KR102015103B1 - Thermosetting resin composition - Google Patents

Abstract

The present invention is excellent in reactivity and polymerization stability, by introducing a high hardness, high sensitivity, high molecular weight ethylenically unsaturated monomer free of impurities, effectively improve the crosslinking progress effectively mechanical properties, heat resistance chemical resistance and adhesion to the substrate in the subsequent process It is related with the thermosetting resin composition which can improve the flatness characteristic in a board | substrate which does not fall and especially a very big uneven | corrugated step | step difference is very large.

Description

Thermosetting resin composition

TECHNICAL FIELD The present invention relates to a thermosetting resin composition, and more particularly, to a thermosetting resin composition useful as a protective film forming material for an optical device.

Optical devices such as liquid crystal display devices (LCDs) are subjected to harsh processing such as immersion treatment with organic solvents, acids, alkali solutions, etc. during the manufacturing process, or localized high-temperature heating of the surface by sputtering when forming wiring electrode layers. Will receive. Therefore, in order to prevent the deterioration at the time of manufacture, a material with high high temperature stability may be provided as a protective film in these elements.

The protective film must be excellent in chemical resistance and water resistance such as solvent resistance, acid resistance, alkali resistance, etc. to withstand the harsh processing conditions as described above, and have excellent adhesion to the substrate or lower layer, and have surface tension, flatness, surface hardness and transparency. It should be high and free from staining, yellowing, whitening, etc. for a long time, and should be excellent in heat resistance and light resistance.

In particular, in the case of flatness characteristics, recently, substrates having a large unevenness level due to the diversification of the structure of the color layer (color filter) should be improved compared to the existing characteristics, and the inherent characteristics of other protective films such as surface tension and surface roughness Development is a very important situation as it affects production yields depending on the characteristics.

Generally, a protective film composition is manufactured in the form of curable resin composition, and is classified roughly into thermosetting and photocurable (photosensitive). When the pattern formation of a protective film is required, the photosensitive resin composition is used, but otherwise, the process is convenient, and the crosslinking density can be raised and the thermosetting resin composition which is excellent in mechanical property and heat resistance is used.

Japanese Patent Laid-Open Nos. 2000-103937, 2000-119472 and 2000-143772 disclose a thermosetting resin composition as a composition constituting a protective film. That is, the composition comprised from the acrylic resin containing a carboxyl group and an epoxy group, the polyfunctional monomer containing an ethylenically unsaturated group, and a thermal polymerization initiator is used.

However, the conventional thermosetting resin composition having such a composition has a sharp decrease in flatness characteristics on a substrate having a very large unevenness level, and a problem of deterioration of adhesion and chemical resistance due to uncured portion inside the protective film when the post process is performed at a high temperature. Hardening shrinkage of the acrylic resin itself causes problems such as deterioration in heat resistance.

In addition, since the final production yield is reduced due to the post-processing problem according to the flatness and surface tension of the cured film, the development of a protective film material that improves this is urgently required.

An object of the present invention is to introduce high hardness, high sensitivity, high molecular weight ethylenically unsaturated monomer, excellent in reactivity and polymerization stability, improve the crosslinking progress quickly and effectively to improve mechanical properties, heat resistance chemical resistance and substrate in the subsequent process It is an object of the present invention to provide a thermosetting resin composition capable of improving the flatness characteristics of a substrate, in which adhesion strength is not lowered, and particularly the uneven step is very large.

In addition, to improve the surface properties through a simple formulation of the resin composition, to provide a cured film that can solve the cause of the reduction in production yield.

The present invention, in order to solve the above problems, [A] (a1) at least one compound selected from the group consisting of unsaturated carboxylic acid or unsaturated carboxylic anhydride, (a2) epoxy group-containing unsaturated compound, (a3) said (a1) And copolymers of olefinically unsaturated compounds other than (a2); And [B] A thermosetting resin composition comprising an unsaturated monomer having 8 to 12 ethylenically unsaturated bonds.

