KR101344872B1 - polymer compositions, film obtained therefrom and manufacturing method thereof - Google Patents

Abstract

80-99.9 parts by weight of methyl methacrylate monomer; And 0.1 to 20 parts by weight of the silsesquioxane polymer having an organic network structure. Films comprising scratch resistant resins prepared from the polymer compositions have a higher hardness than conventional polymethylmethacrylate films.

Description

Polymer compositions, film obtained therefrom and manufacturing method

The present invention relates to a polymer composition, a film obtained therefrom and a method for producing the same. More specifically, the present invention relates to a polymer composition for producing a polymethyl methacrylate-based film having better scratch resistance than a conventional polymethyl methacrylate film, a polymethyl methacrylate-based film obtained therefrom, and a method for producing the same.

Polymethyl methacrylate resin is a polymer of methyl methacrylate, which is prepared by a polymerization process using only methyl methacrylate alone, or a bulk polymerization, suspension polymerization, or a combination of methyl methacrylate and a small amount of acrylate monomer. It is manufactured by processes, such as solution polymerization.

Polymethyl methacrylate resin has excellent transparency and weather resistance, and has excellent mechanical strength such as tensile strength and elastic modulus, surface gloss, chemical resistance, adhesiveness and compatibility with other resins. It is widely used as a modifier of adhesives and other plastic materials. In particular, polymethylmethacrylate resins are widely used as a substitute for glass in optical applications because of their excellent transparency.

When polymethyl methacrylate resin is mainly used for home appliances such as LCD, PDP TV, washing machine, water purifier, air cleaner, and computer peripherals such as monitor and printer, polymethyl methacrylate resin is easily scratched during production and use. Because of this there is a post-treatment process such as UV coating process or surface coating using a coating agent after coating the product with a polymethyl methacrylate resin.

U.S. Patent 6,075,094 discloses A) 30 to 60% by weight of an unsaturated monomer mixture comprising unsaturated monomers having at least two double bonds capable of causing radical polymerization, (B) (i) 20 to 100 parts by weight of partially crosslinked 40 to 70% by weight of resin particles made from a polymer of methyl methacryl unsaturated monomer comprising resin particles and (ii) 0 to 80 parts by weight of uncrosslinked resin particles, and (C) 0.1 to 5% by weight of radical polymerization A methyl methacrylate resin composition comprising an initiator is disclosed. The resin prepared from the methyl methacrylate resin composition has scratch resistance. However, since the methyl methacrylate resin obtained from the composition is obtained by using partially crosslinked resin particles, the methyl methacrylate resin has crosslinking therein, so it is not flowable and molded into a desired form by post-processing such as extrusion or injection. There is a disadvantage that can not.

In addition, U.S. Patent 4,698,373 also discloses (a) 0 to about 50 weight percent of a non-crosslinked polymer soluble in the mixture, (b) about 2 to about 30 weight percent of a polymerizable monomer, and (c) an average particle diameter of about 0.001 to about 500 microns. And a composition of about 10 to about 70 weight percent of a discontinuous particulate crosslinked polymer that can swell in the mixture and (d) about 20 to about 70 weight percent of the crosslinker for the monomer. The methyl methacrylate resin obtained from the composition also has a crosslinking inside, which is disadvantageous in that it is not fluid and cannot be molded into a desired shape by post-processing such as extrusion or injection.

Therefore, there is a need to develop a polymethylmethacrylate resin having sufficient scratch resistance and fluidity enough to be molded into a desired shape by post-processing such as extrusion or injection.

U.S. Patent 6,075,094 United States Patent 4,698,373

The present invention provides a polymethyl methacrylate-based film having excellent scratch resistance compared to a conventional polymethyl methacrylate film in order to solve the above problems.

In order to manufacture the scratch resistant polymethyl methacrylate-based film, a polymer composition having a new composition is provided, and a resin obtained from the polymer composition, a film formed by heat treatment thereof, and a manufacturing method thereof are provided.

The film obtained from the polymer composition has high scratch resistance and satisfactory levels of hardness compared to conventional polymethylmethacrylate films.

According to one aspect of the invention, 80 to 99.9 parts by weight of methyl methacrylate monomer; And 0.1 to 20 parts by weight of the silsesquioxane polymer having an organic network structure.

The organic network may be formed by a silane monomer.

The number average molecular weight of the silsesquioxane polymer may be 1,000 to 10,0000.

