TW202118825A - Polymethacrylate composition and optical device made therefrom, and display apparatus - Google Patents

Abstract

A polymethacrylate composition, an optical device made therefrom, and a display apparatus are provided. The polymethacrylate composition includes 50 to 85 parts by weight of methacrylate series polymer, and 15 to 50 parts by weight of styrene series-maleic anhydride series copolymer. The methacrylate series polymer includes 94wt%-98wt% of methacrylate series monomer unit, 2wt%~6wt% of acrylate series monomer unit and 0wt%-4wt% of first copolymerizable monomer unit, and has weight average molecular weight (Mw) of 70,000 to 95,000. The styrene series-maleic anhydride series copolymer includes 65wt%-76wt% of styrene series monomer unit, 24wt%~35wt% of maleic anhydride series monomer unit, and 0wt%-11wt% of second copolymerizable monomer unit. A total quantity of the methacrylate series polymer and the styrene series-maleic anhydride series copolymer is 100 parts by weight.

Description

Polymethacrylate composition and optical element and display device formed therefrom

The present invention relates to a polymer composition, and more particularly to a polymethacrylate composition and optical elements and display devices formed therefrom.

Polymethacrylate (polymethacrylate) is a versatile polymer. It has good evaluations in terms of processability, physical properties and mechanical properties. Its light transmittance is equivalent to glass and the appearance of molded products is good. Therefore, it has become the best at present. One of the excellent transparent polymer materials, and is often used in various optical components or consumer goods, such as camera lenses, lenses, optical films, automobile taillights, billboards... etc.

In recent years, with the development of thin and lightweight notebook computers, the requirements for thinning and high performance of optical elements in display devices such as liquid crystal display devices have also increased. Moreover, as the application environment of liquid crystal display devices becomes more extensive, optical elements are also required to have durability properties such as heat resistance in a high-temperature environment and humidity resistance in a high-humidity environment.

Although polymethacrylate has excellent optical properties and processability, its heat resistance is slightly insufficient. Therefore, how to make polymethacrylate have good optical properties and heat resistance at the same time is a topic that needs to be improved in this field. In addition, during the subsequent processing and forming, the high-temperature thermal process is likely to cause the polymethacrylate composition to be produced. Deterioration or yellowing, or even appearance defects, will prevent the polymethacrylate composition from fully exhibiting its original good optical properties.

The present invention provides a polymethacrylate composition and an optical element formed from the foregoing composition, which can have the heat resistance and optical properties of the polymethacrylate composition, and a display device having the foregoing optical element.

The polymethacrylate composition of the present invention includes 50 to 85 parts by weight of methacrylate polymer and 15 to 50 parts by weight of styrene-maleic anhydride copolymer. The methacrylate-based polymer includes 94wt% to 98wt% of methacrylate-based monomer units, 2wt% to 6wt% of acrylate-based monomer units, and 0wt% to 4wt% of the first copolymerizable monomer. Body unit. The weight average molecular weight (Mw) of the methacrylate-based polymer is 70,000 to 95,000. The styrene-maleic anhydride copolymer includes 65wt% to 76wt% of styrene monomer units, 24wt% to 35wt% of maleic anhydride monomer units, and 0wt% to 11wt% of the second copolymer. Polymerize monomer units. The total amount of the methacrylate-based polymer and the styrene-maleic anhydride copolymer is 100 parts by weight.

In an embodiment of the present invention, the above-mentioned polymethacrylate composition may further include 200 ppm to 2000 ppm of phenolic compounds with 2,4,8,10-tetraoxaspiro(5,5)undecyl groups .

In an embodiment of the present invention, the ratio of the weight percentage of the styrene monomer unit to the weight percentage of the maleic anhydride monomer unit of the styrene-maleic anhydride copolymer is 1 to 8.5.

In an embodiment of the present invention, the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is 60,000 to 100,000.

In an embodiment of the present invention, the molecular weight distribution index (PDI) of the above-mentioned styrene-maleic anhydride copolymer ranges from 1.5 to 2.05.

In an embodiment of the present invention, the above-mentioned polymethacrylate composition may further include 10,000 ppm to 50,000 ppm of ultraviolet absorber.

In an embodiment of the present invention, the flash point of the ultraviolet absorber is ≧240°C.

In an embodiment of the present invention, the aforementioned ultraviolet absorber is selected from 2-(4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)- 5-octyloxyphenol, 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol], 2-(4,6-diphenyl-1 ,3,5-Triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2,2',4,4'-tetrahydroxydiphenyl ketone, 3-[(2-cyano -3,3-diphenylpropenyl)oxy]-2,2-bis{[(2-cyano-3,3-diphenylpropenyl)oxy]methyl}propyl 2-cyano-3 ,3-Diphenylacrylate, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, and 2-(2'-hydroxy-3',5' -At least one of the group consisting of dipentylphenyl)benzotriazole.

According to an embodiment, the polymethacrylate composition can basically consist of 50 to 85 parts by weight of methacrylate-based polymer, 15 to 50 parts by weight of styrene-maleic anhydride copolymer, and 200 ppm to 2000 ppm. 2,4,8,10-Tetraoxaspiro(5,5)undecyl group phenolic compound and 10,000ppm to 50,000ppm ultraviolet absorber. The methacrylate-based polymer includes 94wt% to 98wt% of methacrylate-based monomer units and 2wt% to 6wt% of acrylate-based monomer units. The weight average molecular weight (Mw) of the methacrylate-based polymer is 70,000 to 95,000. The styrene-maleic anhydride copolymer includes 65wt% to 76wt% of styrene monomer units and 24wt% to 35wt% of maleic anhydride monomer units. The total amount of the methacrylate-based polymer and the styrene-maleic anhydride copolymer is 100 parts by weight.

The optical element of the present invention is formed of the polymethacrylate composition as described above.

In an embodiment of the present invention, the above-mentioned optical element is at least one selected from the group consisting of an optical plate, an optical sheet, and an optical film.

The display device of the present invention includes the optical element as described above, and the display device is selected from a television, a digital camera, a digital video camera, a digital photo frame, a mobile phone, a notebook personal computer, a mobile computer, a screen for a computer, etc. , At least one of the group consisting of a portable game machine, a portable information terminal, an audio reproduction device, a game machine, and a car display.

Based on the above, the polymethacrylate composition of the present invention has a specific composition and the composition has a specific ratio, so it can have excellent heat resistance, thermal stability and optical properties at the same time, so it can be applied to optical elements and has low fog Excellent optical properties of low yellowness and low yellowness. The display device having the above-mentioned optical element also has excellent effects in display.

In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the following embodiments are specially cited, which are described in detail as follows.

Hereinafter, embodiments of the present invention will be described in detail. However, these embodiments are illustrative, and the present disclosure is not limited thereto.

In an embodiment of the present invention, the polymethacrylate composition includes 50 to 85 parts by weight of methacrylate polymer, 15 to 50 parts by weight of styrene-maleic anhydride copolymer, and organophosphorus. Compound. The methacrylate-based polymer includes 94wt%~98wt% methacrylate-based monomer units, 2wt%~6wt% acrylate-based monomer units, and 0wt%~4wt% of the first copolymerizable monomer unit And its weight average molecular weight (Mw) is 70,000 to 95,000. The styrene-maleic anhydride copolymer includes 65wt% to 76wt% of styrene monomer units, 24wt% to 35wt% of maleic anhydride monomer units, and 0wt% to 11wt% of the second copolymer. Polymerize monomer units.

