TW201311770A - Alkali-soluble silicone resin, silicone resin composition comprising the same and preparation method thereof - Google Patents

Abstract

The present invention relates to an alkali-soluble silicone resin, a silicone resin composition comprising the same and preparation a method thereof. More specifically, the present invention relates to an alkali-soluble silicone resin which comprises 60 to 95 mol% of trifunctional structure and has a weight average molecular weight of 5, 000 to 20, 000, a silicone resin composition comprising the same and a preparation method thereof. The silicone resin composition of the present invention can provide excellent coating property, hardness, heat resistance and crack resistance.

Description

Alkali soluble polyoxyn epoxide resin and polyfluorene oxide resin composition containing the same and preparation method thereof

The present invention relates to an alkali-soluble polyoxynoxy resin, a polydecaneoxy resin composition comprising the resin, and a process for the preparation thereof. More specifically, the present invention relates to an alkali-soluble polyoxyxene resin comprising 60 to 95 mol% of a trifunctional structure and having a weight average molecular weight of 5,000 to 20,000, and a polyoxyxylene resin containing the resin. Composition and preparation method thereof. The polyoxyxylene resin composition of the present invention can provide excellent coating properties, hardness, heat resistance and crack resistance.

Organic materials have been widely used in the electronics industry such as displays. Organic materials have advantages in terms of low cost and good line conformity. However, since display devices have recently become large-sized, high-resolution, and thin, the requirements for the properties of coating materials applied to display devices have become more stringent. In view of this, conventional organic materials which are inferior in properties such as heat resistance are limited in their application range.

Therefore, as a coating material having good properties in terms of developing properties (photoresist properties), light transmittance, heat resistance and the like, a silicone resin has been attracting attention. The polyoxyxene resin is applied as a semiconductor insulating film (for example, hydrogen polyoxyalkylene), a solvent type coating agent (for example, a polyoxyl resin diluted with an aromatic organic solvent), a solvent-free conformal coating agent (solvent) -free conformal coating agent), encapsulants and adhesives for electronic products, and molding materials for LED wafers.

Polyoxyxene resin manufacturers have produced various products based on traditional preparation techniques. Products such as polyoxyxene resins for coatings, MQ resins, sesquiterpene oxides, coating resins, and the like. Such preparation techniques are well known to those of ordinary skill in the art. For example, a polyoxyxylene resin can be prepared by concentrating a hydrolyzate of chlorodecane or alkoxydecane. However, when an electronic grade polyoxynitride coating material for a display is prepared by such a conventional method, it may be due to a strong catalyst used, an ion species contained in the raw material, and gel particles generated in the preparation process. Waiting for defects in the surface of the coating. Furthermore, such a display application level poly-oxygen oxide coating material cannot be mass-produced at a low cost, and therefore, economic feasibility is low.

Korean Laid-Open Patent Publication No. 10-2009-0072835 A relates to a water-soluble photosensitive polyoxyxene resin having good heat resistance and electrical insulation for a liquid crystal display device, and discloses that the resin is prepared by a sol-gel reaction. In the method, the polyoxymethylene compound is synthesized by subjecting 4-pentenoic acid or 2-allylphenol to a hydrazine hydrogenation reaction with trimethoxydecane, and adding a hydrochloric acid catalyst thereto. However, such a method requires an expensive starting material, and the platinum catalyst used in the hydrogenation reaction and/or the hydrochloric acid used as the reaction catalyst may remain in the prepared resin, and may have a terminal carboxyl group and a hydroxyphenyl group. Produce chemical changes. The step of removing the residual catalyst such as hydrochloric acid may be further employed, but in this case, the time and cost of production may increase, thereby lowering the productivity.

Korean Laid-Open Patent Publication No. 10-2009-0040079 A relates to a photosensitive polysesquioxane resin composition having good alkali developing properties and pattern resolution, and discloses an acrylic decane in an organic solvent. Another alkoxydecane is reacted with hydrochloric acid, followed by dilution A method of synthesizing a resin having a molecular weight of 1,800 to 4,500 as a resin. However, this method uses only a trifunctional raw material, and does not mention the use of a difunctional group or the like. Therefore, after the prepared resin is coated and pre-baked, cracks or pinholes may occur in the coating. In addition, gelation due to hydrochloric acid may also occur during the polymerization step of the acrylic decane.

