KR100925853B1 - Organic-inorganic hybrid coating composition containing polyvinyl alcohol having a double bond - Google Patents

Abstract

The present invention is an organic-inorganic hybrid coating composition containing a polyvinyl alcohol, an acrylate monomer, an inorganic precursor having a specific double bond, and the coating composition is coated on a support to increase the dispersibility of the inorganic precursor compared to the conventional optical The present invention relates to a coating layer in which physical properties are improved and a drastic reduction in the formation of non-uniform particles is achieved.

Polyvinyl alcohol, coating composition, organic-inorganic hybrid, optical properties, non-uniform particle formation

Description

Organic-Inorganic hybrid coating composition containg polyvinyl alcohol with acrylic functional group}

The present invention is an organic-inorganic hybrid coating composition containing a polyvinyl alcohol, an acrylate monomer, an inorganic precursor having a specific double bond, and the coating composition is coated on a support to increase the dispersibility of the inorganic precursor compared to the conventional optical The present invention relates to a coating layer in which physical properties are improved and a drastic reduction in the formation of non-uniform particles is achieved.

Formation of the coating layer on the glass and transparent plastic film support is carried out for the purpose of increasing the gas or moisture barrier effect and chemical resistance, hardness, wear resistance and the like.

In addition, the method of including the inorganic particles in the layer after forming the coating layer is a method of using an inorganic filler in the coating solution in advance, and the inorganic precursor is included in the composition to form a coating layer or a specific treatment before forming the coating layer The method of forming an inorganic particle and including it in a coating layer is mentioned.

Inorganic particles included in the coating layer have improved wear resistance, durability, chemical resistance, hardness, and the like, compared to the case of forming the organic layer alone. Thus, the organic-inorganic hybrid type coating layer forming coating solution is developed and applied. Has been. However, the coating layer containing such inorganic particles may exhibit the formation of a cloudy coating layer and the formation of non-uniform particles, etc. according to the formation method of the inorganic particles, resulting in a problem of lowering optical properties.

In order to obtain a coating layer in which inorganic particles are uniformly dispersed, a method of adding a dispersant to a composition may be provided. However, the dispersant itself may gradually remain in the interlayer even after the coating layer is formed to contaminate the secondary forming layer on the support. It may cause a decrease in chemical resistance of the coating layer.

The present invention is to overcome the above problems to provide a method for producing an organic-inorganic hybrid type coating layer without uniformly dispersed inorganic particles contained in the coating layer without optical properties.

Accordingly, the present invention provides a method for preparing a coating liquid composition and a method for forming an organic-inorganic hybrid coating layer by coating with a coating liquid composition.

The present invention provides a polyvinyl alcohol having a double bond comprising 60 to 90% by weight of an acrylate monomer, 1 to 39.8% by weight of an inorganic precursor, and 0.2 to 20% by weight of a polyvinyl alcohol having a double bond represented by the following formula (1). It is characterized by the organic-inorganic hybrid coating composition containing.

In Formula 1, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x, y and z are irregular or regular repeatable, block or random copolymer, respectively, free numbers in the range of 0.01 to 1, x + y + z = 1, the weight average molecular weight (Mw) is in the range of 5,000 to 150,000.

In addition, the present invention has another feature on a coating layer formed by coating an organic-inorganic hybrid coating composition containing polyvinyl alcohol having a double bond on a support.

The organic-inorganic hybrid coating composition prepared according to the present invention has high dispersibility of inorganic particles, and thus the coating layer using the same has excellent optical properties and greatly reduces the formation of non-uniform particles.

The present invention is an organic-inorganic hybrid coating composition containing a polyvinyl alcohol having a double bond represented by the formula (1), the polyvinyl alcohol having a double bond is a functional group capable of acting on the inorganic precursor and the inorganic particles produced in the molecule It contains a hydroxyl group and contains the acryl group which can participate in the polymerization reaction with an acrylate monomer. Due to this structure, it is present in the composition combined with the inorganic precursor and plays a role of sufficiently dispersing the inorganic particles in the inorganic particle formation step of the inorganic precursor and keeping the particle size small and uniform. In a later step to participate in the crosslinking reaction with the acrylate monomer to be included in the crosslinked structure of the polymer matrix. That is, the acetate group and the acryl group contained in the polyvinyl alcohol of Chemical Formula 1 prevent phase separation by providing a reactive functional group by controlling the polarity of the polyvinyl alcohol polymer chain during the crosslinking process.