In another embodiment of the present invention, the unsaturated monomer having 8 to 12 ethylenically unsaturated bonds [B] is a compound represented by the following Chemical Formula 1.

      <Formula 1>

R in Formula 1 is hydrogen or any one selected from the group consisting of Formula 2 or Formula 3.

<Formula 2>

<Formula 3>

In another embodiment of the present invention, the thermosetting resin [B] having 8 to 12 ethylenically unsaturated bonds has a weight average molecular weight of 1000 to 5,000.

In another embodiment of the present invention, the thermosetting resin [B] having 8 to 12 ethylenically unsaturated bonds may be included in an amount of 50 to 150 parts by weight based on 100 parts by weight of the copolymer [A].

In another embodiment of the present invention, the thermosetting resin composition may further include a curing agent [C] and other additives [D].

In another embodiment of the present invention, the curing agent [C] is included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the copolymer [A], and the other additive [D] is used in 100 parts by weight of a copolymer [A]. It is characterized by including 0.1 to 5 parts by weight.

In addition, the present invention provides a cured film made of the thermosetting resin composition.

In another embodiment of the present invention, the cured film is characterized in that the protective film for an optical device.

The thermosetting resin composition according to the present invention does not deteriorate heat resistance, chemical resistance and mechanical properties in a post process by using a high hardness and high sensitivity high molecular weight unsaturated monomer having 8 to 12 ethylenically unsaturated bonds, and in particular, produces very large irregularities Since the genie can provide excellent flatness characteristics even in a substrate, it is useful as a high flat protective film forming material for an optical device.

In addition, the simple formulation can improve the surface properties of the cured film to increase the production yield.

Hereinafter, the present invention will be described in more detail.

According to one embodiment of the present invention, (a1) at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, (a2) epoxy group-containing unsaturated compounds, olefinically unsaturated compounds other than the above (a1) and (a2) It is providing the thermosetting resin composition containing the copolymer [A] of (a3) and high hardness and high sensitivity high molecular weight thermosetting resin [B] which has 8-12 ethylenically unsaturated bonds.

First, copolymer [A] is obtained by a known polymerization method, that is, compound (a1), compound (a2) and compound (a3) can be synthesized by radical polymerization in the presence of a polymerization initiator in a solvent.

The copolymer [A] may contain the compound (a1) in an amount of 5 to 40% by weight, preferably 10 to 30% by weight. It is preferable when considering storage stability.

As said compound (a1), For example, Monocarboxylic acids, such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids.

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability. Among these compounds can be used alone or in combination.

In addition, the copolymer [A] may contain the compound (a2) in an amount of 10 to 70% by weight, preferably 20 to 60% by weight, which is considered in terms of heat resistance and surface hardness of the resulting cured film or storage stability of the copolymer. It may be desirable when considering.

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, Acrylic acid-3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7-epoxy Heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like can be preferably used in view of increasing copolymerization reactivity and heat resistance and hardness of the resulting protective film. It may be used alone or in combination by selecting from the above compounds.

The copolymer [A] may contain 10 to 70% by weight of compound (a3), preferably 20 to 50% by weight, which is preferable when the storage stability of the copolymer and the cured film consider heat resistance and surface hardness. can do.

As said compound (a3), For example, Methacrylic acid alkyl esters, such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isoboroyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acacrylate, dicyclopentenyloxyethyl acrylate and isoboroyl acrylate; Methacrylic acid aryl esters such as petyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid; Hydroxyalkyl esters such as 2-hydroxy ethyl methacrylate and 2-hydroxy propyl methacrylate; And styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene, and the like may be preferable in terms of copolymerization reactivity and heat resistance. . Among these compounds, they may be used alone or in combination.

Such a copolymer [A] has a carboxyl group and / or a carboxylic anhydride group, and an epoxy group, and can harden | cure easily by heating, even without using a special hardening | curing agent.

As an example of the solvent which can be used for the synthesis | combination of the said copolymer [A], Alcohol, 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.

