KR101740461B1 - Transparent high anti-scratch extrusion plate having excellent falling ball impact - Google Patents
Transparent high anti-scratch extrusion plate having excellent falling ball impact Download PDFInfo
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- KR101740461B1 KR101740461B1 KR1020150190657A KR20150190657A KR101740461B1 KR 101740461 B1 KR101740461 B1 KR 101740461B1 KR 1020150190657 A KR1020150190657 A KR 1020150190657A KR 20150190657 A KR20150190657 A KR 20150190657A KR 101740461 B1 KR101740461 B1 KR 101740461B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
Description
The present invention relates to a transparent high-hardness pressure-press machine excellent in the strength of the drop impact. In particular, the present invention relates to a pressure-sensitive printing plate comprising a polycarbonate and a hardness improver prepared from an aromatic (meth) acrylate monomer, a methyl methacrylate monomer, an acrylate monomer and a crosslinking agent, and having improved impact strength, transparency and hardness.
Transparent pressure printing has a lower specific gravity than glass and has excellent moldability and is used in various fields. In recent years, demands for lightening and thinning of electronic devices have increased, and it is necessary to be able to withstand impacts and loads in a bag or the like. In order to satisfy such a demand, resins used in housings are required not only to have high rigidity and impact resistance, but also to have high appearance and surface hardness and high impact resistance upon dropping.
Particularly, polycarbonate resin is excellent in mechanical strength, transparency and weather resistance, and is excellent in impact resistance, thermal stability, self-extinguishing property and dimensional stability, and is widely used in electrical and electronic products and automobile parts. In addition, glass can be substituted for parts where transparency and impact resistance, such as lenses, are required at the same time. However, despite its excellent physical properties, there is a limitation in its use as an exterior material due to the low surface hardness of the polycarbonate resin.
On the other hand, the acrylic resin has excellent transparency and weatherability, but has a disadvantage in that the impact resistance is poor.
In order to solve the above problem, Japanese Laid-Open Patent Application No. 2010-116501 has devised compounding with a polycarbonate by using a low molecular weight acrylic copolymer as a hardness improver. However, due to a decrease in impact strength of a molded article, There is a problem that the impact resistance can not be secured. It is known that the impact resistance to be applied to a product requiring impact resistance at the time of dropping has a high correlation with the surface impact strength measured by an impact test, and the correlation with the Izod or Charpy impact strength is low. Thus, the above-mentioned patent, which measures the Izod impact strength, is difficult to apply to press-stamping having excellent impact strength.
Korean Patent No. 10-1188349 also contemplates compounding with polycarbonate using the same ultra low molecular weight high refractive index acrylic copolymer, but there is a difference in the range of application for application to impact pressure printing having excellent impact strength , There is a problem that sufficient impact resistance as mechanical properties can not be secured by applying a low molecular weight.
In order to solve the above-mentioned problems, the present invention is to extrude a hardness improver comprising an aromatic (meth) acrylate monomer, a methyl methacrylate monomer, an acrylate monomer and a crosslinking agent with a polycarbonate, It is aimed to produce press publishing.
In order to accomplish the above object, the present invention aims to provide a hardness-improving agent having an optimum composition and a polycarbonate copolymer and a transparent hardness pressure-pressing machine excellent in the drop impact strength.
Specifically, the present invention relates to a method for producing a thermoplastic resin composition comprising 15 to 30% by weight of an aromatic (meth) acrylate monomer, 68 to 80% by weight of a methyl methacrylate monomer, 0.5 to 2% by weight of an acrylate monomer and 0.1 to 5% 20 to 45 wt% of a hardness improver, and 55 to 85 wt% of a polycarbonate.
The weight average molecular weight of the hardness improver is not limited as long as the object of the present invention can be achieved, but may include, for example, an acrylic polymer having a weight average molecular weight of 25,000 to 60,000 g / mol.
The aromatic (meth) acrylate monomers include phenyl methacrylate, phenyl acrylate, benzyl methacrylate, benzyl acrylate. Phenoxy methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthio phenyl methacrylate, 2-hydroxy-3-phenoxy propyl acrylate, 2-hydroxy- , Phenoxyethyl acrylate, phenoxyethyl methacrylate, and the like.