Methacrylate-based polymer

The methacrylate-based polymer is mainly polymerized from a monomer mixture mainly composed of methacrylate-based monomers. In one embodiment, the methacrylate-based polymer is polymerized from a mixture containing methacrylate-based monomers and acrylate-based monomers, and its weight average molecular weight (Mw) is 20,000 to 200,000. For example, it is 50,000 to 150,000, or 70,000 to 110,000; preferably, the methacrylate-based polymer is composed of a methacrylate-based monomer, an acrylate-based monomer, and the first copolymerizable monomer. A mixture of bodies is formed by polymerization.

Specific examples of methacrylate-based monomers include, but are not limited to: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, Amyl methacrylate, cyclohexyl methacrylate, heptyl methacrylate, n-octyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Benzyl methyl ester or 2-ethylhexyl methacrylate (2-ethylhexyl methacrylate), etc., and the above monomers can be used alone or in combination.

Specific examples of acrylate monomers include but are not limited to: methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, heptyl acrylate, dodecane acrylate Base ester, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, octadecyl acrylate, etc. The above-mentioned monomers can be used alone or in combination.

Specific examples of the above-mentioned first copolymerizable monomer include but are not limited to: (1) Unsaturated carboxylic acid monomers, such as but not limited to acrylic acid, methacrylic acid, maleic acid, itaconic acid, citrine Citraconic acid, or aconitic acid, etc.; (2) Maleimide monomers, such as but not limited to maleimide, nitrogen-methylmaleimide, nitrogen-isopropyl Nitromaleimide, nitrogen-butylmaleimide, nitrogen-hexylmaleimide, nitrogen-octylmaleimide, nitrogen-dodecylmaleimide, nitrogen-ring Hexylmaleimide, nitrogen-phenylmaleimide, nitrogen-2,3-tolylmaleimide, nitrogen-2,4-tolylmaleimide, nitrogen-2,3 -Ethylphenylmaleimide, nitrogen-2,4-ethylphenylmaleimide, nitrogen-2,3-butylphenylmaleimide, nitrogen-2,4-butylphenylmaleimide Leximine, nitrogen-2,6-tolylmaleimide, nitrogen-2,3-chlorophenylmaleimide, nitrogen-2,4-chlorophenylmaleimide, nitrogen -2,3-bromophenylmaleimide, nitrogen-2,4-bromophenylmaleimide, etc.; (3) monomers of compounds containing acrylic groups, such as but not limited to acrylamide ), acrylonitrile, α-methacrylonitrile, allyl glycidyl ether or glycidyl (meth)acrylate; (4) containing Vinyl compound monomers, such as but not limited to vinyl acetate or chloroethene; (5) Styrenic monomers, such as but not limited to styrene, 2-chlorostyrene, 4-chloro Styrene, bromostyrene, vinyl toluene, α-methylstyrene, p-tertiary butylstyrene, p-methylstyrene, o-methylstyrene, M-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, etc. The above-mentioned monomers can be used alone or in combination.

Preferably, the methacrylate-based polymer includes a methacrylate-based monomer unit, an acrylate-based monomer unit, and a first copolymerizable monomer unit. The "monomer unit" referred to herein refers to the repeating structure formed by the polymerization reaction of the aforementioned methacrylate-based monomer, acrylate-based monomer or the first copolymerizable monomer.

In one embodiment, in order to make the methacrylate-based polymer in the polymethacrylate composition have better compatibility with the styrene-maleic anhydride-based copolymer, the methacrylate-based The polymer contains 94 wt% (wt%) to 98wt% of methacrylate monomer units and 2wt% to 6wt% of acrylate monomer units, and the weight average molecular weight of the methacrylate polymer (Mw) is 70,000 to 95,000. In addition, the methacrylate-based polymer may optionally contain 0 wt% to 4 wt% of the first copolymerizable monomer unit.

In another embodiment, the content of the acrylate monomer unit of the methacrylate polymer is 3.5wt%~6wt%, such as 3.5wt%~5.5wt% or 4wt%~5.5wt% .

In one embodiment, the weight average molecular weight (Mw) of the methacrylate-based polymer is 70,000 to 95,000, for example, 75,000 to 95,000, 80,000 to 95,000, and 85,000 to 95,000.

The methacrylate-based polymer contains 94 wt% to 98 wt% of methacrylate-based monomer units and 2 wt% to 6 wt% of acrylate-based monomer units, and the methacrylate-based polymer When its weight average molecular weight (Mw) is 70,000 to 95,000, in addition to improving compatibility with styrene-maleic anhydride copolymers, it also has a balance between processability and heat resistance. Therefore, in When extruding and granulating, it can reduce the residence time of the composition in the extruder, reduce the degree of deterioration of the styrene-maleic anhydride copolymer, and thereby maintain the heat resistance, thermal stability and yellowness of the composition .

The methacrylate-based polymer can be prepared using a solution or bulk polymerization method, and the polymerization reaction is preferably carried out in the presence of a solvent to avoid the situation where the viscosity of the crude polymer increases and the polymerization reaction is difficult to control. The viscosity of the methacrylate polymer is usually expressed in terms of solid content, and the amount of solvent needs to be adjusted so that the solid content of the crude polymer is less than 50% by weight, or preferably less than 40% by weight.

If the boiling point of the above-mentioned solvent is close to the boiling point of the main monomer to be polymerized, the mixture formed by the solvent and monomer will have a narrower boiling point range, which can reduce the chance of mixing contaminants in the recycled mixture, and at the same time Eliminates the step of intermediate fractionation of the recycled monomer and solvent mixture. For example, a solvent with a boiling point similar to that of methacrylate monomers can be selected. Preferably, the solvent has a boiling point of 40°C to 225°C; more preferably, it has a boiling point of 60°C to 150°C. The boiling point. Specific examples of the above solvents include but are not limited to: hexane, heptane, octane, benzene, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, cyclohexane, cyclodecane, isooctane, Or various low-boiling hydrocarbon or aromatic hydrocarbon solvents. The aforementioned solvents can be used alone or in combination.

The polymerization reaction of methacrylate polymers is initiated by a free radical initiator. The free radical initiator is not particularly limited. Specific examples include but are not limited to: (1) Azo compounds: such as 2, 2'-azobisisobutyronitrile (2,2'-azobis- (isobutyronitrile), referred to as AIBN), 2,2'-azobis(2-methylbutyronitrile) (2,2'-azobis- (2-methylbutyronitrile), referred to as AMBN), 2,2'-azobis(2,4-dimethylvaleronitrile) (2,2'-azobis-(2,4-dimethylvaleronitrile), referred to as ADVN) Etc.; (2) Diacyl peroxides compounds: such as dilauroyl peroxide, decanoyl peroxide, dibenzoyl peroxide, BPO for short ), etc.; (3) Dialkyls (dialkyls) compounds: such as 2,5-dimethyl-2,5-tertiary butylperoxyhexane (2,5-dimethyl-2,5-di -(t-butylperoxy)hexane), dicumyl peroxide, 1,3-bis-(t-butyl peroxy isopropyl) benzene (1,3-bis-(t-butyl peroxy isopropyl) )benzene), etc.; (4) peroxyesters (peroxyesters) compounds: such as t-butylperoxypivalate, 2,5-dimethyl-2,5-bis(2- Ethyl hexanoylperoxy) hexane (2,5-dimethyl-2,5-di(2-ethyl hexanoylperoxy) hexane), etc.; (5) peroxycarbonates (peroxycarbonates) compounds: such as 2-ethylhexyl Tert-amylperoxy 2-ethylhexyl carbonate, tert-butylperoxy 2-ethylhexyl carbonate, etc.; (6) Peroxy dicarbonate (peroxydicarbonates) compounds: such as dimyristyl peroxydicarbonate, di(4-tert-butylcyclohexyl peroxydicarbonate), etc.; (7) Peroxyketal Alcohol (peroxyketal) compounds: such as 1,1-di(tert-butylperoxy) 3,3,5-trimethylcyclohexane (1,1-di(tert-butylperoxy)-3,3,5) -trimethylcyclohexane), 2,2-di(4,4-di(tert-butyl peroxy)cyclohexyl) propane (2,2-di(4,4-di(tert-butyl peroxy)cyclohexyl) propane), etc. ; (8) Hydroperoxides compounds: such as t-butyl hydroperoxide, isopropylcumyl hydroperoxide, etc.; (9) Others: 2 ,3-Dimethyl-2,3-diphenyl-butane (2,3-dimethyl-2,3-diphenyl-butane), potassium persulfate, sodium persulfate, persulfuric acid Ammonium (ammonium persulfate) and so on. Preferably, the free radical initiator is 2,2'-azobisisobutylnitrile. Based on 100 parts by weight of the total amount of the monomer mixture fed in, the amount of the free radical initiator used may be 0.01 to 1 part by weight, preferably 0.03 to 0.5 part by weight, more preferably 0.07 to 0.1 parts by weight.