As a polymerization initiator which can be used for the synthesis | combination of the said copolymer [A], what is generally known as a radical polymerization initiator can be used. For example, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, t-butyl peroxy pibarate, 1,1'-bis- (t-butyl peroxy) cyclohexane; And hydrogen peroxide.

When a peroxide is used as a radical polymerization initiator, you may use it as a redox initiator by using a peroxide together with a reducing agent.

The thermosetting resin composition of the present invention comprises a high hardness, high sensitivity high molecular weight thermosetting resin [B] having 8 to 12 ethylenically unsaturated bonds together with the copolymer [A], and thus excellent heat resistance and chemical resistance of the acrylic resin itself. It has excellent abrasion resistance and ethylene group at the terminal, which is excellent in reactivity, and as a result, the cured film can secure a higher curing density. As a result, the heat resistance, UV resistance, and chemical resistance of the cured film can be prevented from being lowered. .

The high hardness and high sensitivity high molecular weight unsaturated monomer [B] which has such 8-12 ethylenically unsaturated bonds is a thermosetting resin composition characterized by the compound represented by following formula (1).

<Formula 1>

R in Formula 1 is hydrogen or any one selected from the group consisting of Formula 2 or Formula 3.

<Formula 2>

<Formula 3>

The high hardness and high sensitivity high molecular weight unsaturated monomer [B] which has the said 8-12 ethylenically unsaturated bond is a thermosetting resin composition characterized by the weight average molecular weight 1000-5,000.

In the case where the weight average molecular weight of the high hardness and high sensitivity high molecular weight unsaturated monomer is greater than 5,000, there is a problem such as heat shrinkage and chemical resistance deterioration in the post-process due to the presence of an uncured portion in the composition, and in particular, the followability to the substrate is increased. Therefore, in the case of a large uneven step, the flatness has a problem that the flatness is sharply lowered.

The content of the unsaturated monomer [B] is 50 to 150 parts by weight, preferably 70 to 130 parts by weight based on 100 parts by weight of the copolymer [A] to form a cured film having a high crosslinking density or satisfy various resistances of the cured film. It is advantageous in terms of preventing the problem that the property of the cured film becomes unstable or the adhesion decreases.

When content of the said unsaturated monomer [B] is less than 50 weight part with respect to 100 weight part of copolymers [A], hardenability cannot be improved, and when it exceeds 150 weight part, the adhesiveness of the protective film obtained will fall easily.

On the other hand, in another embodiment of the present invention, in addition to the copolymer [A] and high hardness and high sensitivity high molecular weight unsaturated monomer [B] having 8 to 12 ethylenically unsaturated bonds, a curing agent [C] and other additives [D] It may contain.

In the present invention, the curing agent [C] is a component that causes a curing reaction with the component [A]. Examples of the curing agent include 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, pyromellitic anhydride, trimellitic anhydride, phthalic anhydride, and the like. These anhydrides may be used by chemical modification.

The curing agent [C] is preferably 1 to 50 parts by weight, preferably 5 to 20 parts by weight based on 100 parts by weight of the copolymer [A], but the content is less than 1 part by weight based on 100 parts by weight of the copolymer [A]. In this case, it is difficult to obtain a protective film having a sufficiently high crosslinking density and there is a problem that various resistances of the protective film are lowered. When it exceeds 50 parts by weight, a large amount of unreacted material is likely to remain in the film of the protective film obtained, and as a result, the properties of the protective film. There is a problem that this destabilization or adhesiveness tends to be degraded.

In addition, the thermosetting resin composition of the present invention may further include one or more kinds optionally from the group consisting of a surfactant, an adhesion aid, an antioxidant, and an ultraviolet absorber as other additives [D].

The surfactant serves to improve applicability, and may include fluorine or silicone-based surfactants, for example, FC-129, FC-170C, FC-430, etc. of 3M. It can be used in an amount of 0.1 to 5 parts by weight, more preferably 0.1 to 2 parts by weight based on 100 parts by weight of the copolymer [A].