The acrylate monomer may be at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, octyl acrylate, , 2-methylhexyl acrylate, 2-methyl octyl acrylate, 2-tert-butyl heptyl acrylate, 3-isopropyl heptyl acrylate, decyl acrylate, undecyl acrylate, 5-methylundecyl acrylate, dodecyl acrylate , Methyldodecyl acrylate, tridecyl acrylate, 5-methyltridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, 2-methylhexadecyl acrylate, heptadecyl acrylate, 5-ethylheptadecyl acrylate, 5-ethyl octadecyl acrylate, octadecyl acrylate, nonadecyl acrylate And eicosyl acrylate. The term " anionic surfactant "
The polycarbonate has a melt viscosity (MI) of 3 to 5 g / 10 min measured at a temperature of 300 캜 under a load of 1.2 kg to achieve the object of the present invention.
The polycarbonate may include any one or two or more selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin, and a polyester carbonate copolymer resin.
The hardness improver may be one prepared by suspending an aromatic (meth) acrylate monomer, a methyl methacrylate monomer, an acrylate monomer, and a crosslinking agent.
The crosslinking agent may be at least one selected from the group consisting of ethylene glycol dimethacrylate, bis (4-methacryloxyethoxyphenyl) propane, urethane dimethyrate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, Butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethylol propane, triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate and divinylbenzene ≪ RTI ID = 0.0 > and / or < / RTI >
The pressure was more than pencil hardness F. The drop impact strength was such that when specimens of 2 mm thickness, 20 cm width and 20 cm length were dropped at a height of 500 g, the specimen was not broken and the light transmittance was 89% or more And may be a haze of 1.0 or less.
The transparent high hardness plated press according to the present invention can improve the surface hardness of the polycarbonate by producing the platen using the low flow polycarbonate resin and the hardness improver, There is an advantage that it can be.
Hereinafter, a transparent high hardness plated paper having excellent impact strength of an impact strength according to the present invention will be described in more detail with reference to the following Examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.
Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Hereinafter, the present invention will be described in detail.
The present invention relates to a hardness improver comprising 15 to 30% by weight of an aromatic (meth) acrylate monomer, 68 to 80% by weight of a methyl methacrylate monomer, 0.5 to 2% by weight of an acrylate monomer and 0.1 to 5% 20 to 45 wt% and 55 to 85 wt% of polycarbonate.
When the content of the aromatic (meth) acrylate of the present invention is less than 15% by weight, the compatibility with the polycarbonate is lowered to increase the haze. When the content exceeds 30% by weight, the effect of improving the hardness is deteriorated. Economic problems arise.
The aromatic (meth) acrylate is phenyl methacrylate, phenyl acrylate, benzyl methacrylate, benzyl acrylate. Phenoxy methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthio phenyl methacrylate, 2-hydroxy-3-phenoxy propyl acrylate, 2-hydroxy- , Phenoxyethyl acrylate, phenoxyethyl methacrylate, and the like. Preferably one selected from phenyl methacrylate, benzyl methacrylate, and mixtures thereof. Most preferably, it is not limited to phenyl methacrylate.
If the content of the methyl methacrylate of the present invention is less than 68% by weight, the fluidity is low and the processability is deteriorated and the hardness improving effect is inferior. If it is more than 80% by weight, the impact and mechanical properties deteriorate severely, which is not preferable.
If the content of the acrylate monomer of the present invention is less than 0.5% by weight, the effect of preventing thermal decomposition is small, and if it exceeds 2% by weight, compatibility with polycarbonate is poor.
The acrylate monomer is an acrylate monomer other than methyl methacrylate. Specific examples of the acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, propyl acrylate, Acrylate, 2-methylhexyl acrylate, 2-methylhexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl acrylate, Acrylate, 5-methylundecyl acrylate, dodecyl acrylate, 2-methyldodecyl acrylate, tridecyl acrylate, 5-methyltridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate 2-methylhexadecyl acrylate, heptadecyl acrylate, 5-isopropyl heptadecyl acrylate And may include any one or two or more that 5-ethyl octadecyl acrylate, octadecyl acrylate, nonadecyl selected from decyl acrylate, eicosyl acrylate. Preferably methyl acrylate and ethyl acrylate, but are not limited thereto.