The polymerization reaction used to prepare the methacrylate polymer can be carried out at room temperature, but in order to increase the polymerization rate, the reaction system can be heated. The general reaction temperature is about 5°C to 200°C, the preferred reaction temperature is 20°C to 130°C, and the more preferred reaction temperature is 30°C to 100°C. During the polymerization reaction, a chain transfer agent can be added as needed to facilitate molecular weight control; the chain transfer agent includes, but is not limited to: n-dodecyl mercaptan (NDM), stearyl Stearyl mercaptan, t-dodecyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, third-octyl mercaptan, third -Nonyl mercaptan or terpinolene, etc.

Styrene - Maleic anhydride copolymer

Styrenic-maleic anhydride copolymer is any polymer obtained by copolymerizing a styrene-based monomer, a maleic anhydride-based monomer and a second copolymerizable monomer, such as linear or branched random copolymerization Compounds, linear or branched block copolymers, or mixtures thereof.

In one embodiment, the styrene-maleic anhydride copolymer is polymerized by a mixture containing a styrene-based monomer, a maleic anhydride-based monomer, and a second copolymerizable monomer.

The above-mentioned maleic anhydride-based monomers can be used alone or in combination, and the maleic anhydride-based monomers include, but are not limited to, maleic anhydride, itaconic anhydride, citraconic anhydride, or aconitic anhydride. Preferably, the maleic anhydride monomer is maleic anhydride.

The above-mentioned styrenic monomers can be used alone or in combination, and styrenic monomers such as but not limited to styrene, (1) halogen-substituted styrenes such as but not limited to 2-chlorostyrene, 4-chlorostyrene or Bromostyrene, etc.; (2) Alkyl substituted styrenes such as but not limited to vinyl toluene (vinyl toluene), α-methyl styrene (α-methylstyrene), p-tertiary butyl styrene, -Methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, etc. In one embodiment, the styrenic monomer is at least one selected from the group consisting of styrene, halogen-substituted styrene, and alkyl-substituted styrene. In one embodiment, the styrenic monomer is at least one selected from the group consisting of styrene and α-methylstyrene.

The second copolymerizable monomer used to polymerize the styrene-maleic anhydride copolymer can be used alone or in combination, and the second copolymerizable monomer is, for example, but not limited to, selected from those used for methacrylates as described above. The methacrylate-based monomers and acrylate-based monomers of the polymer form a group, so I will not repeat them.

Preferably, the styrene-maleic anhydride copolymer includes a styrene-based monomer unit, a maleic anhydride-based monomer unit, and a second copolymerizable monomer unit. The "monomer unit" referred to herein refers to the repeating structure formed by the polymerization reaction of the aforementioned styrene-based monomer, maleic anhydride-based monomer or second copolymerizable monomer. Therefore, the styrene-based monomer unit is derived from the above-mentioned styrene-based monomer, the maleic anhydride-based monomer unit is derived from the above-mentioned maleic anhydride-based monomer, and the second copolymerizable monomer unit is derived from the above-mentioned second copolymerizable monomer unit. monomer.

In one embodiment, the styrene-maleic anhydride copolymer includes 65wt% to 76wt% of styrene monomer units, 24wt% to 35wt% of maleic anhydride monomer units, and 0wt% to 11wt%. The second copolymerizable monomer unit.

In another embodiment, the content of the styrene monomer unit in the styrene-maleic anhydride copolymer is 65wt%~76wt%; preferably 65wt%~75wt%; more preferably 66wt% ~74wt%, when the content of styrene monomer unit is higher than 65wt%, it will make the composition of polymethacrylate with styrene-maleic anhydride copolymer containing such styrene monomer unit content It has good light transmittance (T%), haze (HAZE) and yellowness (YI) performance; when the content of styrene monomer unit is below 76wt%, it will make styrene-maleic anhydride The content of the maleic anhydride-based monomer unit in the copolymer is more than 24wt%. Therefore, the polymethacrylate composition containing this styrene-maleic anhydride copolymer can have good heat resistance (glass transition temperature). , Tg).

In one embodiment, the content of styrene monomer units in the styrene-maleic anhydride copolymer ranges from 65 wt% to 76 wt%, and the content of maleic anhydride monomer units ranges from 24 wt% to 24 wt%. 35wt%, a polymethacrylate composition with a styrene-maleic anhydride copolymer containing this ratio can be applied to optical elements with high heat resistance requirements. Preferably, a styrene-based copolymer with this ratio -The molecular weight distribution index (PDI) of maleic anhydride copolymers is in the range of 1.5 to 2.05, which can maintain good light transmittance (T%), haze (HAZE) and yellowness (YI) while maintaining high performance Heat resistance performance.

In one embodiment, the ratio of the weight percentage of the styrene-based monomer units to the maleic anhydride-based monomer units in the styrene-maleic anhydride copolymer is between 1 and 8.5; preferably between 1.3 and 8. Between; more preferably 1.5~7.

In one embodiment, the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is 60,000 to 100,000, preferably 65,000 to 95,000, and more preferably 65,000 to 90,000.

In one embodiment, the number average molecular weight (Mn) of the styrene-maleic anhydride copolymer is 30,000 to 55,000, preferably 35,000 to 50,000, and more preferably 37,000 to 48,000.

In one embodiment, the molecular weight distribution index (PDI) of the styrene-maleic anhydride copolymer ranges from 1.5 to 2.05, preferably from 1.7 to 2.0, and more preferably from 1.7 to 1.9. When the molecular weight distribution index (PDI) of the acetic anhydride copolymer is greater than 2.05, the optical properties (low haze) of the polymethacrylate composition containing the styrene-maleic anhydride copolymer with this molecular weight distribution index will be improved. And low yellowness).

The polymerization method of the styrene-maleic anhydride copolymer is not particularly limited, and it may be free radical polymerization using a free radical initiator. The method obtained by the treatment of suspension polymerization and emulsion polymerization sometimes fails to obtain sufficient transparency. The radical initiator used is, for example, but not limited to, selected from the radical initiators used in the methacrylate polymer as described above, so it will not be repeated.

