittance according to high temperature exposure

The compositions of Examples 4 to 6 and Comparative Examples 5 to 7 were spin-coated on glass at 450 rpm for 12 seconds to form a coating film having a thickness of 2 μm, and then pre-baked (PRB) at 100° C. for 90 seconds on a hot plate. Then, exposure (UV) 80mJ/cm ² (igh line), development 50 seconds (2.38% TMAH), and cured at 150° C. for 30 minutes in a convection oven. The transmittance change after exposure to the cured film at a high temperature (250° C. for 90 minutes) was measured using a UV/Vis Spectrometer (Thermo, Evolution600) at a wavelength of 400 nm, and is shown in Table 5.

(3) Measurement of high temperature and high humidity adhesion characteristics

The compositions of Examples 4 to 6 and Comparative Examples 5 to 7 were spin-coated on ITO Glass at 450 rpm for 12 seconds to form a coating film, and then pre-baked (PRB) at 100° C. for 90 seconds on a hot plate, and exposure ( UV) 80mJ/cm ² (igh line), development 50 seconds (2.38% TMAH), cured at 150°C for 30 minutes in a convection oven. The cured film was exposed at 120° C. at 100% RH for 6 hours, and then the adhesion was observed with an optical microscope (NIKON, MM-400) (Table 6). At this time, the measurement was repeated three times.

division Example 4 Example 5 Example 6 Comparative Example 5 Comparative Example 6 Comparative Example 7 Pencil hardness
(Hardness by temperature) Hardening
(100℃ for 30 minutes) H H H B or less B or less H Hardening
(120℃ for 30 minutes) H 2H H B or less B or less H Hardening
(140℃ for 30 minutes) 3-4H 3H 3-4H B or less B or less 3H Hardening
(150℃ for 30 minutes) 4-5H 4-5H 4-5H H H 3-4H Transmittance
(%, 400nm) Hardening
(150℃ for 30 minutes) 99.7 99.8 99.7 98.4 98.1 99.5 High temperature exposure
(240℃ for 90 minutes) 98.5 98.2 98.9 85.1 79.8 98.1

As shown in Table 5, it was confirmed that the silicone resin compositions of Examples 4 to 6 had excellent pencil hardness at a lower temperature than the acrylic-epoxy compositions of Comparative Examples 5 and 7.

In addition, it was found that the transmittance of the silicone resin compositions of Examples 1 to 3 was much smaller than that of the acrylic-epoxy compositions of Comparative Examples 5 and 7 according to high temperature exposure.

division Optical microscope image (×200 magnification) Presence or absence Example 4

No peeling Example 5

No peeling Example 6

No peeling Comparative Example 5

Some peeling Comparative Example 6

Some peeling Comparative Example 7

Complete peeling

As shown in Table 6, in the case of adhesion to the substrate (ITO Glass) at high temperature/high humidity, in the case of Comparative Examples 5 and 6, some peeled off, and in the case of Comparative Example 7, completely peeled, whereas in Examples 4 to 6 In the case, it was found that the adhesion was all excellent without peeling.

All simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (14)

It is a condensation reaction product of at least one compound selected from compounds represented by the following formulas 1 to 3 and at least one compound selected from compounds represented by the following formulas 4 to 6, and includes a repeating unit represented by the following formula 7, Silicone resin having a weight average molecular weight of 1,000 to 100,000 g/mol:
<Formula 1>
R _1(n) SiX _(4-n)
<Formula 2>
R _2(n) SiX _(4-n)
<Formula 3>
SiX ₄
<Formula 4>
R _1(n) MeX _(4-n)
<Formula 5>
R _2(n) MeX _(4-n)
<Formula 6>
MeX ₄
<Formula 7>

<Formula 8>

In Formulas 1 to 8, R ₁ is each independently a vinyl group, methacryl group, methacryloxy group, acetate group, acrylic group, acryloxy group, or mercapto group; R ₂ is each independently a hydroxy group, a hydrogen atom, a fluorine atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group, X Is a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group, wherein R ₂ and X are not the same as each other, and Me is a metal,

Is represented by Formula 8, n in Formulas 1 to 6 is an integer of 1 to 3, and n in Formula 7 is 10 or less.
delete The silicone resin according to claim 1, wherein the Me is selected from the group consisting of zirconium, titanium, manganese and tungsten.
A silicone resin having a weight average molecular weight of 1,000 to 100,000 g/mol by condensation reaction of at least one compound selected from the compounds represented by the following formulas 1 to 3 and at least one compound selected from the compounds represented by the following formulas 4 to 6 A method for producing a silicone resin according to claim 1, characterized in that to prepare:
<Formula 1>
R _1(n) SiX _(4-n)
<Formula 2>
R _2(n) SiX _(4-n)
<Formula 3>
SiX ₄
<Formula 4>
R _1(n) MeX _(4-n)
<Formula 5>
R _2(n) MeX _(4-n)
<Formula 6>
MeX ₄
In Formulas 1 to 6, R ₁ is each independently a vinyl group, a methacryl group, a methacryloxy group, an acetate group, an acrylic group, an acryloxy group, or a mercapto group; R ₂ is each independently a hydroxy group, a hydrogen atom, a fluorine atom, a straight or branched chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, an aryl group having 2 to 10 carbon atoms, an epoxy group or a phenylene group, X Is a hydroxy group, an alkoxy group having 1 to 10 carbon atoms, an acetate group or a halogen group, wherein R ₂ and X are not the same, Me is a metal, and n is an integer of 1 to 3.
delete The method of claim 4, wherein the Me is selected from the group consisting of zirconium, titanium, manganese and tungsten.
The method of claim 4, wherein the silicone resin comprises at least one compound selected from compounds represented by Formulas 1 to 3 and at least one compound selected from compounds represented by Formulas 4 to 6 in a molar ratio of 100:1 to 100 A method for producing a silicone resin, characterized in that produced by condensation.
The method of claim 4, wherein the condensation reaction is performed at room temperature to 150°C for 1 to 48 hours.
A silicone resin composition comprising 1 to 70% by weight of the silicone resin of any one of claims 1 and 3.
The silicone resin composition of claim 9, wherein the silicone resin composition has a property of curing at 100 to 300°C.
A cured product formed of the silicone resin composition of claim 9.
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