The cross-linking agent of the present invention can obtain a proper weight average molecular weight by using a cross-linking agent within the range of 0.1 to 5 wt%. If the content of the cross-linking agent exceeds 5% by weight, the molecular weight rapidly increases and the workability decreases. When the content of the cross-linking agent is less than 0.1% by weight, the impact strength is poor.
The crosslinking agent may be at least one selected from the group consisting of ethylene glycol dimethacrylate, bis (4-methacryloxyethoxyphenyl) propane, urethane dimethyrate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, Butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethylol propane, triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate and divinylbenzene , But it is not limited thereto.
The present invention includes 20 to 45 wt% of the hardness improver and 55 to 85 wt% of polycarbonate. When the content of the hardness improver is less than 20% by weight, the effect of improving hardness is insignificant. When the content of the hardness improver is more than 45% by weight,
The weight average molecular weight of the hardness improver of the present invention is not limited as long as the object of the present invention can be achieved, but may include, for example, an acrylic polymer having a weight average molecular weight of 25,000 to 60,000 g / mol . Preferably 30,000 to 50,000 g / mol. When the weight average molecular weight is within the above range, the strength of the drop impact is improved, and phase separation with polycarbonate does not occur and high transparency is exhibited.
The polycarbonate of the present invention may include one or more selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin and a polyester carbonate copolymer resin, but is not limited thereto.
As the linear polycarbonate resin, a bisphenol A-based polycarbonate resin can be used. As the branched polycarbonate resin, those prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride or trimellitic acid with a dihydric phenol compound and a carbonate precursor may be used. As the polyester carbonate copolymer resin, those prepared by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor may be used. In addition, conventional linear polycarbonate resin, branched polycarbonate resin or polyester carbonate copolymer resin can be used without limitation.
The polycarbonate of the present invention preferably has a melt viscosity (MI) of 3 to 5 g / 10 min as measured at 300 캜 under a load of 1.2 kg. If the above-mentioned melt viscosity is obtained, the intended properties of the present invention can be exhibited. Examples of the polycarbonate within the above range include Lupoy 1300-03 and Lupoy 1302-05 of LG Chemie.
The hardness improver may be prepared by any one of the methods selected from suspension polymerization, solution polymerization and bulk polymerization. Preferably, the hardness improver may be prepared by suspending an aromatic (meth) acrylate monomer, a methyl methacrylate monomer, an acrylate monomer and a crosslinking agent Followed by polymerization. In addition, it may include an initiator, a chain transfer agent and a dispersant in the suspension polymerization.
The initiator of the present invention can be widely used as long as it is a conventional initiator that can be used in the (meth) acrylate-based suspension polymerization. The initiator may be selected from the group consisting of 2,2'-azobis 2,4-dimethyl-valeronitrile, azobisisobutyronitrile, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,2'-azobis (4-methoxy-2,4-dimethylpentanitril), dimethyl-2,2'-azodiisobutyric acid, tertiary-butylperoxy-3,5,5 -Trimethylhexanoate, 2,2'-azobis (2-amidinopropane) dihydrochloride, di-n-propylperoxydicarbobonite and the like can be used. The content of the initiator is most preferably 0.01 to 1 part by weight based on 100 parts by weight of one or more monomer mixture, but is not limited thereto.
The chain transfer agent of the present invention may be included to maintain the fluidity of the (meth) acrylate-based copolymer through controlling the molecular weight of the (meth) acrylate-based copolymer.
The chain transfer agent of the present invention is most preferably an alkyl mercaptan having 1 to 12 carbon atoms in the alkyl group and a thiol functional group or a polythiomercaptan having two or more thiol functional groups. The alkyl mercaptan may be isopropyl mercaptan, t-butyl mercaptan, n-butyl mercaptan, n-amyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and the like, but is not limited thereto. The amount of the chain transfer agent may be in the range of 0.1 to 5 parts by weight based on 100 parts by weight of one or more of the monomer mixture to ensure sufficient fluidity for the purpose of the present invention when the chain transfer agent is included, . Within this range, sufficient fluidity for the purpose of the present invention can be secured.