When using the said surfactant more than 5 weight part with respect to 100 weight part of copolymers [A], there exists a problem which foams easily at the time of application | coating.

The adhesion assistant plays a role of improving adhesion to the substrate. As the adhesion assistant, a functional silane coupling agent is preferably used. For example, a trimethoxy silyl benzoic acid, (gamma) -isocyanate propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are mentioned. It may be used in an amount of 0.1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the copolymer [A]. When used, heat resistance tends to decrease.

The thermosetting resin composition of this invention can be manufactured by melt | dissolving other additive [D] selectively with a copolymer [A], an unsaturated monomer [B], and a hardening agent [C] mentioned above in a solvent.

It is preferable to use what does not react with any component of the solvent used at this time. For example, a solvent used for the polymerization of the copolymer [A] may be used, and among them, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and propylene glycol methyl ether in view of solubility, reactivity, and convenience of coating film formation. Acetate is preferred. It is also possible to use a high boiling point solvent together with the solvent.

As the high boiling point solvent, for example, N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether Etc. can be mentioned. When using such a high boiling point solvent together, it is preferable that the mixing ratio with the said solvent is said solvent: high boiling point solvent = 100: 0-40.

The total solids content of the solution comprising the copolymer [A], high hardness, high sensitivity high molecular weight unsaturated monomer [B], curing agent [C], other additives [D] and a solvent having 8 to 12 ethylenically unsaturated bonds is It is preferable that it is 10 to 40% by weight, when the solid content is less than 10% by weight, the coating thickness cannot be obtained sufficiently, and when the solid content is 40% by weight or more, the storage stability is lowered.

The thermosetting resin composition mixed as described above may be used after filtering using a filter having a diameter of about 0.1 ~ 5㎛.

The thermosetting resin composition of this invention can form the protective film for optical devices by the following method, for example.

The thermosetting resin composition is applied to a substrate, the solvent is removed to form a coating film of the thermosetting resin composition, and then heat treated to obtain a protective film for an optical device.

As the substrate, for example, glass, quartz, silicone, resin, etc. may be used, and the resin may be a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide and cyclic olefin and Hydrogenated substance etc. are mentioned.

It does not specifically limit as a coating method of the said thermosetting resin composition solution, For example, a spray method, a roll coating method, a rotary coating method, etc. can be used.

The removal of the solvent is preferably carried out by heat treatment (pre-firing). Although the conditions of such preliminary baking differ with kinds, ratios, etc. of each component of a composition solution, it is preferable to bake about 0.5 to 20 minutes at 60-120 degreeC.

Subsequent heat treatment, the treatment temperature at this time can be treated for 5 to 100 minutes at 150 ~ 250 ℃ to produce a protective film for an optical device.

As for the thickness of the protective film formed as mentioned above, 0.1-6 micrometers is preferable, and when there is an unevenness | corrugation on the board | substrate which forms the protective film for optical devices, the said value should be understood as a value in the uppermost surface of an unevenness | corrugation.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the scope of the present invention is not limited to these Examples and Experimental Examples.

<Production example>

2,2'-azo as a polymerization initiator based on 100 parts by weight of the total amount of monomers (compound (al), compound (a2), compound (a3)) used for the synthesis of the copolymer in a reaction vessel equipped with a cooling tube and a stirrer. 5 parts by weight of bis isobutyronitrile was dissolved in 200 parts by weight of diethylene glycol dimethyl ether as a solvent.

Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid (a1), 40 parts by weight of glycidyl methacrylate (a2) and 10 parts by weight of dicyclopentenyloxyethyl methacrylate (a3) were added and nitrogen-substituted. After gently stirring started.

The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution containing copolymer [A]. Solid content concentration of the obtained polymer solution was 33 weight%.