The polymer composition may further include a polymerization initiator and a release agent.

According to another aspect of the invention, there is provided a scratch resistant resin formed by polymerizing and curing the polymer composition.

According to another aspect of the invention, there is provided a scratch resistant film formed by heat treatment of the scratch resistant resin.

According to another aspect of the invention, i) a first step of preparing a silsesquioxane polymer having an organic network structure by adding water and acid to the silane monomer; Ii) a second step of adding a methyl methacrylate monomer, a polymerization initiator and a releasing agent to the silsesquioxane polymer to polymerize to obtain a resin; And iii) a third step of heat treating the resin.

The silane monomer may include a compound represented by Formula 1 below:

≪ Formula 1 >

(In Formula 1, R ¹ and R ² refer to the corresponding part of the present specification.)

The silane monomers are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N -(3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acrylic Oxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Liethoxysilane, 3-acryloxypropyltripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltriprop Foxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane or bis (triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, At least one of 1,2-bis (triethoxysilyl) ethane and 1,2-bis (trimethoxysilyl) ethane.

The silane monomer may include a mixture of vinyltrimethoxysilane and tetraethoxysilane in a molar ratio of 1:99 to 99: 1, respectively.

The second step may be to use 0.1 to 20 parts by weight of the silsesquioxane-based polymer and 80 to 99.9 parts by weight of the methyl methacrylate monomer.

The polymerization initiator is 2,2'-azobis2,4-dimethyl-valeronitrile (2,2'-Azobis (2,4-dimethyl-valronitrile)), 2,2'-azobis4-methoxy- 2,4-dimethyl valeronitrile ((2,2'-Azobis (4-methoxy-2,4-dimethyl valeronitrile)), α, α'-bis neodecanoylperoxy diisopropyl benzene (α, α ' -bis (neodecanoyl peroxy) diisopropyl benzene, isobutyryl peroxide, cumyl peroxyneodecanoate, di-normal-propyl peroxy dicarbonate, di- Diisopropyl peroxy dicarbonate, 1,1,3,3, -tetramethylbutyl peroxy neodecanoate (1,1,3,3, -tetramethylbuthyl peroxyneodecanoate), 1-cyclohexyl-1 -Methylethyl peroxy neodecanoate, di-2-ethoxyethyl peroxy dicarbonate, di-2-ethoxyhexyl dicarbo Di-2-ethoxyhexyl dicarbonate, tertary-hexyl peroxyneodecanoate, dimethoxybutyl peroxy dicarbonate, bis 3-methyl-3methoxybutyl per Bis (3-methyl-3-methoxybutyl) peroxy dicarbonate, tertiary-butyl peroxyneodecanoate, tertary-hexylperoxypivalate, tertiary-butyl peroxyneodecanoate And at least one of tertiarybutylperoxypivalate and 3,5,5-trimethylhexanoyl peroxide (3,5,5-trimethylhexanoyl peroxide).

The scratch resistant film obtained from the polymer composition according to one aspect of the present invention has a significantly increased hardness and is easy to handle without being easily scratched. In addition, since it can be produced and used without undergoing post-treatment process, manufacturing cost is economical because the production line can be shortened and space and cost can be reduced. On the other hand, when the coating on the scratch-resistant film using a coating, it is possible to obtain a much higher hardness than bringing hardness improvement using the existing coating.

In addition, the scratch-resistant film has a very high surface hardness can replace the high-hardened tempered glass currently used in game consoles, mobile phones, etc., acrylic material, and can be used as an exterior material of home appliances such as digital TVs as well as optical displays It can be applied to various products requiring high hardness surface hardness.

Polymer composition according to an embodiment of the present invention comprises 80 to 99.9 parts by weight of methyl methacrylate monomer and 0.1 to 20 parts by weight of silsesquioxane-based polymer having an organic network structure.

The polymer composition is a composition for producing a scratch-resistant polymethyl methacrylate resin by a polymerization reaction, and contains a small amount of silsesquioxane polymer having an organic network structure in addition to the methyl methacrylate monomer.

The content of the silsesquioxane polymer having an organic network structure is 0.1 to 20 parts by weight, preferably 1 to 5 parts by weight based on 80 to 99.9 parts by weight of the methyl methacrylate monomer. When the content of the silsesquioxane polymer having an organic network structure is 0.1 parts by weight or more, the polymethyl methacrylate resin prepared therefrom has satisfactory scratch resistance and a light transmittance of 90% or more can be secured. The fluidity at high temperature for the sake is also not significantly impaired. If the silsesquioxane-based polymer having an organic network structure enters more than 20 parts by weight, the fluidity is inferior and it does not fall from the mold (glass or stainless).