In addition, the present invention forms a polyvinyl alcohol having the double bond and a specific inorganic precursor by using alkoxy substitution reaction to form a form, containing an inorganic particle when the acrylic group is polymerized in the coating layer forming conditions, the polymer Crosslinked in the matrix, it is advantageous to uniformly distribute the inorganic particles in the organic polymer layer, which prevents the inorganic particles from excessively growing or agglomerating to a few hundred nanometers or more, thereby providing good mechanical properties and coating film. Prevents cloudiness

Referring to the organic-inorganic hybrid coating composition containing a polyvinyl alcohol having a double bond according to the present invention in more detail as follows.

Through the hydroxy group contained in the polymer chain of the polyvinyl alcohol represented by the formula (1) of the present invention performs a primary reaction with the inorganic precursor, thereby maintaining the particle size small and uniform in the step of forming the inorganic particles Will be performed. Such polyvinyl alcohol is obtained by hydrolyzing polyvinylacetate in a manner generally performed in the art, wherein the hydrolysis ratio is preferably adjusted in the range of 50 to 100%. When the hydrolysis ratio is less than 50%, the effect of the action with the inorganic precursor may be lowered. In order to attach the acryl group to the hydroxy group, the reaction is carried out with acryloyl chloride in an aprotic organic solvent, wherein polyvinyl alcohol In order to improve the solubility, it is recommended to use about 80% of hydrolyzed. More preferably, polyvinyl alcohol having a hydrolysis ratio of 70 to 80% is preferably used. The proportion of the acryl group introduced into the polyvinyl alcohol is maintained in the range of 5 to 20% with respect to the hydroxy group. If the ratio is less than 5%, the participation of the crosslinking reaction is deteriorated, and if the ratio exceeds 20%, the hydroxy group and the inorganic precursor May affect the effects of

The polyvinyl alcohol represented by Chemical Formula 1 may be used alone or in combination of two or more kinds having different acryl group and acetate content ratios, and the amount of the polyvinyl alcohol maintained in the range of 0.2 to 20 wt%. At this time, if the amount of use is less than 0.2% by weight, the amount is insignificant, so that it is difficult to express the desired effect. If the amount is more than 20% by weight, deterioration of mechanical properties such as decrease in hardness of the coating film may occur. Do.

The acrylate monomer used in the present invention may be used by mixing a bifunctional or trifunctional acrylate monomer as part of the main organic polymer layer of the coating layer. The di- or tri-functional acrylate monomers are specifically hexanediol diacrylate, neopentyl glycol diacrylate, tri (propylene glycol) diacrylate, tri (ethylene glycol) diacrylate, di (ethylene glycol) diacryl Elate, pentaerythritol triacrylate, etc. can be mixed and used.

When the acrylate monomer is used in the range of 60 to 90% by weight, it is difficult to obtain the hardness and mechanical properties of the coating layer when the amount is less than 60% by weight, and when the amount exceeds 90% by weight, it is difficult to control the viscosity of the coating liquid. .

The inorganic precursor used in the present invention may be selected from tetra alkoxy silane, metal alkoxide and (trialkoxysilyl) alkyl acrylate. The inorganic precursor may be a tetraalkoxy silane having an alkoxy group having 1 to 6 carbon atoms: a transition metal having an alkoxy group having 1 to 6 carbon atoms, specifically an alkoxide of a metal such as titanium, zirconium, zinc or tin: an alkoxy group having 1 to 6 carbon atoms (Trialkoxysilyl) alkylacrylates having alkyl groups of 1 to 6 carbon atoms can be used, preferably titanium tetraisopropoxide, titanium tetrabutoxide, tetraethoxysilane and 3- (trimethoxysilyl) propyl Methacrylate, etc. can be used. Such inorganic precursors may be used in the range of 1 to 39.8% by weight, and if the amount is less than 1% by weight, the use effect is insignificant, and when the amount is more than 39.8% by weight, the coating layer becomes cloudy or irregular particles are large in the coating layer. Problems are formed.