Based on 100 parts by weight of the total monomers, the added amount of the free radical initiator is preferably 0.001 to 5 parts by weight. A small amount of solvents can also be used during polymerization, such as butane, pentane, hexane, isopentane, heptane, octane, isooctane and other aliphatic hydrocarbons; cyclopentane, methylcyclopentane, cyclohexane Alicyclic hydrocarbons such as alkanes, methylcyclohexane, and ethylcyclohexane; or aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene. In addition, known molecular weight modifiers such as 4-methyl-2,4-diphenylpent-1-ene, tertiary-dodecyl mercaptan, and n-dodecyl mercaptan may be added during polymerization. The polymerization temperature is preferably 80°C to 170°C, more preferably 100°C to 160°C.

In addition, any additives may be mixed according to various purposes within a range that does not significantly impair the effects of the present invention. The types of these additives are not particularly limited, as long as they are generally used in resin compositions or rubber compositions, such as antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, processing aids, fillers, strengthening agents, Colorants, antistatic agents, other additives, etc., and the above additives are not limited to being added during the polymerization reaction, after the polymerization reaction, or during extrusion and kneading. The content of additives is generally calculated when the total amount of polymer in the polymethacrylate composition is 100 parts by weight, that is, based on the methacrylate-based polymer and the styrene-maleic anhydride copolymer The total amount is 100 parts by weight.

With 2,4,8,10- Tetraoxa ( 5,5) Undecyl phenolic compounds

式(1)In one embodiment, the phenolic compound with 2,4,8,10-tetraoxaspiro(5,5) undecyl group, for example, contains the structure of the following formula (1).

Formula 1)

In the above formula, R _a and R _b each independently represent a C6-C12 alkyl, cycloalkyl, ether, ester, or combination thereof; R ₁ and R ₂ each independently represent hydrogen or C1-C10 Linear, branched or cyclic alkyl. Specific examples of antioxidants include but are not limited to:

3-(1,1-dimethylethyl)-4-hydroxy-5-(1-methylethyl)-,2,4,8,10-tetraoxaspiro[5.5]undecane-3 ,9-Diylbis(2,2-dimethyl-2,1-diethyl) Benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5-(1- methylethyl)-, 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2- dimethyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3-(1,1-Dimethylethyl)-5-ethyl-4-hydroxy-,1,1'-[2,4,8,10-tetraoxaspiro[5.5]undecane-3 ,9-Diylbis(2,2-dimethyl-2,1-diethyl))benzenepropanoic acid (Benzenepropanoic acid, 3-(1,1-dimethylethyl)-5-ethyl-4-hydroxy- , 1,1'-[2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2-dimethyl-2,1-ethanediyl)] ester), its chemical formula is as follows.

3,5-bis(1,1-dimethylethyl)-4-hydroxy-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2 ,2-Dimethyl-2,1-diethyl)Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diylbis(2,2-dimethyl-2,1-ethanediyl) ester), its chemical formula is as follows.

4-hydroxy-3,5-bis(1,1,2,2-tetramethylbutyl)-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-bis Benzenepropanoic acid,4-hydroxy-3,5-bis(1,1,2,2-tetramethylbutyl) -,2 ,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2-dimethyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3-(1,1-Dimethylethyl)-4-hydroxy-5-methyl-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis (2-Ethyl-2-methyl-2,1-diethyl)Benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-, 2,4, 8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-ethyl-2-methyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3,5-bis(1,1-dimethylethyl)-4-hydroxy-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2 -Ethyl-2-methyl-2,1-diethyl)phenylpropanoic acid (Benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, 2,4,8,10 -tetraoxaspiro[5.5]undecane-3,9-diylbis(2-ethyl-2-methyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3-(1,1-Dimethylethyl)-4-hydroxy-5-methyl-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis (2-Methyl-2-propyl-2,1-diethyl)Benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-, 2,4, 8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methyl-2-propyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3-(1,1-Dimethylethyl)-4-hydroxy-5-methyl-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis (2,2-Diethyl-2,1-diethyl)Benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-, 2,4,8, 10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2-diethyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3-(1,1-dimethylethyl)-4-hydroxy-5-(1-methylethyl)-,2,4,8,10-tetraoxaspiro[5.5]undecane-3 ,9-Diylbis(2-methyl-2-propyl-2,1-diethyl)benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5- ( 1-methylethyl)-, 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methyl-2-propyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3-(1,1-Dimethylethyl)-5-ethyl-4-hydroxy-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis (2,2-Diethyl-2,1-diethyl)Benzenepropanoic acid, 3-(1,1-dimethylethyl)-5-ethyl-4-hydroxy-, 2,4,8, 10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2-diethyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3-(1,1-Dimethylethyl)-4-hydroxy-5-methyl-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis (2-Butyl-2-ethyl-2,1-diethyl)Benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-, 2,4, 8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-butyl-2-ethyl-2,1-ethanediyl) ester), its chemical formula is as follows.

4-hydroxy-3,5-bis(1-methylcyclohexyl)-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2,2- Benzenepropanoic acid,4-hydroxy-3,5-bis(1-methylcyclohexyl)-,2,4,8,10-tetraoxaspiro [5.5]undecane- 3,9-diylbis(2,2-dimethyl-2,1-ethanediyl) ester), its chemical formula is as follows.

3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-,[1-[9-[1-[[3-[3-(1,1-dimethylethyl) )-4-hydroxy-5-methylphenyl]-1-oxopropoxy]methyl]cyclohexyl]-2,4,8,10-tetraoxaspiro[5.5]undec-3-yl ]Cyclohexyl]Benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5-methyl-, [1-[9-[1-[[3-[3-(1 ,1-dimethylethyl)-4-hydroxy-5-methylphenyl]-1- oxopropoxy]methyl]cyclohexyl]-2,4,8,10-tetraoxaspiro[5.5]undec-3-yl]cyclohexyl]methyl ester), its chemical formula as follows.

3-(1,1-Dimethylethyl)-4-hydroxy-5-methyl-,2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis [2,2-Bis(1,1-Dimethylethyl)-2,1-diethyl]Benzenepropanoic acid, 3-(1,1-dimethylethyl)-4-hydroxy-5- methyl-, 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis[2,2-bis(1,1-dimethylethyl)-2,1-ethanediyl] ester), its chemical formula is as follows.

3,9-bis(2-(3-(3-tertiary-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2, 4,8,10-Tetraoxaspiro(5,5)undecane, (3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy-1, 1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane), its chemical formula is as follows.

The content of phenolic compounds with 2,4,8,10-tetraoxaspiro (5,5) undecyl groups in the polymethacrylate composition ranges from 200 ppm to 2000 ppm, for example, from 300 ppm to 1500 ppm or It is 550ppm to 1300ppm. In one embodiment, the polymethacrylate composition can adjust the compatibility of the methacrylate polymer and the styrene-maleic anhydride copolymer in the polymethacrylate composition, for example, The methacrylate-based polymer contains 94 wt% (wt%) to 98wt% of methacrylate-based monomer units and 2wt% to 6wt% of acrylate-based monomer units, and the methacrylate-based polymer The weight average molecular weight (Mw) is 70,000 to 95,000. At the same time, phenolic compounds with 2,4,8,10-tetraoxaspiro (5,5) undecyl groups are added. In addition to making polymethyl Acrylate composition has good heat resistance (high Tg), good thermal stability (high Td) and low yellowness performance, but also has low haze optical performance.