The organic network has a three-dimensional network structure in which linear polymers are connected by crosslinking to form a three-dimensional network. Specifically, three-dimensionally connected silsesquioxane-based polymers formed by polymerization of silanes are crosslinked. It is a structure forming a net structure.

The silsesquioxane-based polymer having an organic network structure is an organic-inorganic hybrid compound as a polymer having a Si-O-Si skeleton structure. The organic network structure is formed by Si-O-Si bonds. In the case of having an organic network structure, the organic functional group is involved in the formation or modification of the silsesquioxane and increases the solubility in methyl methacrylate in the silsesquioxane type film in the polymethyl methacrylate-based film (substrate). Uniform distribution of polymers. In addition, the silsesquioxane-based polymer having a double bond is polymerized with a methyl methacrylate monomer to further enhance scratch resistance.

The organic network may be formed by a silane monomer. For example, the organic network structure may be formed by adding acid and water to a mixture of silane monomers including vinyltrimethoxysilane and tetraethoxysilane, and optionally, using a solvent such as propylene glycol mono methyl ether. It can also form by adding. The organic network structure thus formed forms a three-dimensional network.

The silsesquioxane polymer preferably has a number average molecular weight of 1,000 to 10,0000. When the number average molecular weight satisfies the above range, the solubility of the silsesquioxane polymer in methyl methacrylate is appropriate, the fluidity of the resulting polymethyl methacrylate resin is appropriate, the moldability is good, and the polymethylmeth The scratch resistance of the acrylate film becomes homogeneous.

The polymer composition may include a methyl methacrylate monomer, a silsesquioxane polymer having an organic network structure, a polymerization initiator, and a release agent. The polymer composition may be polymerized to obtain a scratch resistant polymethyl methacrylate resin, or the obtained scratch resistant polymethyl methacrylate resin may be heat treated to prepare a scratch resistant polymethyl methacrylate film. .

The scratch resistant polymethylmethacrylate-based polymer formed from the polymerization of the polymer composition may have a number average molecular weight of 100,000 to 10,000,000.

Hereinafter, a method of manufacturing a scratch resistant film according to another embodiment of the present invention.

The scratch-resistant film according to another embodiment of the present invention comprises the first step of preparing a silsesquioxane polymer having an organic network structure by adding acid and water to the silane monomer; A second step of adding a methyl methacrylate monomer, a polymerization initiator and a releasing agent to the silsesquioxane polymer to polymerize to obtain a resin; And a third step of heat treating the resin.

The first step is to obtain a silsesquioxane polymer having an organic network structure, specifically, a step of reacting a silane monomer under water and a sulfuric acid catalyst.

The silane monomer is hydrolyzed by an acid catalyst and subjected to a condensation reaction to form a silsesquioxane polymer having an organic network structure.

The silane monomer may include a compound represented by Formula 1 below.

≪ Formula 1 >

In Formula 1, R ¹ is a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ mercapto group, a substituted or unsubstituted C ₁ ~ C ₂₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₂₀ alkoxy group, substituted Or an unsubstituted C ₅ to C ₂₀ aryl group, a substituted or unsubstituted C ₁ to C ₂₀ alkyl acrylic group, a substituted or unsubstituted C ₁ to C ₂₀ alkyl methacryl group, an aminoalkyl group, a sulfone group, a urethane group, and vinyl group and at least one kind of an epoxy group, R ² is a substituted or unsubstituted C ₁ ~ C ₇ alkyl group.

Such silane monomers are specifically 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetrae Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane , N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3 -Acryloxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-arc Oxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxy Propyltripropoxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane or bis (triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) At least one of disulfide, 1,2-bis (triethoxysilyl) ethane and 1,2-bis (trimethoxysilyl) ethane may be included, but is not limited thereto.

For example, a mixture of vinyltrimethoxysilane and tetraethoxysilane in a molar ratio of 1:99 to 99: 1 may be used as the silane monomer.