The present invention uses a solvent for controlling the viscosity of the solution and controlling the properties for application on the support. Since the solvent may affect the formation of a uniform coating layer during the control of the drying rate and UV curing, the amount of the solvent may be used in an appropriate range at a skilled person's level. As the solvent, alcohols, furans, ketones, acetates and nitriles may be used. Specifically, isopropanol, ethanol, methanol, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate and acetonitrile may be used. . Such a solvent is used in the range of 10 to 200 parts by weight based on 100 parts by weight of the composition consisting of an acrylate monomer, an inorganic precursor and a polyvinyl alcohol. When the amount is less than 10 parts by weight, it is difficult to control the viscosity and exceeds 200 parts by weight. In this case, it is preferable to maintain the above range because problems of lowering of viscosity and longer drying time occur.

The coating composition of the present invention can be carried out in the curing reaction generally used in the art specifically, such as heat curing or ultraviolet curing, preferably UV curing. At the time of UV curing, a UV decomposition initiator is included to allow the curing reaction according to UV irradiation to proceed. The initiator is generally used in the art and is not particularly limited, but specifically, acetophenone, benzophenone, 2,2-diethoxyacetophenone, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, and benzoyl methyl ether, etc. The initiator may be used in an amount of 0.01 to 5% by weight with respect to the acrylate monomer. When the amount is less than 0.01% by weight, the initiator effect is small, and when the amount is greater than 5% by weight, the coating layer discoloration and It may cause a decrease in physical properties.

A coating composition is prepared by mixing polyvinyl alcohol, an acrylate monomer, an inorganic precursor, an initiator, and a solvent having a double bond represented by Chemical Formula 1 described above to a certain range, and the coating solution is basic on the support before being cured. An aqueous solution is added to form inorganic particles from the inorganic precursors. The basic aqueous solution is added to the pH 8-14 basic aqueous solution in the range of 100 to 300% by weight with respect to the inorganic precursor to shake and shake for 30 minutes to 12 hours to form inorganic particles. If the amount of the basic aqueous solution is less than 100% by weight, the inorganic particle formation time is long, and if it exceeds 300% by weight, it is preferable to maintain the above range because excessive base remains to cause a problem of deterioration of physical properties.

It is applied to the support using the coating composition prepared above to form a coating layer. In this case, the support is generally used in the art, but is not particularly limited, and glass, metal, polymer film, ceramic, and the like may be used. The method of applying on the support may use a suitable method generally used in the art depending on the properties of the support, for example, in the case of a flexible plastic film may be applied on the film using a roll coating, glass For substrates, dipping and solution casting methods can be used. The support on which the coating solution is applied is dried at 40 to 60 ° C., and cured by irradiation with 1000 mJ to 4000 mJ ultraviolet rays to prepare a coating layer.

The coating layer prepared in this manner has a pencil hardness of 2H to 3H, and shows a range of 5 to 54 in the number of particles having a nonuniform particle formation (300 nm or more particle number / 10 ^-8 m ² ).

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

Example 1

Next, polyvinyl alcohol having a double bond represented by Formula 1a shown in Table 1, 60% by weight of tri (propylene glycol) diacrylate and 8% by weight of 3- (trimethoxysilyl) propyl methacrylate as an inorganic precursor, tetra 5% by weight of ethoxysilane and 7% by weight of titanium tetrabutoxide were mixed with 10% by weight of ethanol and stirred for 20 minutes. Thereafter, an aqueous 0.5 wt% sodium hydroxide solution was added at a 5 wt% ratio with respect to the mixed solution, and stirred at room temperature for 2 hours. Thereafter, 0.1 wt% of 2,2-diethoxyacetophenone was added to the mixed solution as a photoinitiator, followed by further stirring for 30 minutes to prepare a coating composition.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Example 2

In the same manner as in Example 1, 5% by weight of polyvinyl alcohol having a double bond represented by the formula (1a) shown in Table 1, 65% by weight of tri (propylene glycol) diacrylate, and 3- ( A coating composition was prepared by mixing 8% by weight of trimethoxysilyl) propyl methacrylate, 5% by weight of tetraethoxysilane, and 7% by weight of titanium tetrabutoxide to 10% by weight of ethanol.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Example 3