Phosphorus resistance Oxidant

Specific examples of phosphorus antioxidants include, but are not limited to: tris(2,4-di-tert-butylphenyl) phosphite, bis[2,4-bis(1,1-dimethylethyl)- 6-Methylphenyl] ethyl ester, tetrakis(2,4-di-tert-butylphenol)-4,4'-biphenyl diphosphite, bis(2,4-di-tert-butylbenzene) Yl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite Ester, di-tert-butyl m-tolyl phosphite, etc., and the above-mentioned compounds can be used alone or in combination.

The addition amount of the phosphorus antioxidant in the polymethacrylate composition ranges from 0 ppm to 2000 ppm.

Heat stabilizer

式(2)In one embodiment, general heat stabilizers can be used in the present invention. In another embodiment, the present invention can use the heat stabilizer represented by the following formula (2).

Formula (2)

In the above formula, R ₃ and R ₆ each independently represent hydrogen or a methyl group, and R ₄ and R ₅ each independently represent a C1-C9 linear, branched or cyclic alkyl group. R _{4 is,} for example, selected from tertiary butyl or tertiary pentyl; R _{5 is,} for example, selected from tertiary butyl, tertiary pentyl, or tertiary octyl.

The addition amount of the heat stabilizer in the polymethacrylate composition ranges from 0 ppm to 2000 ppm.

UV absorber

The ultraviolet absorber can be selected to have a flash point higher than the processing temperature, such as an ultraviolet absorber with a flash point greater than or equal to 240°C, to avoid the precipitation of the ultraviolet absorber during the high-temperature molding process of processing the optical element, which may cause serious problems. The problem of mold fouling.

Specific examples of ultraviolet absorbers include but are not limited to: 2-(4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-octyloxy Phenol (2-(4,6-Bis-(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-(octyloxy)-phenol), 2,2'-methylene Bis[6-(benzotriazol-2-yl)-4-tert-octylphenol] (2,2'-Methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol]), 2- (4,6-Diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (2-(4,6-diphenyl-1,3,5- triazin-2-yl)-5-[(hexyl)oxy]-phenol), 2,2',4,4'-Tetrahydroxybenzophenone (2,2',4,4'-Tetrahydroxybenzophenone), 3 -[(2-cyano-3,3-diphenylpropenyl)oxy]-2,2-bis{[(2-cyano-3,3-diphenylpropenyl)oxy]methyl}propane 2-cyano-3,3-diphenylacryloyl (3-[(2-Cyano-3,3-diphenylacryloyl)oxy]-2,2-bis{[(2- cyano-3,3-diphenylacryloyl) oxy]methyl}propyl 2-cyano-3,3- diphenylacrylate, uvinul 3030), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (2-( 2H-Benzotriazol-2-yl)-6-dodecyl-4- methylphenol), 2-(2'-hydroxy-3',5'-dipentylphenyl)benzotriazole (2-(2'-Hydroxy -3',5'-dipentylphenyl)benzotriazole), etc., and the above-mentioned ultraviolet absorbers can be used alone or in combination.

The content of the ultraviolet absorber in the polymethacrylate composition ranges from 10000 ppm to 50000 ppm, for example, 15000 ppm to 40000 ppm or 20000 ppm to 35000 ppm. Within this range, the ultraviolet absorber can be mixed with the composition uniformly, and it will not be affected by subsequent The thermal processing process causes the ultraviolet absorber to separate out to produce mold fouling, and can make the composition have good ultraviolet light stability. In one embodiment, when the polymethacrylate composition contains both ultraviolet absorbers and phenolic compounds with 2,4,8,10-tetraoxaspiro(5,5) undecyl groups, and ultraviolet rays The content ratio of absorbent to phenolic compound with 2,4,8,10-tetraoxaspiro(5,5) undecyl group ranges from 5 to 250, such as 10 to 200 or 15 to 150 , Can make the polymethacrylate composition not only have good heat resistance (high Tg) and good thermal stability (high Td), but also can make it have low yellowness and low haze optical performance. In one embodiment, the polymethacrylate composition contains 10,000 ppm to 50,000 ppm of ultraviolet absorber and 200 ppm to 2000 ppm of 2,4,8,10-tetraoxaspiro(5,5) undecyl group Phenolic compounds.

Slip agent

Specific examples of slip agents include, but are not limited to: calcium stearate, magnesium stearate, lithium stearate and other metal soaps, ethylene distearyl amide, methylene distearyl amide, palmitate amide, Butyl stearate, palmityl stearate, polypropionol tristearate, n-behenic acid, stearic acid, stearyl alcohol and other compounds, polyethylene wax, octadecanoic acid wax, Carnuba wax, petroleum wax, etc., and the above-mentioned slip agents can be used alone or in combination.

In the polymethacrylate composition, the additive amount of the slip agent is, for example, 300 ppm to 50,000 ppm.

Processing aids

Specific examples of processing aids include, but are not limited to: core-shell acrylate processing aids with a weight average molecular weight (Mw) of more than 500,000 to improve extrusion moldability, thermoformability, and the like.

Anti-charge agent

Specific examples of anti-charge agents include, but are not limited to, low-molecular-weight compounds such as tertiary amine compounds and quaternary ammonium salt compounds; or polyamide polyethers such as 3-chloro-1,2-propylene oxide polymerization It is a high-molecular-weight substance that prevents permanent charging of the body. The aforementioned antistatic agents can be used alone or in combination.

Filler

Specific examples of fillers include, but are not limited to: calcium carbonate, silica, mica, etc. The aforementioned fillers can be used alone or in combination.

Enhancer

Specific examples of the strengthening agent include, but are not limited to: glass fiber, carbon fiber, various whiskers, etc. The aforementioned strengthening agent can be used alone or in combination.

Colorant

Specific examples of colorants include, but are not limited to: titanium oxide, iron oxide, graphite, phthalocyanine dyes, etc., and the foregoing colorants can be used alone or in combination.

The use of the polymethacrylate composition of the present invention is not particularly limited, and it can be applied to injection molding, compression molding, extrusion molding, blow molding, thermoforming, vacuum molding, and hollow molding. Method, it can be made into, for example: pressed board, film molded products, etc., can be formulated according to the formula to achieve high fluidity, high thermal stability and other requirements.

The polymethacrylate composition can be obtained by general mixing and kneading mechanisms such as Brabender plastometer, Banbury mixer, kneader-mixer, rolling machine, single-shaft or double-shaft extruder. Usually, after mixing and kneading with an extruder, the extruded material is cooled and granulated. The polymethacrylate composition is generally kneaded at 160°C~280°C, preferably at a temperature of 180°C~250°C. In addition, there is no particular restriction on the order of mixing and kneading of the ingredients.

The optical element of another embodiment of the present invention is formed of the polymethacrylate composition as described above, and has excellent optical properties of low haze and low yellowness. In an embodiment, the optical element may be an optical material with a planar structure such as an optical plate, an optical sheet, or an optical film. In one embodiment, the method for preparing the optical material of the planar structure is not particularly limited. The polymethacrylate composition can be melted through an extruder, and then extruded into a plate, sheet or film. Shaped unstretched optical plate, optical sheet or optical film. In another embodiment, a tenter can also be used to stretch the aforementioned unstretched optical plate, optical sheet, or optical film at a temperature above the glass transition temperature or the like for lateral stretching or biaxial stretching.

In one embodiment, the optical element is, for example, an optical plate with a planar structure, which includes a flake-shaped body, and the body includes a flat surface. Wherein, the main body has a rectangular shape and is composed of the aforementioned polymethacrylate composition.