Meanwhile, in addition to the silane monomers, monomers capable of radical polymerization of other types may also be used, and the monomers capable of radical polymerization of the other types may all be C ₁ -C ₁₀ acid anhydrides or C ₁ -C ₁₀ cycloalkenes having a double bond. , C ₁ -C ₁₀ bicycloalkenes or C ₁ -C ₁₀ cycloalkyl and the like.

The number average molecular weight of the silsesquioxane polymer formed by the first step may be 1,000 to 10,000.

The second step is to obtain a scratch-resistant resin, specifically, 0.1 to 20 parts by weight of the silsesquioxane polymer having the network structure is added to 80 to 99.9 parts by weight of methyl methacrylate monomer and a polymerization initiator and a release agent are added. By polymerization.

The methyl methacrylate monomer forms a basic unit of a scratch resistant polymethyl methacrylate-based polymer together with the silsesquioxane-based polymer by polymerization, and the content of methyl methacrylate is silsesquioxane-based polymer in the polymer. Since it is more than a polymer, it makes up most of the polymer structure.

As the polymerization initiator, those having a half life of 10 hours at 60 ° C. or less can be used. When such a polymerization initiator is used, a yellowing phenomenon does not occur, and thus a polymethyl methacrylate-based resin having excellent light transmittance can be produced, and this can be used for an optically transparent resin.

As the initiator, for example, 2,2'-azobis2,4-dimethyl-valeronitrile, 2,2'-azobis4-methoxy-2,4-dimethyl valeronitrile, α, α ' Bis neodecanoylperoxy diisopropyl benzene, isobutyryl peroxide, cumyl peroxyneodecanoate, di-normal-propyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, 1,1,3, 3, -tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2-ethoxyethyl peroxy dicarbonate, di-2-ethoxyhexyl dicarbonate , Tert-hexyl peroxy neodecanoate, dimethoxybutyl peroxy dicarbonate, bis 3-methyl-3 methoxybutyl peroxy dicarbonate, tert-butyl peroxy neodecanoate, tertary-hexyl per Oxypibarate, tertiary-butylperoxypibarate and 3,5,5-trimethylhexanoylperoxide, or their You can use the sum, but is not limited to this. Moreover, as a polymerization initiator, it is also possible to use together the high temperature polymerization initiator whose half life is 10 hours at 60 degrees C or less, and the half life is 10 hours at 70 degreeC or more.

The polymerization initiator may be used in 0.01 to 1 part by weight, preferably 0.05 to 0.2 part by weight based on 100 parts by weight of the polymer composition.

As said mold release agent, what is used for normal polymethyl methacrylate polymerization can be used.

Finally, the third step is a step of obtaining a scratch resistant film by heat-treating the resin.

As used herein, in the expression "substituted or unsubstituted A (A is any functional group)", the term "substituted A" means "at least one hydrogen atom of A is a deuterium atom, a halogen atom, a hydroxyl group, Cyano group, nitro group, carboxyl group, silyl group or salt derivative thereof, sulfonic acid group or salt derivative thereof, phosphoric acid group or salt derivative thereof, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group A ”substituted with at least one of the groups represented by a C ₁ -C ₂₀ alkoxy group, a C ₃ -C ₂₀ cycloalkyl group and a C ₃ -C ₂₀ cycloalkenyl group. For example, “substituted A” means “at least one hydrogen atom of A is a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a silyl group, a methyl group, an ethyl group, a propyl group, a butyl group And A ″ substituted with at least one of pentyl groups.

The invention can be better understood through the following examples. However, the following examples are for illustrative purposes of the present invention and are not intended to limit the protection scope defined by the appended claims.

Example  One

60 g (0.4 mol) of vinyltrimethoxysilane and 140 g (0.67 mol) of tetraethoxysilane were added to a 500 ml flask, and 10% sulfuric acid aqueous solution was added as a catalyst to 50 parts by weight relative to 100 parts by weight of silane and stirred at room temperature for 5 hours. The resulting droplets were immersed after stirring to give 118 g of silsesquioxane polymer (yield: 59%).

99.67 parts by weight of methyl methacrylate monomer is mixed with 0.33 parts by weight of the silsesquioxane polymer, 1,1,3,3-tetramethylbutylperoxy neodecanoate (polymerization initiator) and stearic acid (release agent). The composition was made.

After filling the polymer composition in a glass frame of 20cm × 20cm, the surroundings were sealed with rubber packing, and then cured for 13 hours in a 43 ° C. water bath and further heat treated at a temperature of 105 ° C. for 1 hour to strengthen the surface strength of the film. Prepared.