Therefore, it is necessary to develop a polyoxynitride coating material which can satisfy major requirements such as alkali development property, light transmittance, coating property, heat resistance, hardness, and crack resistance, and can be produced at a low cost on a large scale.

[Previous Technical Publication] [Patent Publication]

Korean Early Public Patent Publication No. 10-2009-0072835 A

Korean Early Public Patent Publication No. 10-2009-0040079 A

[Technical purpose]

The present invention has been made to solve the problems involved in the prior art as described above. The technical object of the present invention is to provide an alkali-soluble polyoxygen oxide which can be used as a coating agent for a thin film transistor liquid crystal display device and the like, and which has good alkali developing properties, coating properties, heat resistance, hardness, crack resistance and productivity. a resin; and a composition comprising the resin.

[Technical solutions]

In order to achieve the above technical object, the present invention provides an alkali-soluble polyoxynoxy resin comprising: (A) at least one heat-curable group selected from the group consisting of a hydroxyl group, an alkoxy group, and an epoxy group (thermally Curable); (B) at least one alkali-developable functional group selected from the group consisting of a hydroxyl group and an alkoxy group; (C) at least one group selected from the group consisting of a C ₁ -C ₂₀ alkyl group and an aromatic group And (D) 60 to 95 mol% of a trifunctional structure derived from an organotrialkoxydecane, wherein the resin has a weight average molecular weight of 5,000 to 20,000.

In another aspect, the present invention provides a polyoxyxylene resin composition comprising the alkali-soluble polyoxyxylene resin and a solvent, and a method for preparing the polyoxyxene resin composition, the method comprising the steps of: a) mixing the alkoxydecane starting material with a diluent solvent, an organic acid and water for hydrolysis; (b) distilling the obtained product under normal pressure to remove the organic acid and water; (c) further adding an organic acid and water To the obtained product, to hydrolyze the remaining raw materials; (d) distilling the obtained product under low temperature and reduced pressure to further remove the organic acid and water; and (e) further adding a dilution solvent and performing an aging procedure The weight average molecular weight of the polyoxysiloxane resin is controlled to be 5,000 to 20,000.

In another aspect, the invention provides a coating formed by applying the polyoxyxene resin composition.

[Beneficial effect]

The alkali-soluble polyoxynene resin composition of the present invention has good coating properties, heat resistance, hardness and crack resistance, and can be mass-produced using a raw material which is cheaper than conventional raw materials, thereby expanding polyoxyl Coating materials are used in the electronics industry. In particular, the polyoxyxylene resin composition of the present invention has an alkali developability of about 15 μm on the surface of the coating layer, and a light transmittance of 95% or more (400 nm, t = 3 μm) and weight can be obtained. Loss of 1% or less (280 to 350 ° C * 10 minutes) heat resistance and about 6H pencil hard The hardness of the degree.

Hereinafter, the present invention will be more specifically described.

The alkali-soluble polyoxymethylene resin of the present invention comprises (A) at least one heat-curable functional group selected from the group consisting of a hydroxyl group, an alkoxy group and an epoxy group; (B) at least one selected from the group consisting of a hydroxyl group and an alkoxy group. a group of base developable functional groups; (C) at least one functional group selected from the group consisting of C ₁ -C ₂₀ alkyl groups and aromatic groups; and (D) 60 to 95 mole % derived from A trifunctional structure of an organotrialkoxydecane wherein the resin has a weight average molecular weight of 5,000 to 20,000. In another aspect, the polyoxyxylene resin composition of the present invention comprises the alkali-soluble polyoxynoxy resin and a solvent (solvent-diluted polyoxyl polymer).

The heat-curable functional group means a structure which initiates a curing reaction of a resin by radiation from a heat source or a light source, and is derived from the functionality of a raw material used in resin synthesis. Examples of the heat-curable functional group may include a hydroxyl group, an alkoxy group, an epoxy group, and the like, and are preferably a hydroxyl group. In one embodiment, when a film of the resin composition is applied and heated, the solvent evaporates via heat, while the -OH groups in the resin rapidly react with each other to initiate curing.