In another embodiment, the optical element is, for example, an optical plate with microstructures. Please refer to FIG. 1A, which is an optical plate 10 with microstructures. The optical plate has a main body 12. The main body includes a surface 122. A plurality of first microstructures 132 are disposed on the surface 122. As shown in FIG. 1A, each first microstructure 132 of this embodiment is a concave point structure, but the present invention is not limited to this. In other embodiments, each first microstructure 132 may be a bump structure or a structure with other shapes.

Please refer to FIG. 1B, which shows another embodiment of the optical element, except for the first microstructure 132 in FIG. 1A, on the other surface of the microstructure optical plate 10', such as the surface 124 or the surface 122 opposite to the surface 122 The side surface 126 of the vertical surface 122 can also be provided with a second microstructure 134, for example, a lens structure is provided on the surface 124. Each second microstructure 134 of this embodiment is semi-protruding round, but the invention is not limited to this. In other embodiments, each second microstructure 134 may be a protruding structure with a suitable shape such as a prism or a corner post. In addition, the optical element may also be an optical plate having the second microstructure 134 alone.

In some embodiments, the optical element may be applied to various display devices. As a display device, a television (also known as a TV or a television receiver) (such as Figure 2A), a digital camera (such as Figure 2B), a digital camera (such as Figure 2C), a digital photo frame (such as the 2D Figure), mobile phones (such as Figure 2E), notebook personal computers, mobile computers, screens for computers, etc., portable game consoles, portable information terminals, audio reproduction devices, game consoles, and car monitors .

Hereinafter, referring to several experiments, the polymethacrylate composition of the present invention will be described in more detail. Although the following experiments are described, without going beyond the scope of the present invention, the materials used, their amounts and ratios, processing details, processing procedures, etc. can be appropriately changed. Therefore, the present invention should not be interpreted restrictively based on the experiments described below.

>Raw materials used in Examples and Comparative Examples>

Preparation of methacrylate-based polymer 1: First, 95 parts by weight of methyl methacrylate, 5 parts by weight of methyl acrylate, 0.4 parts by weight of n-dodecyl mercaptan, and 2,2'-azobisiso After 0.08 parts by weight of butyronitrile and 66 parts by weight of toluene are mixed, they are continuously fed into a reaction tank for continuous solution polymerization. The above-mentioned reaction tank has a sandwich structure with heat medium oil circulation, and the reaction temperature is maintained at 100°C and the pressure is 600 torr. Fully stir the components in the reaction tank to make them uniformly mixed, and heat the resulting polymer solution to 265°C, then use a continuous devolatilizer to devolatilize the polymer solution under reduced pressure, and then make it by extrusion equipment. Into strips. After cooling and pelletizing treatment, polymethyl methacrylate plastic particles are prepared. The polymethyl methacrylate plastic particles contain 97 wt% of methyl methacrylate monomer units and 3 wt% of methyl acrylate monomer units. The weight average molecular weight (Mw) of the polymethyl methacrylate plastic particles measured by GPC and polystyrene as the standard is 100,000, and the melt flow rate (MVR) (230°C×3.8kg)=1.9.

Preparation of methacrylate-based polymer 2: First, 94 parts by weight of methyl methacrylate, 6 parts by weight of methyl acrylate, 0.5 parts by weight of n-dodecyl mercaptan, 0.1 parts by weight of 2,2'-azobisisobutyronitrile, and 66 parts by weight of toluene are mixed. After that, it is continuously fed into a reaction tank for continuous solution polymerization. The above-mentioned reaction tank has a sandwich structure with heat medium oil circulation, and the reaction temperature is maintained at 100°C and the pressure is 600 torr. Fully stir the components in the reaction tank to make them uniformly mixed, and heat the resulting polymer solution to 265°C, then use a continuous devolatilizer to devolatilize the polymer solution under reduced pressure, and then make it by extrusion equipment. Into strips. After cooling and pelletizing treatment, polymethyl methacrylate plastic particles are prepared. The polymethyl methacrylate plastic particles contain 95.5 wt% of methyl methacrylate monomer units and 4.5 wt% of methyl acrylate monomer units. The weight average molecular weight (Mw) of the polymethyl methacrylate plastic particles measured using GPC and polystyrene as the standard is 90,000, and the melt flow rate (MVR) (230°C×3.8kg)=3.0.

Preparation of styrene-maleic anhydride copolymer 1:

In a 40L stirred reactor, purge with nitrogen for 10 minutes, add 9570 g of maleic anhydride, raise the temperature to 130° C., and then keep the temperature constant for 30 minutes. Then the temperature is still maintained at 130°C, and a mixed solution containing 20430g styrene and 12g 2,2'-azobisisobutyronitrile is continuously added within 1 hour, and then the temperature is reduced to 110°C after the feeding is completed, and the reaction is performed at a constant temperature After 4 hours, the unreacted maleic anhydride is washed away with acetone, and the unreacted styrene is removed in a vacuum oven at 80° C. to obtain a block styrene-maleic anhydride copolymer. The styrene-maleic anhydride copolymer contains 67.9% by weight of styrene-based monomer units and 32.1% by weight of maleic anhydride-based monomer units. The number average molecular weight (Mn) measured using GPC and polystyrene as the standard product is 36560, the weight average molecular weight (Mw) is 65810, and PDI=1.80.

Preparation of styrene-maleic anhydride copolymer 2:

In a 40L stirred reactor, purge with nitrogen for 10 minutes, add 8190 g of maleic anhydride, increase the temperature to 130° C., and then keep the temperature constant for 30 minutes. Then the temperature is still maintained at 130°C, and a mixed solution containing 21810 styrene and 14g 2,2'-azobisisobutyronitrile is continuously added within 1 hour, and then the temperature is reduced to 110°C after the feeding is completed, and the reaction is performed at a constant temperature After 4 hours, the unreacted maleic anhydride is washed away with acetone, and the unreacted styrene is removed in a vacuum oven at 80° C. to obtain a block styrene-maleic anhydride copolymer. The styrene-maleic anhydride copolymer contains 73.2% by weight of styrene-based monomer units and 26.8% by weight of maleic anhydride-based monomer units. The number average molecular weight (Mn) measured using GPC and polystyrene as the standard is 37260, the weight average molecular weight (Mw) is 65228, and PDI=1.75.

Phenolic compounds with 2,4,8,10-tetraoxaspiro(5,5)undecyl group: 3,9-bis(2-(3-(3-tertiary-butyl-4- Hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane.

Ultraviolet absorber: 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol], with a flash point of 420.5±35.7°C.

Phosphorus antioxidant: bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

Heat stabilizer: In formula (2), R ₃ is a methyl group, R ₄ and R ₅ are both tertiary amyl groups, and R ₆ is hydrogen.

[Evaluation item]

The proportions of methyl methacrylate monomer units, methyl acrylate monomer units, styrene-based monomer units, and maleic anhydride-based monomer units in the composition: the polymethyl methacrylate monomer units of Examples 1 to 3 and Comparative Example 1 The base acrylate composition was analyzed by nuclear magnetic resonance spectroscopy (NMR) and the total amount of methyl methacrylate monomer units, methyl acrylate monomer units, styrene monomer units, and maleic anhydride monomer units was used as 100wt% calculation.

Transmittance (T%): After the polymethacrylate compositions of Examples 1 to 3 and Comparative Example 1 were made into disc test pieces with a diameter of 5.5 cm and a thickness of 3 mm, they were measured with a haze meter (Haze Meter NDH 2000N) It is measured, unit: %. According to the requirements of commercially available optical components, it is generally expected to have a transmittance greater than 90%.