<Examples 1-19 and Comparative Examples 1-5>

Propylene glycol monomethyl ether acetate is blended with the copolymer [A] obtained in the above Production Example and a solvent, to which a high hardness, high sensitivity high molecular weight unsaturated monomer [B] and a curing agent [C] having 8 to 12 ethylenically unsaturated bonds are added. ] And other additives [D] were blended while changing the content as shown in Table 1 and Table 2 to prepare a thermosetting resin composition.

At this time, the content unit is parts by weight based on 100 parts by weight of the copolymer [A] obtained in the preparation example (based on the solid content), and the [B-1] ethylenically unsaturated monomer is V # 800 (Osaka Organic Chemical, 1000 g of weight average molecular weight). / mol, average number of functional groups: 8), [B-2] ethylenically unsaturated monomer is V # 1000 (Osaka Organic Chemistry, weight average molecular weight 2000g / mol, average number of functional groups: 10), [B-3] ethylenically unsaturated The monomer is V # 1020 (Osaka organic chemistry, weight average molecular weight 3500g / mol, average number of functional groups: 11), [B-4] The ethylenically unsaturated monomer is V # 1080 (Osaka organic chemistry, weight average molecular weight 4800g / mol, average Functional number: 12), [C] hardener used trilimellitic anhydride (KYOESHA), and [D] other additive used surfactant FC430 (3M).

[B '] used in the comparative group was similar in molecular weight to [B-1] used in Examples 1 to 3, but monofunctional, bifunctional or trifunctional (meth) acrylates were used.

division [B-1] [B-2] [B-3] [B-4] [B ’] [C] [D] Second solvent Example 1 50 - - - - 10 0.1 10 Example 2 80 - - - - 10 0.1 10 Example 3 120 - - - - 10 0.1 10 Example 4 50 - - - 10 0.1 10 Example 5 - 80 - - - 10 0.1 10 Example 6 - 120 - - - 10 0.1 10 Example 7 - 50 - - 10 0.1 10 Example 8 - 80 - - 10 0.1 10 Example 9 - - 120 - 10 0.1 10 Example 10 - - 50 10 0.1 10 Example 11 - - 80 10 0.1 10 Example 12 - - 120 10 0.1 10 Comparative Example 1 - - - - 50 10 0.1 10 Comparative Example 2 - - - - 80 10 0.1 10 Comparative Example 3 - - - - 120 10 0.1 10

division [B-1] [B-2] [B-3] [B-4] [B ’] [C] [D] Second solvent Example 13 80 - - - - 10 0.08 20 Example 14 80 - - 10 0.08 20 Example 15 80 10 0.05 20 Example 16 80 10 0.08 20 Example 17 80 10 0.05 20 Example 18 80 10 0.08 20 Example 19 80 10 0.05 20 Comparative Example 4 80 10 0.08 20 Comparative Example 5 80 10 0.05 20

Experimental Example

Using the spin coater, the thermosetting resin composition was coated on the glass substrate so that the film thickness was 2 μm, and then fired at 230 ° C. for 30 minutes in a clean oven to form a cured film on the glass substrate.

Evaluation method for the protective film used in the present invention is as follows, the evaluation results for the protective film prepared in Examples and Comparative Examples are shown in Table 3 and Table 4.

(1) adhesion

According to the checkered tape method, using a cutter knife on the cured film, cut 11 rows of cuts 1 mm apart to the upper surface of the glass substrate, and cut 11 rows of cuts 1 mm apart in the vertical direction to the upper surface of the glass substrate. After the checkered pattern was formed, an adhesive test (Elcometer, Part Number K0001539M001) was applied on the checkered pattern and then peeled off, and the number of peeled checkered patterns was measured, and the adhesion of the cured film was evaluated according to the following criteria.

In Tables 3 and 4, the meanings of ○, Δ, and × are as follows.

(Circle): The number of the peeled checkerboard patterns 5 or less

(Triangle | delta): The number of the peeled checkerboard patterns 6-49

×: 50 or more pieces of checkered patterns

(2) surface hardness

The cured film was subjected to the pencil hardness test method according to the pencil hardness method (test standard: ASTM D3363) to evaluate the surface hardness.