The alkali developing property means, for example, that the coating dissolves when the coating surface is contacted with an aqueous solution of 0.4% to 2.38% tetramethylammonium hydroxide (TMAH) commonly used in the electronics industry. Mainly, as the alkali developable functional group, the hydrophilic group is more preferable than the hydrophobic group. Specifically, a hydroxyl group (Si-OH) and an alkoxy group (for example, Si-OCH ₃ ) can be used. In terms of improving heat resistance, it is preferred to replace the alkoxy group with a decyl group as much as possible by processing. In view of this, a preferred alkali developable functional group can be Si-OH, which is also a preferred heat curable functional group as mentioned above. That is, the alkali developable functional group and the heat curable functional group are not the same in terms of use, but may be identical in structure.

Examples of the C ₁ -C ₂₀ alkyl group and the aromatic group (preferably a C ₆ -C ₂₀ aromatic group) may include a methyl group, a phenyl group, a 3-glycidoxypropyl group, and 2 -(3,4-epoxycyclohexyl)ethyl, etc., but is not limited thereto.

These organic groups are irregularly incorporated into the produced resin by hydrolysis of the raw materials. In this case, the curing rate and hardness of the coating may vary depending on the functionality type of the raw materials used. If many trifunctional groups are present, the cure rate is high and the coating becomes hard, but it has the disadvantage of being brittle. If many difunctional groups are present, the storage stability of the resin is improved, but the coating is soft and the curing rate is low. Therefore, an appropriate combination of a difunctional group and a trifunctional group is important. In general, an appropriate combination of a methyl group and a phenyl group is an important factor for improving the properties of the coating layer, and the epoxy group has a function of supplementing heat curability and adhesion.

In the alkali-soluble polyoxynoxy resin of the present invention, the trifunctional structure derived from the organotrialkoxydecane is incorporated in an amount of 60 to 95 mol%, more preferably 70 to 95 mol%, which is a poly The properties of the sesquioxanes are partially supplied to the resin. That is, the present invention excludes 100% polysesquioxanes. As explained above, this is the result of providing optimum coating properties, cure rates, storage stability, and the like. If the content of the trifunctional structure in the resin is less than 60 mol%, the storage stability is improved, but the coating becomes soft and the curing rate becomes low. Curing if the content of the trifunctional structure in the resin is more than 95% by mole The rate is high and the coating becomes hard, but there are fragile problems.

Preferably, the alkali-soluble polyoxyl resin comprises, in addition to the trifunctional structure, a difunctional structure of 5 to 40 mol%. In order to coat a polyoxyxene material, it is necessary to incorporate a large number of trifunctional structures having good coating properties. However, in addition to the trifunctional structure, if the difunctional structure is further appropriately incorporated, other desired properties than the coating properties can be obtained. Those having ordinary skill in the art can incorporate suitable properties (e.g., coating properties, hardness, and high heat resistance) depending on the use of the resin composition, and incorporate an appropriate amount of a bifunctional structure.

In the present invention, the alkali-soluble polyoxynoxy resin has a weight average molecular weight of 5,000 to 20,000, more preferably 5,500 to 15,000. The inventors of the present invention have demonstrated that the optimum coating surface properties are provided when the weight average molecular weight of the resin is controlled in the range of 5,000 to 20,000.

If the weight average molecular weight of the resin is less than 5,000, the dilution viscosity becomes low, so that the coating becomes uneven and adhesion occurs after prebaking, and even if hard baking is performed, it is difficult to obtain a desired coating hardness. On the other hand, if the weight average molecular weight of the resin is more than 20,000, the deficiency of the terminal alkali developable group deteriorates the function as a photoresist, and the surface of the coating may be brittle. If the molecular weight becomes extremely large and thus out of control, gelation may occur during resin production, which may make the production itself impossible.

The present invention uses an alkoxydecane material as a raw material for the alkali-soluble polyoxyxene resin. Examples of the alkoxydecane may include, but are not limited to, methoxydecane, ethoxysilane, and the like. Preferably, methoxydecane is used because it is inexpensive and easy to obtain.