Haze: After making the polymethacrylate compositions of Examples 1 to 3 and Comparative Example 1 into disc test pieces with a diameter of 5.5 cm and a thickness of 3 mm, use a haze meter (Haze Meter NDH 2000N) Measure it, unit: %. According to the requirements of commercially available optical components, it is generally desirable to have a haze of less than 1.5.

Yellow index (YI value): After the polymethacrylate compositions of Examples 1 to 3 and Comparative Example 1 were made into disc test pieces with a diameter of 5.5 cm and a thickness of 3 mm, the computer spectroscopy method of Nippon Denshoku Color difference meter SA-2000 measurement.

Glass transition temperature (Tg): The polymethacrylate compositions of Examples 1 to 3 and Comparative Example 1 were measured with a differential scanning calorimeter (DSC). Unit: °C.

Thermal cracking temperature (5% thermogravimetric loss temperature, Td): Take 5 mg of the polymethyl methacrylate resin composition of Examples 1 to 3 and Comparative Example 1 as samples, and place them in a thermal gravimetric analyzer (Thermal Gravimetric Analysis, TGA for short), the analysis conditions are as follows: in a nitrogen environment, the temperature is increased from 100°C to 600°C at a heating rate of 20°C/min, and the temperature at 5% weight loss is measured.

Temperature-holding bubble performance: Take 20 grams of the polymethyl methacrylate resin composition of Examples 1 to 3 and Comparative Example 1 as samples, place them in an aluminum pan and cover the glass sheet on it, and hold it at 240°C. When the temperature was 4 hours, the bubble behavior was observed with an optical microscope (Optical Microscope).

Example 1 to 3

In Examples 1 to 3, the methacrylate-based polymer 2 and the styrene-maleic anhydride-based copolymer 2 were mixed according to the ratio listed in Table 1. Among them, the methacrylate-based polymer 2 and the styrene-based copolymer were mixed. The total of the maleic anhydride-based copolymer 2 is 100 parts by weight. After that, phenolic compounds with 2,4,8,10-tetraoxaspiro(5,5) undecyl groups, ultraviolet absorbers, phosphorus antioxidants (only in Example 1) and thermal After the stabilizer (only in Example 1 was added), the polymethacrylate composition was prepared separately after mixing and extruding granulation with an extruder at 240°C. The content values of phenolic compounds, ultraviolet absorbers, phosphorus antioxidants and heat stabilizers with 2,4,8,10-tetraoxaspiro(5,5) undecyl groups listed in Table 2 are respectively The polymethacrylate compositions of Examples 1 to 3 are respectively analyzed by high performance liquid chromatography (HPLC) and the actual content values of the components in the polymethacrylate composition are measured. The detection results of the haze (HAZE), yellowness (YI), light transmittance (T%), glass transition temperature (Tg), and thermal cracking temperature (Td) of the polymethacrylate compositions of Examples 1 to 3 Also recorded in Table 2.

Comparative example 1

In Comparative Example 1, the methacrylate-based polymer 1 and the styrene-maleic anhydride copolymer 1 were mixed according to the ratio listed in Table 1. Among them, the methacrylate-based polymer 1 and the styrene-maleic anhydride copolymer were mixed. The acid anhydride-based copolymer 1 is 100 parts by weight in total, and the polymethacrylate composition is prepared in the same manner as in Examples 1 to 3. The content of phenolic compounds, ultraviolet absorbers, phosphorus antioxidants and heat stabilizers with 2,4,8,10-tetraoxaspiro(5,5) undecyl groups listed in Table 1 is The actual content value of the polymethacrylate composition of Comparative Example 1 was analyzed by high performance liquid chromatography (HPLC). The test results of the haze (HAZE), yellowness (YI), transmittance (T%), glass transition temperature (Tg), and thermal cracking temperature (Td) of the polymethacrylate composition are also recorded in Table 2. . Table 1 Comparative example 1 Example 1 Example 2 Example 3 Methacrylate-based polymer 1 (parts by weight) 71 - - - Methacrylate-based polymer 2 (parts by weight) - 72.8 72.8 72.8 Styrene-maleic anhydride copolymer 1 (parts by weight) 29 - - - Styrene-maleic anhydride copolymer 2 (parts by weight) 27.2 27.2 27.2 Table 2 Comparative example 1 Example 1 Example 2 Example 3 Methyl methacrylate monomer unit (wt%) 70 70.9 70.9 70.9 Methyl acrylate monomer unit (wt%) 1.3 1.9 1.9 1.9 Styrene monomer unit (wt%) 19.5 19.9 19.9 19.9 Maleic anhydride monomer unit (wt%) 9.2 7.3 7.3 7.3 Phenolic compounds with 2,4,8,10-tetraoxaspiro(5,5) undecyl group (ppm) 1191 586 550 1050 UV absorber (ppm) 22031 21969 22467 22450 UV absorber/phenolic compound with 2,4,8,10-tetraoxaspiro(5,5) undecyl group (ratio) 18.50 37.49 40.85 21.38 Phosphorus antioxidant (ppm) 410 231 - - Heat stabilizer (ppm) 1183 858 - - Tg (℃) 127.3 125.3 125 125 Td(℃) 325 330 328 328 YI 9.0 6.43 5.74 5.88 HAZE(%) 0.6 0.54 0.48 0.48 T% 91.9 92.1 92.2 92.2

As can be obtained from Table 2, compared with Comparative Example 1, the polymethacrylate composition used includes 94wt%~98wt% methacrylate monomer units, 2wt%~6wt% acrylate monomer units and 0wt%~4wt% of the first copolymerizable monomer unit with a weight average molecular weight (Mw) of 70,000 to 95,000 methacrylate-based polymers including 65wt%~76wt% of styrene monomer units , 24wt%~35wt% of maleic anhydride-based monomer units and 0wt%~11wt% of the second copolymerizable monomer unit of styrene-maleic anhydride-based copolymers in Examples 1~3 in addition to maintaining relatively Excellent heat resistance (higher Tg), better thermal stability (higher Td), and both lower yellowness and higher transmittance, which means that the composition can be heat-resistant Sexual and optical properties. In addition, in the composition, only the phenolic compound with 2,4,8,10-tetraoxaspiro(5,5) undecyl group and the ultraviolet absorber were used in Examples 2~3, which also used phosphorus-based compounds in combination. Comparative Example 1 and Example 1 of antioxidant and heat stabilizer have better haze performance.

In addition, the polymethacrylate composition with styrene-maleic anhydride copolymer has high heat resistance (glass transition temperature, Tg), but it is easy to generate bubbles during the subsequent molding process, which may lead to molding. The problem of product defects. Therefore, it is necessary to reduce the occurrence of bubbles by controlling the addition ratio of each component in the polymethacrylate composition of the styrene-maleic anhydride copolymer without sacrificing processability.