The dispersing agent of the present invention is not limited as long as it is a conventional dispersing agent used in suspension polymerization, but a polymeric dispersing agent such as polyvinyl alcohol, cellulose, starch, methyl cellulose, copolymer of (meth) acrylic acid and methyl methacrylate may be used And dispersing aids such as boric acid, calcium carbonate, magnesium carbonate, calcium sulfate, sodium sulfate, sodium dihydrogenphosphate, disodium hydrogenphosphate and the like may be used, but are not limited thereto. The content of the dispersant may be 0.001 to 0.02 parts by weight based on 100 parts by weight of one or more monomer mixtures, but is not limited thereto. It is possible to minimize the phenomenon that the particle size is excessively increased or the fine particles are increased within the above range.
The pressing of the press according to the present invention had a surface hardness of not less than F as measured by a pencil hardness tester and a fall impact strength of 500 g in a thickness of 2 ㎜, 20 ㎝ and 20 ㎝ The specimen is not broken, the light transmittance is 89% or more, and the haze is 1.0 or less. The pressure-pressing has a surface hardness that can be used as a sheathing material when the surface hardness is F or more, and when the manufactured product is not damaged during the measurement of the impact strength of the drop, the impact resistance is good. Further, when the light transmittance is 89% or more and the haze is 1.0 or less, a transparent extrusion board is produced. When such physical properties are satisfied, a product which requires an extruded plate excellent in transparency, surface strength and impact strength of fall impact can be applied.
In the production of the transparent hard pressed press according to the present invention, one or more additives selected from an antioxidant, a plasticizer, a heat stabilizer, an antistatic agent, a nucleating agent, a flame retardant, a lubricant and an ultraviolet absorber may be further included if necessary. The content of the additive may suitably be included within a range that does not impair the physical properties of the transparent high hardness pressed product of the present invention. If necessary, surface hardness can be increased through surface hard coating.
Hereinafter, the present invention will be described in more detail based on examples and comparative examples. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention.
Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, the unit of the additives not specifically described in the specification may be% by weight.
The physical properties of the pressure-pressed sheets prepared through the following examples and comparative examples were measured as follows.
1) Pencil Hardness
The pressure plate thus prepared was extruded to a thickness of 2 mm, cut into a width of 5 cm and a length of 10 cm, and then pencil hardness was measured at a load of 1 kg using a pencil hardness tester. The measurement was made by measuring the pencil hardness at the time of 5 times per pencil with a Mitsubishi pencil and when scratches occurred twice or less.
2) Measuring the impact strength
The pressed sheet was extruded to a thickness of 2 mm, cut into a width of 20 cm and a length of 20 cm, and then detached at a height of 1 m from a 500 g pad.
3) Transmittance and haze measurement
The pressed sheet was extruded to a thickness of 2 mm and cut to a width of 20 cm and a length of 20 cm, and the transmittance and haze were measured according to ASTM D1003 standard.
Equipment: Hazemeter NDH 2000 from Nippon Denshoku
4) Measurement of weight average molecular weight (Mw)
The hardness improver prepared as described below was dissolved in tetrahydrofuran (THF) and then measured by gel permeation chromatography (GPC). As a standard material, a calibration curve was prepared using polymethyl methacrylate.
Equipment name: Waters Alliance GPC system
Column: Waters Styragel HR-3, HR-4, HR-5
Flow rate: 1 ml / min
5) Measurement of melt viscosity (MI)
The polycarbonate resin was dried in an oven at 80 DEG C for 8 hours, and melt flow was measured at 300 DEG C under a load of 1.2 kg according to ASTM D1238 using a melt viscosity meter.
Equipment name: GOTTFERT company MI-2
I. Preparation of Hardness Improver Polymer
[Production Example 1]
To 100 parts by weight of a monomer mixture containing 73% by weight of methyl methacrylate, 20% by weight of phenyl methacrylate, 2% by weight of methyl acrylate and 5% by weight of ethylene glycol dimethacrylate was added 150 parts by weight of distilled water, 0.2 part by weight of 2,2'-azobis 2,4-dimethyl-valeronitrile, 2 parts by weight of n-octylmercaptan as a chain transfer agent, and 2 parts by weight of methacrylic acid and methyl methacrylate neutralized with sodium hydroxide A copolymer (weight average molecular weight: 5,000,000 g / mol) 0.01 part by weight of a solid content 0.7% by weight aqueous solution and 0.005 part by weight of sodium dihydrogenphosphate were added to the reactor and suspended in the aqueous phase with stirring at 400 rpm to prepare a hardness improver. The suspension polymerization was carried out at 80 ° C. for 90 minutes and then polymerized at 105 ° C. for 20 minutes to prepare a suspension polymer from which the residual monomer had been removed. The suspension polymer thus prepared was washed with water and dried to obtain beads of the hardness improver No. 1 .