In one embodiment, if methoxydecane is used as the starting material, hydrolysis of the terminal methoxy group under an acid atmosphere results in displacement of the sterol group and simultaneous formation of a decane linkage. In this case, by adjusting the acidity or concentration method of the catalyst used, many terminal sterol groups may be left or almost all of them may be removed. Although the remaining -OH groups are condensed with other -OHs in the same or adjacent molecules, the activity may be inhibited by excessive use of the solvent or storage at low temperatures. On the other hand, if the resin composition is applied as a film and heated, as explained above, the solvent is evaporated by heat, and the rapid reaction between -OH is simultaneously involved in curing.

Examples of starting materials suitable for use in preparing the alkali-soluble polyoxynene resin composition of the present invention are shown in Table 1 below.

In a specific embodiment, the alkali-soluble polyoxyl resin can be represented by the following Chemical Formula 1 (the order of combination of the units can be changed).

In the above Chemical Formula 1, R ₁ is independently a methyl group, a 3-glycidoxypropyl group or a hydroxyl group; R ₂ is independently a hydroxyl group; and R ₃ is independently a methyl group, a phenyl group, a 3-glycidoxy group. Propyl or 2-(3,4-epoxycyclohexyl)ethyl, preferably 2-(3,4-epoxycyclohexyl)ethyl; and a, b and c satisfy a+b The molar fraction of +c=1.

The nature of the surface of the coating varies depending on the specific type of R ₁ , R ₂ and R ₃ and the adjustment of a, b and c. This problem will be specifically described in the examples described below.

In the above Chemical Formula 1, the relationship between the specific kinds of R ₁ , R ₂ and R ₃ and the raw materials (Table 1) is shown in Table 2 below.

In a preferred embodiment, the alkali-soluble polyoxynoxy resin has the structure of the following chemical formula 2 after curing (the order of combination of the units can be changed).

In the above Chemical Formula 2, n1 to n6 are the molar fractions satisfying n1+n2+n3+n4+n5+n6=1, and 0 N1 0.4,0 N2 0.4,0 (n1+n2) 0.4,0 N3 0.95,0 N4 0.95,0 N5 0.95,0 N6 0.95 and 0 (n3+n4+n5+n6) 0.95.

The polyoxyxylene resin composition of the present invention contains a solvent in addition to the alkali-soluble polyoxyl resin. The kind of the solvent which can be used is not particularly limited, and a solvent conventionally used for two or more kinds of polyoxynitride coating materials such as propylene glycol monomethyl ether acetate (PGMEA) may be used alone or in combination. In a preferred embodiment, PGMEA is used as a solvent for the reaction (synthesis) and as a diluent for aging. The amount of the solvent to be used is not particularly limited, and it is preferably used in such a manner that the viscosity of the composition is in the range of 10 to 200 cP.

The method for preparing the polyoxymethylene resin composition of the present invention is not particularly limited and can be produced by using a method generally used in the art.

Preferably, the polyoxyxylene resin composition of the present invention can be prepared by a process comprising the steps of: (a) mixing alkoxydecane starting material with a diluent solvent, an organic acid and water for hydrolysis; (b) obtaining the obtained The product is distilled under normal pressure to move In addition to the organic acid and water; (c) further adding an organic acid and water to the obtained product to hydrolyze the remaining raw material; (d) distilling the obtained product under low temperature and reduced pressure to further remove the organic acid and water; And (e) further adding a dilution solvent and performing an aging procedure to control the weight average molecular weight of the polyoxyxylene resin to 5,000 to 20,000.

First, an alkoxydecane material as a starting material is added dropwise to an aqueous mixed solution of a diluent solvent (for example, PGMEA) and an organic acid, and hydrolysis is carried out therein. In the present invention, a suitable catalyst is an organic acid, preferably acetic acid and/or oxalic acid, more preferably acetic acid. If a strong acid such as hydrochloric acid or sulfuric acid is used, an additional step such as a neutralization step or a water washing step or the like is required, and a chlorine group or the like may remain in the resin, resulting in deterioration of the properties of the final product. On the other hand, since the organic acid (for example, acetic acid) has a low boiling point and a high water solubility, it can be removed as much as possible by distillation after use, and even if it remains in the resin in an amount that does not affect the storage stability, Evaporation during the subsequent pre-bake and hard-bake steps. Therefore, organic acids are very advantageous as catalysts.