The same procedure as in Example 1, except that 1% by weight of polyvinyl alcohol having a double bond represented by the formula (1a) shown in Table 1, 69% by weight of tri (propylene glycol) diacrylate, and 3- (inorganic precursor) A coating composition was prepared by mixing 8% by weight of trimethoxysilyl) propyl methacrylate, 5% by weight of tetraethoxysilane, and 7% by weight of titanium tetrabutoxide to 10% by weight of ethanol.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Example 4

In the same manner as in Example 1, 5% by weight of polyvinyl alcohol having a double bond represented by the formula (1b) shown in Table 1, 65% by weight of tri (propylene glycol) diacrylate, and 3- ( A coating composition was prepared by mixing 8% by weight of trimethoxysilyl) propyl methacrylate, 5% by weight of tetraethoxysilane, and 7% by weight of titanium tetrabutoxide to 10% by weight of ethanol.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Example 5

In the same manner as in Example 1, 5 wt% of polyvinyl alcohol having a double bond represented by Formula 1c shown in Table 1, 65 wt% of tri (propylene glycol) diacrylate, and 3- ( A coating composition was prepared by mixing 8% by weight of trimethoxysilyl) propyl methacrylate, 5% by weight of tetraethoxysilane, and 7% by weight of titanium tetrabutoxide to 10% by weight of ethanol.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Example 6

In the same manner as in Example 1, 5 wt% of polyvinyl alcohol having a double bond represented by Formula 1a shown in Table 1, 65 wt% of neopentylglycol diacrylate, and 3- (trimeth) as an inorganic precursor A coating composition was prepared by mixing 8% by weight of oxysilyl) propyl methacrylate, 5% by weight of tetraethoxysilane, and 7% by weight of titanium tetrabutoxide to 10% by weight of ethanol.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Comparative Example 1

In the same manner as in Example 1, 70% by weight of tri (propylene glycol) diacrylate, 8% by weight of 3- (trimethoxysilyl) propyl methacrylate, 5% by weight of tetraethoxysilane, titanium tetrabutoxide Coating compositions were prepared using a range of 7 wt% and 10 wt% ethanol.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Comparative Example 2

In the same manner as in Example 1, except that 80% hydrolyzed poly (vinyl alcohol-co-vinylacetate) 10% by weight, tri (propylene glycol) diacrylate 60% by weight, 3- (trimethoxysilyl) propyl The coating composition was prepared using a range of 8% by weight methacrylate, 5% by weight tetraethoxysilane, 7% by weight titanium tetrabutoxide, and 10% by weight ethanol.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Comparative Example 3

In the same manner as in Example 1, 70 wt% of neopentyl glycol diacrylate, 8 wt% of 3- (trimethoxysilyl) propyl methacrylate, 5 wt% of tetraethoxysilane, and 7 wt% of titanium tetrabutoxide Coating compositions were prepared using the range%, ethanol 10% by weight.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

Comparative Example 4

The same procedure as in Example 1, except that 10% by weight of 80% hydrolyzed poly (vinyl alcohol-co-vinylacetate), 60% by weight of neopentylglycol diacrylate, 3- (trimethoxysilyl) propyl methacryl The coating composition was prepared using a range of 8% by weight, 5% by weight tetraethoxysilane, 7% by weight titanium tetrabutoxide and 10% by weight ethanol.

The polyether sulfone resin film was immersed in the coating composition prepared above, and after 30 seconds, it was pulled out of the solution at a rate of 1 mm / s, and dried at 50 ° C. for 10 minutes. The UV lamp was irradiated for 5 minutes on the irradiated bed and cured to a total of 3000 mJ, followed by heat treatment in an oven at 100 ° C. for 1 hour.