(3) transparency

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101, Shimadzu Corporation), and the transparency of the protective film was evaluated according to the following criteria. In Tables 3 and 4, the meanings of ○, Δ, and × are as follows.

○: 95% minimum transmittance

△: minimum transmittance of 90 to 95%

X: less than 90% of the lowest transmittance

(4) UV resistance

The transmittance of the protective film was measured at 400 to 700 nm using a spectrophotometer (UV-3101PC, manufactured by Shimadzu Corporation). Separately, UV (wavelength 254 nm, irradiation amount 200mJ / cm 2) was irradiated to the cured film, and the transmittance was measured by the same method. From each transmittance, UV resistance of the protective film was evaluated according to the following criteria. In the following Table 3 and Table 4, the meaning of ○ and × is as follows.

(Circle): The change of a transmission spectrum is within 1%.

×: change in transmission spectrum is more than 1%

(5) flatness

The substrate used to measure the flatness is a collection of several pixels, as is typically used for display purposes, with one pixel size of 30 * 60 μm (horizontal * vertical), with one empty space for every three pixels. It is a board | substrate with the unevenness | corrugation which a step of an empty space is 2.8 micrometers exists.

After the cured film is coated on the substrate, the surface level of the flattened film is measured again using α-step (manufacturer: KLA Tencor, equipment name: AS-500) to display this value.

(6) Heat resistance characteristic (heat resistance thickness)

As shown in the following Equation 1, after measuring the thickness of the cured film is finished in the oven process for 30 minutes at 230 ℃, after adding an additional 230 ℃ 60min oven process to measure the thickness of the cured film to change the difference (%) Calculated as

At this time, the thickness of the cured film investigated the surface profile using the alpha step (manufacturer: KLA Tencor company, equipment name: AS-500) in the state which cut out the cured film with the knife, and measured from this.

In the above formula, T1 means the thickness of the cured film after the oven process, T2 means the thickness of the cured film after the additional oven process.

(7) acid resistance

After the glass substrate on which the protective film was formed was immersed in a 25 wt% aqueous hydrochloric acid solution for 30 minutes at 30 ° C., the appearance change of the protective film was observed to evaluate the acid resistance of the protective film.

(8) alkali resistance

After the glass substrate on which the protective film was formed was immersed in a 10 wt% sodium hydroxide aqueous solution for 30 ° C. for 60 minutes, the appearance change of the protective film was observed to evaluate the alkali resistance of the protective film.

(9) Device life

The glass substrate on which the protective film was formed was left for 12 hours in a 100% environment at 120 ° C., and the adhesive test was performed in the same manner as in (1).

(10) surface tension

The surface tension (mN / m) was calculated by measuring the contact angle of the glass substrate on which the protective film was formed with secondary distilled water and formamide.

division Adhesiveness surface
Hardness surface
stain Transparency UV resistance flatness
(Μm) Heat resistant
characteristic Acid resistance Alkali resistance  stain Example 1 ○ 5H ○ ○ 0.43 95% Slightly cloudy Slightly cloudy ○ Example 2 ○ 5H ○ ○ 0.30 97% Slightly cloudy Slightly cloudy ○ Example 3 ○ 5H ○ ○ 0.38 98% Slightly cloudy Slightly cloudy ○ Example 4 ○ 5H ○ ○ 0.59 97% Slightly cloudy Slightly cloudy ○ Example 5 ○ 5H ○ ○ 0.26 98% No change Slightly cloudy ○ Example 6 ○ 5H ○ ○ 0.37 98% No change No change ○ Example 7 ○ 5H ○ ○ 0.41 97% No change No change ○ Example 8 ○ 5H ○ ○ 0.22 98% No change Slightly cloudy ○ Example 9 ○ 6H ○ ○ 0.36 98% No change Slightly cloudy △ Example 10 ○ 5H ○ ○ 0.39 97% No change No change ○ Example 11 ○ 6H ○ ○ 0.21 98% No change No change ○ Example 12 ○ 6H ○ ○ 0.26 98% No change Slightly cloudy △ Comparative Example 1 ○ 4H ○ ○ 0.71 86% No change Slightly cloudy ○ Comparative Example 2 ○ 4H ○ ○ 0.55 92% No change Slightly cloudy ○ Comparative Example 3 ○ 4H ○ ○ 0.62 93% No change Slightly cloudy △