Next, the hydrolyzate is refluxed to produce a bonding solid, which is then distilled under normal pressure to remove organic acids, water, and by-products (eg, methanol).

Once again, the hydrolysis process of the aqueous solution of the organic acid is repeated to remove as much as possible the alkoxy group remaining in the resin, and usually 2 to 3 times. In this case, if it is heated to a high temperature under normal pressure to carry out distillation to remove the organic acid and water, the molecular weight may rapidly increase as the temperature rises. Therefore, the distillation is carried out under reduced pressure at room temperature, and then the temperature can be slowly increased. The internal turbidity is clarified with the removal of water by distillation under reduced pressure at room temperature. The vacuum distillation may be stopped at this time, or, in order to remove as much as possible the organic acid (for example, acetic acid) remaining in the resin, the heating step may be accompanied. In this case, in terms of preventing rapid increase in molecular weight and gelation, it is preferred to maintain the internal temperature at 90 ° C or lower (for example, 20 to 90 ° C). This vacuum distillation is not a general method and is referred to herein as "low temperature vacuum distillation".

A specific amount of a diluent solvent (for example, PGMEA) is added to the prepared polyoxyxene resin to adjust the concentration to a desired level. Although PGMEA is preferably used as the diluent solvent for the reaction, any solvent conventionally used in the electronics industry can be used as a further dilution solvent added after low-temperature vacuum distillation.

Next, the resulting product is slowly stirred at a moderate temperature such as 50 to 80 ° C (for example, about 50 ° C) for aging until the desired molecular weight distribution (i.e., Mw of 5,000 to 20,000) is reached.

In addition, based on the solids content of magnesium silicate Synthesis of 1 to 2% (2MgO.6SiO ₂ .xH ₂ O; e.g., tradename KYOWAAD-600; treating agent which is an ion (ion adsorbent)) to handle the transmission of aging The polyxanthene resin, which has a completely controlled molecular weight distribution, is then filtered with diatomaceous earth (for example, trade name Dicalite Speed-plus) to completely remove impurities.

Finally, the resulting composition was filtered through a 0.1 micron filter cartridge (KAREI) and packaged and stored. At this time, in order to minimize the activity of the catalyst and obtain storage stability, the prepared composition is prepared under a nitrogen atmosphere and a low temperature (preferably 5 ° C or lower, more preferably 3 ° C or lower). It is tightly sealed and stored in glass bottles for up to six (6) months of storage stability.

According to the present invention, a general alkoxydecane starting material can be used (which The standardized process of not being a special raw material) prepares the polyanthracene resin composition stably and easily. Further, since the polyoxymethylene resin composition can be prepared with good productivity and economic feasibility, it is expected to greatly contribute to the popularization of the polyoxynized coating material.

According to another aspect of the present invention, there is provided a coating formed by applying a polyoxymethylene resin composition as described above. The method of applying the polyoxyxylene resin composition of the present invention to a substrate and forming a coating layer thereon is not particularly limited. The coating can be formed using any method conventionally used in the art such as spin coating, dip coating, or the like. Further, the curing method and curing conditions after coating are not particularly limited. For example, the coating can be thermally cured using conditions of 150 ° C, 30 minutes, and t = 1 to 3 μm. Further, the curing can be carried out by a dual method (that is, by heat (thermal curing) and UV irradiation (photocuring)).

The coating formed by the composition of the present invention is soluble in 0.4% to 2.38% aqueous solution of TMAH after prebaking, and is therefore suitable for a photoresist process, and can provide high hardness, high light transmittance and high heat resistance. Coating surface. In particular, the composition of the present invention is suitable for use as a film coating liquid crystal display device or the like as a level coating agent, an overcoating agent and the like.

Hereinafter, the present invention will be more specifically described by way of examples. However, the embodiments are only provided to assist in understanding the invention, and the scope of the invention is not limited thereto.