The physical properties of the coating layers prepared in Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1 below.

division Acrylate monomer (% by weight) Polyvinyl Alcohol (PVA, wt%) Inorganic precursor Heterogeneous particle formation (number of particles above 300 nm / 10 ^-8 m ² ) Pencil hardness Example 1 Tri (propylene glycol) diacrylate (60) Formula 1a (10) a 5 2H Example 2 Tri (propylene glycol) diacrylate (65) Formula 1a (5) a 12 2H Example 3 Tri (propylene glycol) diacrylate (69) Formula 1a (1) a 42 3H Example 4 Tri (propylene glycol) diacrylate (65) Formula 1b (5) a 22 2H Example 5 Tri (propylene glycol) diacrylate (65) Formula 1c (5) a 18 2H Example 6 Neopentylglycol Diacrylate (65) Formula 1a (5) a 33 2H Comparative Example 1 Tri (propylene glycol) diacrylate (70) - a 110 2H Comparative Example 2 Tri (propylene glycol) diacrylate (60) Poly (vinyl alcohol-co-vinylacetate) 80% hydrolysis (10) a 43 1H Comparative Example 3 Neopentylglycol Diacrylate (70) - a 189 3H Comparative Example 4 Neopentylglycol Diacrylate (60) Poly (vinyl alcohol-co-vinylacetate) 80% hydrolysis (10) a 55 1H

(x=0.7, y=0.2, z=0.1, 및 중량평균분자량=10,000) 화학식 1b :

(x=0.7, y=0.2, z=0.1, 및 중량평균분자량=10,000) 화학식 1c :

(x=0.6, y=0.2, z=0.2, 및 중량평균분자량=11,300) a : 3-(트리메톡시실릴)프로필 메타아크릴레이트 8 중량% + 테트라에톡시실란 5 중량% + 티타늄테트라부톡사이드 7 중량%Formula 1a:

(x = 0.7, y = 0.2, z = 0.1, and weight average molecular weight = 10,000) Formula 1b:

(x = 0.7, y = 0.2, z = 0.1, and weight average molecular weight = 10,000) Formula 1c:

(x = 0.6, y = 0.2, z = 0.2, and weight average molecular weight = 11,300) a: 8% by weight of 3- (trimethoxysilyl) propyl methacrylate + 5% by weight of tetraethoxysilane + titanium tetrabutoxide 7 wt%

As shown in Table 1, when forming a coating layer using a coating liquid containing a specific polyvinyl alcohol containing a double bond in the composition according to the present invention, the formation of non-uniform particles of the coating layer is greatly reduced The results could be confirmed. As illustrated in the results of Examples 1 to 6, it can be seen that the nonuniform particle formation tendency is greatly reduced compared to the results shown in Comparative Examples 1 and 3. These results were not affected by different difunctional acrylate monomers used together in the composition.

Polyvinyl alcohol that does not contain a double bond, that is, a copolymer of polyvinyl alcohol and polyvinyl acetate hydrolyzed to 80% may exhibit an effect of reducing non-uniform particle formation, but there is a problem of hardness reduction of the coating layer formed It could be confirmed in Example 2 and Comparative Example 4, it is not a structure that is cross-linked to the polymer matrix of the coating layer can be said to have a high possibility of being separated from the coating layer during use. On the other hand, in the composition containing polyvinyl alcohol including the double bond proposed in the present invention, the effect of reducing non-uniform particle formation was excellent and the hardness was not found at all.

Therefore, through the coating solution of the composition proposed in the present invention, the size of the inorganic particles formed in the coating layer is made small and even, thereby preventing the formation of non-uniform particles, thereby forming a coating layer without problems of hardness.

Claims (3)

Polyvinyl having a double bond comprising 60 to 90% by weight of acrylate monomer, 1 to 39.8% by weight of inorganic precursor, and 0.2 to 20% by weight of polyvinyl alcohol having a double bond represented by the following formula (1): Organic-inorganic hybrid coating composition containing alcohol: [Formula 1]

In Formula 1, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x, y and z are irregular or regular repeatable, block or random copolymer, respectively, free numbers in the range of 0.01 to 1, x + y + z = 1, the weight average molecular weight (Mw) is in the range of 5,000 to 150,000. The composition of claim 1 wherein the inorganic precursor is selected from tetra alkoxy silanes, metal alkoxides and (trialkoxysilyl) alkylacrylates. Coating layer formed by coating the organic-inorganic hybrid coating composition of any one of claims 1 to 2 on the support.