Example  2

Except for using 99.67 parts by weight of methyl methacrylate monomer and 0.33 parts by weight of silsesquioxane polymer in Example 1, except that 99.34 parts by weight of methyl methacrylate monomer and 0.66 parts by weight of silsesquioxane polymer were used. An acrylic sheet was prepared in the same manner as in Example 1.

Example  3

Except for using 99.67 parts by weight of methyl methacrylate monomer and 0.33 parts by weight of silsesquioxane polymer in Example 1, except that 99.00 parts by weight of methyl methacrylate monomer and 1.00 parts by weight of silsesquioxane polymer are used. An acrylic sheet was prepared in the same manner as in Example 1.

Example  4

Except for using 99.67 parts by weight of methyl methacrylate monomer and 0.33 parts by weight of silsesquioxane polymer in Example 1, except that 98.67 parts by weight of methyl methacrylate monomer and 1.33 parts by weight of silsesquioxane polymer were used. An acrylic sheet was prepared in the same manner as in Example 1.

Example  5

Except for using 99.67 parts by weight of methyl methacrylate monomer and 0.33 parts by weight of silsesquioxane polymer in Example 1, except that 98.34 parts by weight of methyl methacrylate monomer and 1.66 parts by weight of silsesquioxane polymer were used. An acrylic sheet was prepared in the same manner as in Example 1.

Example  6

Except for using 99.67 parts by weight of methyl methacrylate monomer and 0.33 parts by weight of silsesquioxane polymer in Example 1, except that 98.00 parts by weight of methyl methacrylate monomer and 2.00 parts by weight of silsesquioxane polymer are used. An acrylic sheet was prepared in the same manner as in Example 1.

Example  7

Except for using 99.67 parts by weight of methyl methacrylate monomer and 0.33 parts by weight of silsesquioxane polymer in Example 1, except that 96.67 parts by weight of methyl methacrylate monomer and 3.33 parts by weight of silsesquioxane polymer were used. An acrylic sheet was prepared in the same manner as in Example 1.

Example  8

Except for using 99.67 parts by weight of methyl methacrylate monomer and 0.33 part by weight of silsesquioxane polymer in Example 1, except that 93.34 parts by weight of methyl methacrylate monomer and 6.66 parts by weight of silsesquioxane polymer were used. An acrylic sheet was prepared in the same manner as in Example 1.

Example  9

Except for using 99.67 parts by weight of methyl methacrylate monomer and 0.33 parts by weight of silsesquioxane polymer in Example 1, except that 90.00 parts by weight of methyl methacrylate monomer and 10.00 parts by weight of silsesquioxane polymer were used. An acrylic sheet was prepared in the same manner as in Example 1.

Comparative Example  One

The reaction composition was prepared by mixing the methyl methacrylate monomer with 1,1,3,3-tetramethylbutylperoxyneodecanoate and stearic acid.

After filling the obtained reaction composition into a glass frame of 20cm * 20cm, the surroundings were sealed with rubber packing, and then cured for 13 hours in a 43 ℃ water bath, and further heat treated at a temperature of 105 ℃ for 1 hour to obtain an acrylic sheet having an enhanced surface strength of the sheet. Prepared.

The surface hardness and the light transmittance of the acrylic sheet according to Examples 1 to 9 and the acrylic sheet according to Comparative Example 1 were measured and shown in Table 1 below. The surface hardness of the acrylic sheet was measured by using a standard pencil (6B-9H) at a 45 degree angle and applying a constant load (1Kg) to the surface hardness of the acrylic sheet. Was measured using a GENESYS 5 spectrophotometer of Spectoronic instruments in accordance with ASTM D 1003.

division Silsesquioxane-based polymer content (parts by weight) Methyl methacrylate content (parts by weight) Used mold Hardness Light transmittance
(%) Example 1 0.33 99.67 Glass 2H 92.4 Example 2 0.66 99.34 Glass 2H 92.4 Example 3 1.00 99.00 Glass 3H 92.3 Example 4 1.33 98.67 Glass 4H 92.2 Example 5 1.66 98.34 Glass 5H 92.3 Example 6 2.00 98.00 Stainless steel 6H 92.2 Example 7 3.33 96.67 Stainless steel 7H 92.2 Example 8 6.66 93.34 Stainless steel 7H 92.1 Example 9 10.00 90.00 Stainless steel 7H 92.1 Comparative Example 1 0 100 Glass 1H 91.5