As can be seen in Table 3, Examples 1 to 1 comprising a high hardness and high sensitivity high molecular weight unsaturated monomer [B-1, B-2, B-3, B-4] having 8 to 12 ethylenically unsaturated bonds In the case of the thermosetting resin composition of 12, the heat resistance, the chemical resistance, the adhesiveness and the like are good, and in particular, even the substrate having a large uneven step shows excellent flatness characteristics.

In addition, when comparing Example 2, Example 5, Example 8, and Example 11, it was confirmed that the higher the molecular weight, the more uneven step becomes, and the more favorable the heat resistance characteristics. This is because unsaturated monomers having 10 or more ethylenically unsaturated bonds have high sensitivity and thus increase the curing density.

In addition, the ethylenically unsaturated monomers [B-1, B-2, B-3, B-4] of high molecular weight level (2000 to 5000 g / mol) are not only stacked on the uneven surface of the substrate but also well on the uneven portion. It can be seen that the filling and acts as a planarization, the molecular weight is large, due to the excellent heat resistance characteristics.

When Examples 1, 2, and 3 and Comparative Examples 1, 2, and 3 were applied, when a medium molecular weight [B-1] having 10 or more ethylenically unsaturated bonds was applied, a mono- or bi-functional or It can be seen that the flatness is excellent and the surface hardness is also increased compared to Comparative Examples 1, 2, and 3 to which the (meth) acrylate having a trifunctionality or less is applied.

However, when the content of the ethylenically unsaturated resins [B-1], [B-2], [B-3], and [B-4] is 80% by weight or more, the followability to the surface of the substrate is increased, resulting in poor flatness. In addition, it can be seen that problems such as chemical resistance, heat resistance, and adhesion decrease due to a large amount of uncured portion.

As can be seen in Table 4, the surface tension was improved by lowering the content of the other additives [E] by a small amount at a constant ethylenically unsaturated resin content, and further, the second solvent content was increased to improve stain characteristics of the cured film.

The higher the surface tension and the better the uneven characteristic of the cured film, the better the liquid crystal and polyimide coating properties, which is a post-process, which shortens the vacuum assembly time required for injecting liquid crystal during the ODF process and bonding the upper and lower substrates in a high vacuum state. This has the advantage of increasing the production yield.

As described above in detail specific parts of the present invention, it will be apparent to those skilled in the art that these specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. will be. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (7)

[A] (a1) at least one compound selected from the group consisting of unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides, (a2) epoxy group-containing unsaturated compounds, (a3) air of olefinically unsaturated compounds other than (a1) and (a2) coalescence; And
[B] A thermosetting resin composition containing an unsaturated monomer having 8 to 12 ethylenically unsaturated bonds,
The unsaturated monomer having 8 to 12 ethylenically unsaturated bonds is a compound represented by the following formula (1).
<Formula 1>

In Formula 1, R is any one selected from the group consisting of Formulas 2 and 3 below, and n is an integer of 4-6.
<Formula 2>

<Formula 3>

delete The thermosetting resin composition according to claim 1, wherein the unsaturated monomer having 8 to 12 ethylenically unsaturated bonds has a weight average molecular weight of 1,000 to 5,000. The thermosetting resin composition according to claim 1, wherein the unsaturated monomer having 8 to 12 ethylenically unsaturated bonds is included in an amount of 50 to 150 parts by weight based on 100 parts by weight of the copolymer [A]. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition further comprises a curing agent [C] and other additives [D]. The cured film manufactured from the thermosetting resin composition of any one of Claims 1-5. The cured film according to claim 6, wherein the cured film is a protective film for an optical device.