Examples 1 to 4 and Comparative Examples 1 and 2: Preparation of Resins 1 to 6

PGMEA (712.01 g), acetic acid (7.12 g) and water (487.74 g) were added to a 3000 ml round bottom flask and stirred. The mixture was maintained at 40 ° C while PTMS (364.29 g) was added dropwise thereto over a period of 1 hour. A liquid mixture of MTMS (850 g), GPTMS (108.54 g) and GPMDMS (101.19 g). Next, the temperature was slowly raised to the reflux point for 2 to 5 hours, and then distilled to 110 ° C under normal pressure to remove the low boiling point material. Again, water (487.74 g) and acetic acid (2.14 g) were added thereto, refluxed for 3 to 6 hours, and the resulting mixture was cooled to room temperature. The cooled mixture is stripped at 80 ° C by a low temperature-decompression method, the pressure is released, PGMEA is added thereto to be diluted to a solid content of 40 to 50%, and then continuously stirred at 50 ° C until the desired amount is obtained. The molecular weight (the molecular weight is shown in Table 5 below). The polyoxymethylene coating resin having a controlled molecular weight was filtered through a diatomaceous earth filter and a 0.1 micron filter. The final resin composition is tightly sealed and stored at 5 ° C or lower to avoid contact with air. Regarding the resins 1 to 5, the amounts of the raw materials added were the same, but the aging procedures (aging time) were not the same, whereby the prepared resins had weight average molecular weights different from each other. Regarding the resin 6, the gelation was caused by excessive aging, and thus the resin was not substantially produced.

Examples 5 and 6, and Comparative Example 3: Preparation of Resins 7 to 9

The resin composition was prepared by the same procedure as described above using the ingredients and amounts shown in Table 3 below. Regarding the resins 7 to 9, the amounts of the raw materials added were the same, but the aging procedures (aging time) were not the same, whereby the prepared resins had weight-average molecular weights different from each other.

Comparative Example 4 and Example 7: Preparation of Resins 10 and 11

The resin composition was prepared by the same procedure as described above using the ingredients and amounts shown in Table 3 below.

Comparative Examples 5 and 6: Preparation of Resins 12 and 13

The resin composition was prepared by the same procedure as described above using the ingredients and amounts shown in Table 3 below. Regarding Comparative Example 6, the resin 13 could not be produced because gelation occurred during the synthesis.

The bifunctional and trifunctional molar ratios of the prepared resins 1 to 13 are shown in Table 4 below, which is related to the structure of Chemical Formula 1. Chemical Formula 1 is a diagram considering the -OH group. Table 4 shows the moie ratio of bifunctional to trifunctional based on the fact that all of the -OH groups in the coating are involved in curing.

The following Chemical Formulas 3 to 8 show the functionalities in Table 4 above in structure.

As can be seen from the above Table 4, the resins 1 to 6 had a D/T of 5/95 (5% difunctionality and 95% trifunctionality). Resins 7 to 9 and 10 have a D/T of 15/85, resin 11 has a D/T of 10/90, and resin 12 has a D/T of 50/50. The resin 13 has only T of 100. For its part, the ratio of difunctional (D) to trifunctional (T) is a preferred factor in the preparation of polyoxyxides, and thereby, the properties of the surface of the coating can be predicted to some extent.

Nature assessment

With respect to the resins (compositions) 1 to 13 prepared in the examples and the comparative examples, the properties of the respective coating layers were measured/evaluated by the following methods, and the results are shown in Table 5.

1) Coating method: PGMEA is added to make the solid content 30% (by weight) The base meter was stirred and diluted by using a vortex mixer for 1 minute. The resulting mixture was applied to a glass substrate (150 x 300 x 2 mm) by using a rod applicator (RDS3, 6.86 micron thick wet coating) and maintained at room temperature for 1 minute.

2) Pre-bake: The coating of the above 1) was placed in an electric oven set at 110 ° C, maintained therein for 90 seconds, taken out of the electric oven, and cooled to room temperature.

3) alkali solubility: 2 drops of 0.4% TMAH aqueous solution were added dropwise to the coated surface prepared in the above 2), and left for 60 seconds. After washing with water, the appearance of the coating was observed.

4) Coating properties: The surface of the coating prepared in the above 2) was touched by hand to evaluate the tackiness.

5) Hard bake: After pre-baking, the coated glass substrate was placed in an electric oven set at 150 ° C, maintained therein for 30 minutes, taken out of the electric oven, and cooled to room temperature.