Referring to Table 1, it can be seen that the acrylic sheets according to Examples 1 to 9 have a higher hardness and slightly higher or similar light transmittance than the acrylic sheets according to Comparative Example 1. From this, the acrylic sheet obtained by using the scratch resistant resin formed from the polymer composition according to the embodiment of the present invention is more resistant to scratches and slightly light transmittance than the acrylic sheet obtained by using a conventional polymethylmethacrylate resin. It can be seen that it is increased or similar. In addition, it can be seen that the scratch-resistant resin obtained from the polymer composition according to the embodiment of the present invention is easier to process than a conventional polymethyl methacrylate resin.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the scope of the present invention . Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

Claims (12)

80-99.9 parts by weight of methyl methacrylate monomer; And
0.1 to 20 parts by weight of the silsesquioxane polymer having an organic network structure
Including;
A polymer composition further comprising a polymerization initiator and a release agent. The method of claim 1,
Polymer composition, wherein the organic network is formed of a silane monomer. The method of claim 1,
A polymer composition having a number average molecular weight of the silsesquioxane polymer based on 1,000 to 10,0000. delete The scratch resistant resin formed by polymerizing and hardening the polymer composition of any one of Claims 1-3. The scratch resistant film formed by heat-treating the scratch resistant resin of claim 5. Iii) a first step of preparing a silsesquioxane polymer having an organic network structure by adding water and an acid to the silane monomer;
Ii) a second step of adding a methyl methacrylate monomer, a polymerization initiator and a releasing agent to the silsesquioxane polymer to polymerize to obtain a resin; And
Iii) a third step of heat treating the resin;
Including;
The second step is a method of producing a scratch resistant film using 0.1 to 20 parts by weight of the silsesquioxane-based polymer and 80 to 99.9 parts by weight of the methyl methacrylate monomer. The method of claim 7, wherein
Method for producing a scratch resistant film comprising the compound represented by Formula 1 wherein the silane monomer:
≪ Formula 1 >

In Formula 1, R ¹ is a hydrogen atom, a substituted or unsubstituted C ₁ -C ₂₀ mercapto group, a substituted or unsubstituted C ₁ ~ C ₂₀ alkyl group, a substituted or unsubstituted C ₁ ~ C ₂₀ alkoxy group, substituted Or an unsubstituted C ₅ to C ₂₀ aryl group, a substituted or unsubstituted C ₁ to C ₂₀ alkyl acrylic group, a substituted or unsubstituted C ₁ to C ₂₀ alkyl methacryl group, an aminoalkyl group, a sulfone group, a urethane group, and vinyl group and at least one kind of an epoxy group, R ² is a substituted or unsubstituted C ₁ ~ C ₇ alkyl group. The method of claim 7, wherein
The silane monomer is 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N -(3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acrylic Oxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Liethoxysilane, 3-acryloxypropyltripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltriprop Foxysilane, N- (aminoethyl-3-aminopropyl) trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, heptadecafluorodecyltrimethoxysilane or bis (triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, A method for producing a scratch resistant film comprising at least one of 1,2-bis (triethoxysilyl) ethane and 1,2-bis (trimethoxysilyl) ethane. The method of claim 7, wherein
The silane monomer is a method of producing a scratch-resistant film comprising a mixture of vinyl trimethoxysilane and tetraethoxysilane in a molar ratio of 1:99 to 99: 1, respectively. delete The method of claim 7, wherein
The polymerization initiator is 2,2'-azobis2,4-dimethyl-valeronitrile, 2,2'-azobis4-methoxy-2,4-dimethyl valeronitrile, α, α'-bis neodeca Noylperoxy diisopropyl benzene, isobutyryl peroxide, cumyl peroxy neodecanoate, di-normal-propyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, 1,1,3,3, -tetra Methylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-2-ethoxyethyl peroxy dicarbonate, di-2-ethoxyhexyl dicarbonate, tertiary Hexyl peroxy neodecanoate, dimethoxybutyl peroxy dicarbonate, bis 3-methyl-3methoxybutyl peroxy dicarbonate, tertiary-butyl peroxy neodecanoate, tertiary-hexyl peroxy pibarate, At least one of tert-butylperoxy pibarate and 3,5,5-trimethylhexanoylperoxide The method of scratch resistance film.