In order to simulate the severe processing conditions, the particles of Examples 1 to 3 and Comparative Example 1 were placed in aluminum pans and covered with glass sheets. The temperature was maintained at 240°C for 4 hours. Table 3 summarizes Examples 1 to 3 and The results of measurement under an optical microscope of the bubbles generated in Comparative Example 1 under the aforementioned experimental conditions. The outer diameters of the largest bubbles in Examples 1 to 3 and Comparative Example 1 were measured, and the bubble area was converted to the aforementioned outer diameter. Measure the area occupied by bubbles per unit area (13.8um⨯10.4um) in the central area. In addition, after baking the particles at 240°C for 15 minutes, the organic components that escaped from the particles due to baking were collected by a Thermal Desorption Unit (TDU), and the collected organic components were analyzed by gas chromatograph. The total amount of organic ingredients is also recorded in Table 3. table 3 Comparative example 1 Example 1 Example 2 Example 3 TDU(ppm) 7520 3570 2004 1718 The longest outer diameter of the bubble (um) 2082 1419 1300 1088 Maximum bubble area (um ² ) 3404484 1581447 1327323 929710 Proportion of bubbles per unit area (%) 100 98.8 90.05 66.24

It can be obtained from Table 3 that compared with Comparative Example 1, the particles of Examples 1 to 3 emit less organic volatile components under high-temperature baking, which means that the particles may contain less volatile components during the subsequent molding process. Organic volatile components, so it is less likely to produce air bubbles in the process of processing and molding. That is, by controlling the composition of the methacrylate-based polymer and the styrene-maleic anhydride-based copolymer in the polymethacrylate composition, the polymethacrylate composition includes 94wt% ~98wt% methacrylate-based monomer units, 2wt%~6wt% acrylate-based monomer units and 0wt%~4wt% of the first copolymerizable monomer unit and its weight average molecular weight (Mw) is 70,000 to 95,000 methacrylate-based polymers include 65wt%~76wt% styrene monomer units, 24wt%~35wt% maleic anhydride monomer units and 0wt%~11wt% of the second copolymerizable The styrene-maleic anhydride copolymer of the monomer unit can improve the compatibility of the methacrylate-based polymer and the styrene-maleic anhydride copolymer. Therefore, it can be reduced during extrusion and granulation. The residence time of the composition in the extruder reduces the degree of ring-opening deterioration of the styrene-maleic anhydride copolymer, so it can reduce the low-molecular organic volatile components (such as oligomers) that are generated due to deterioration in the composition. , To reduce the risk of bubbles in the subsequent processing and molding process, and to maintain the heat resistance, thermal stability and yellowness of the composition. In addition, from the test results of the particles holding the temperature at 240°C for 4 hours, it can be seen that even if the temperature is held for a long time at a severe high temperature, both Examples 1 to 3 and Comparative Example 1 have a large number of bubbles. However, the examples The size of bubbles generated by particles 1 to 3 is significantly smaller than that of Comparative Example 1. In addition, in the unit area, Comparative Example 1 is completely filled with bubbles, so the proportion of bubbles (%) is as high as 100%. The proportion of bubbles in Examples 1 to 3 is smaller than that of Comparative Example 1, that is, by adjusting the methyl group The molecular weight of acrylate polymer and the ratio of methacrylate monomer unit and acrylate monomer unit to the styrene monomer unit and maleic anhydride monomer in the styrene-maleic anhydride copolymer The ratio of the units can improve the compatibility of the methacrylate-based polymer and the styrene-maleic anhydride copolymer, and reduce the probability of bubble generation during subsequent processing and molding.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the relevant technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The protection scope of the present invention shall be subject to those defined by the attached patent application scope.

10, 10’: Optical plate 12: body 122, 124: Surface 126: side surface 132: The first microstructure 134: The second microstructure

FIG. 1A is a schematic cross-sectional view of an optical element according to an embodiment of the invention. FIG. 1B is a schematic cross-sectional view of an optical element according to another embodiment of the present invention. 2A to 2E are schematic diagrams of display devices according to various embodiments of the present invention.

10: Optical plate

12: body

122: Surface

132: The first microstructure

Claims (12)

A polymethacrylate composition comprising: 50 to 85 parts by weight of methacrylate-based polymer, wherein the methacrylate-based polymer includes 94wt%~98wt% of methacrylate-based monomer units, 2wt%~6wt% of acrylate-based monomers Unit and 0~4wt% of the first copolymerizable monomer unit, the weight average molecular weight (Mw) of the methacrylate-based polymer is 70,000-95,000; and 15 to 50 parts by weight of a styrene-maleic anhydride copolymer, the styrene-maleic anhydride copolymer comprising 65wt%~76wt% of styrene monomer units, 24wt%~35wt% of horse Acid anhydride monomer unit and 0~11wt% of the second copolymerizable monomer unit, Wherein, the total amount of the methacrylate-based polymer and the styrene-maleic anhydride copolymer is 100 parts by weight. The polymethacrylate composition described in item 1 of the scope of the patent application further includes 200 ppm to 2000 ppm of phenolic compounds with 2,4,8,10-tetraoxaspiro(5,5)undecyl groups . The polymethacrylate composition according to item 1 of the scope of patent application, wherein the weight percentage of the styrene-based monomer unit of the styrene-maleic anhydride copolymer and the maleic anhydride-based monomer are The ratio of the weight percentage of the body unit is 1 to 8.5. The polymethacrylate composition according to the first item of the patent application, wherein the weight average molecular weight (Mw) of the styrene-maleic anhydride copolymer is 60,000 to 100,000. The polymethacrylate composition according to the first item of the scope of patent application, wherein the molecular weight distribution index (PDI) of the styrene-maleic anhydride copolymer is in the range of 1.5 to 2.05. The polymethacrylate composition described in item 1 of the scope of patent application further includes 10,000 ppm to 50,000 ppm of ultraviolet absorber. The polymethacrylate composition described in item 6 of the scope of patent application, wherein the flash point of the ultraviolet absorber is ≧240°C. The polymethacrylate composition described in item 6 of the scope of patent application, wherein the ultraviolet absorber is selected from 2-(4,6-bis-(2,4-dimethylphenyl)-1,3 ,5-Triazine-2-yl)-5-octyloxyphenol, 2,2'-methylenebis[6-(benzotriazol-2-yl)-4-tert-octylphenol], 2 -(4,6-Diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2,2',4,4'-tetrahydroxydiphenyl Ketone, 3-[(2-cyano-3,3-diphenylpropenyl)oxy]-2,2-bis{[(2-cyano-3,3-diphenylpropenyl)oxy] Methyl) propyl 2-cyano-3,3-diphenyl acrylate, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, and 2- At least one of the group consisting of (2'-hydroxy-3',5'-dipentylphenyl)benzotriazole. A polymethacrylate composition consisting essentially of: 50 to 85 parts by weight of methacrylate-based polymer, wherein the methacrylate-based polymer includes 94wt%~98wt% of methacrylate-based monomer units and 2wt%~6wt% of acrylate-based monomers Body unit, the weight average molecular weight (Mw) of the methacrylate-based polymer is 70,000 to 95,000; 15 to 50 parts by weight of a styrene-maleic anhydride copolymer, the styrene-maleic anhydride copolymer comprising 65wt%~76wt% of styrene monomer units and 24wt%~35wt% of horse Acetic anhydride-based monomer unit, wherein the total amount of the methacrylate-based polymer and the styrene-maleic anhydride-based copolymer is 100 parts by weight; 200 ppm to 2000 ppm of phenolic compounds with 2,4,8,10-tetraoxaspiro(5,5) undecyl groups; and 10,000ppm to 50,000ppm UV absorber composition. An optical element is formed of the polymethacrylate composition as described in any one of items 1 to 9 in the scope of the patent application. The optical element according to claim 10, wherein the optical element is at least one selected from the group consisting of an optical plate, an optical sheet, and an optical film. A display device includes: As the optical element described in item 10 of the scope of patent application, The display device is selected from the group consisting of televisions, digital cameras, digital cameras, digital photo frames, mobile phones, notebook personal computers, mobile computers, screens for computers, etc., portable game consoles, portable information terminals , At least one of the group consisting of audio reproduction devices, game consoles, and car displays.

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