6) Pencil hardness: For the coated glass substrate prepared in the above 5), the surface of the coating was scratched using a YOSHIMITSU Model 221-D equipped with a Mitsubishi pencil, and a Peak magnification of 22 was used. Measure the degree of scratching.

7) Heat resistance: 1.0 to 1.2 g of the coating composition was placed on a pre-weighed aluminum pan (Ace Sciences, Co. Ltd.) and accurately weighed, pre-baked and hard-baked, and then the weight of the coating was calculated. . The sample was maintained in an electric oven at 280 ° C for 10 minutes, cooled to room temperature, and the ratio of weight loss was calculated.

As can be seen from the above Table 5, the composition of the present invention comprising a polyfluorene oxide resin having 60 to 95 mol% of T units and having a molecular weight of 5,000 to 20,000 all showed good properties. On the contrary, Comparative Examples 1 and 4 were still sticky after coating, and exhibited poor heat resistance. In Comparative Example 3, cracking occurred. Comparative Example 5 remained tacky after coating and was in an uncured state, so that the coating test could not be performed. In Comparative Examples 2 and 6, gelation occurred during the synthesis, and thus it was substantially impossible to prepare a resin.

Claims (10)

An alkali-soluble polyoxynoxy resin comprising: (A) at least one heat-curable functional group selected from the group consisting of a hydroxyl group, an alkoxy group and an epoxy group; (B) at least one selected from the group consisting of a hydroxyl group and an alkoxy group a base-developable functional group of the group; (C) at least one functional group selected from the group consisting of a C ₁ -C ₂₀ alkyl group and an aromatic group; and (D) a derivative of 60 to 95 mol% A trifunctional structure derived from an organotrialkoxydecane wherein the resin has a weight average molecular weight of 5,000 to 20,000. The alkali-soluble polyoxynoxy resin as described in claim 1, which is represented by the following chemical formula 1: Wherein, in the above Chemical Formula 1, R ₁ is independently a methyl group, a 3-glycidoxypropyl group or a hydroxyl group; R ₂ is independently a hydroxyl group; and R ₃ is independently a methyl group, a phenyl group, a 3-epoxy group. Propyloxypropyl or 2-(3,4-epoxycyclohexyl)ethyl; and a, b and c are the molar fractions satisfying a+b+c=1. The alkali-soluble polyoxynoxy resin as described in claim 2, which has the structure of the following chemical formula 2 after curing: Wherein, in the above chemical formula 2, n1 to n6 are molar fractions satisfying n1+n2+n3+n4+n5+n6=1, and 0 N1 0.4,0 N2 0.4,0 (n1+n2) 0.4,0 N3 0.95,0 N4 0.95,0 N5 0.95,0 N6 0.95 and 0 (n3+n4+n5+n6) 0.95. The alkali-soluble polyoxymethylene resin according to claim 1, wherein the complex contains 5 to 40 mol% of a difunctional structure. A polyoxyxylene resin composition comprising the alkali-soluble polyoxyxylene resin according to any one of claims 1 to 4, and a solvent. A method for preparing a polyoxyxylene resin composition according to claim 5, which comprises the steps of: (a) mixing alkoxydecane starting material with a diluent solvent, an organic acid and water for hydrolysis; (b) distilling the obtained product under normal pressure to remove the organic acid and water; (c) further adding an organic acid and water to the obtained product to hydrolyze the remaining raw material; (d) distilling the obtained product under low temperature and reduced pressure to further remove the organic acid and water; and (e) further adding dilution The solvent is subjected to an aging procedure to control the weight average molecular weight of the polyoxyxene resin to 5,000 to 20,000. The method for preparing the polyoxyxylene resin composition according to claim 6, wherein the diluent solvent in the step (a) is propylene glycol monomethyl ether acetate (PGMEA). The method for producing the polyoxyxylene resin composition according to claim 6, wherein the organic acid is at least one selected from the group consisting of acetic acid and oxalic acid. The method for producing the polyoxyxylene resin composition according to claim 6, wherein the step (d) is carried out at a temperature of 90 ° C or lower. A coating formed by applying the polyoxymethylene resin composition described in claim 5 of the patent application.