The weight average molecular weight of the thus-prepared hardener No. (1) beads was measured by gel permeation chromatography, and the weight average molecular weight was 50,000 g / mol.
[Production Example 2]
In the same manner as in Production Example 1 except that 81.5% by weight of methyl methacrylate and 15% by weight of phenyl methacrylate, 0.5% by weight of methyl acrylate and 3% by weight of ethylene glycol dimethacrylate were used in Preparation Example 1 Hardness improver No. (2) was prepared.
The weight average molecular weight of the thus-prepared hardener No. 2 (No. 2) bead was measured by gel permeation chromatography, and the weight average molecular weight was 41,000 g / mol.
[Production Example 3]
Except that 68% by weight of methyl methacrylate and 30% by weight of phenyl methacrylate, 1% by weight of methyl acrylate and 1% by weight of ethylene glycol dimethacrylate were used in the preparation example 1, Hardness improver No. (3) was prepared.
The weight average molecular weight of the produced No. 3 hardener (3) beads was measured by gel permeation chromatography, and the weight average molecular weight was 31,000 g / mol.
[Production Example 4]
A hardness improver No. 4 was prepared in the same manner as in Preparation Example 1 except that 20% by weight of benzylmethacrylate was used in Preparation Example 1.
The weight average molecular weight of the thus-prepared hardener No. 4 was measured by gel permeation chromatography, and the weight average molecular weight was 49,000 g / mol.
[Production Example 5]
A hardness improver No. 5 was prepared in the same manner as in Preparation Example 1 except that 2% by weight of ethyl acrylate was used in the above Production Example 1.
The weight average molecular weight of the prepared No. 5 hard bead was measured by gel permeation chromatography, and the weight average molecular weight was 38,400 g / mol.
[Production Example 6]
A hardness improver No. 6 was prepared in the same manner as in Preparation Example 1, except that 5% by weight of 1,4-butanediol dimethacrylate was used.
The weight average molecular weight of the prepared No. 6 hard bead was measured by gel permeation chromatography, and the weight average molecular weight was 49,100 g / mol.
[Comparative Production Example 1]
In the same manner as in Production Example 1 except that 80% by weight of methyl methacrylate and 13% by weight of phenyl methacrylate, 2% by weight of methyl acrylate and 5% by weight of ethylene glycol dimethacrylate were used in the preparation example 1 A hardness improver No. (7) was prepared.
The weight average molecular weight of the prepared No. 7 hard bead was measured by gel permeation chromatography and the weight average molecular weight was 48,000 g / mol.
[Comparative Production Example 2]
The same procedure as in Production Example 1 was conducted except that 68% by weight of methyl methacrylate and 31% by weight of phenyl methacrylate, 0.5% by weight of methyl acrylate and 0.5% by weight of ethylene glycol dimethacrylate were used in the preparation example 1 Hardness improver No. 8 was prepared.
The weight average molecular weight of the prepared No. 8 hardening improver bead was measured by gel permeation chromatography, and the weight average molecular weight was 31,500 g / mol.
[Comparative Production Example 3]
In the same manner as in Production Example 1 except that 65% by weight of methyl methacrylate and 30% by weight of phenyl methacrylate, 2% by weight of methyl acrylate and 5% by weight of ethylene glycol dimethacrylate were used in the preparation example 1 A hardness improver No. 9 was prepared.
The weight average molecular weight of the prepared No. 9 hard bead was measured by gel permeation chromatography, and the weight average molecular weight was 46,500 g / mol.
[Comparative Production Example 4]
Except that 84% by weight of methyl methacrylate and 15% by weight of phenyl methacrylate, 0.5% by weight of methyl acrylate and 0.5% by weight of ethylene glycol dimethacrylate were used in the preparation example 1, Hardness improver No. 10 was prepared.
The weight average molecular weight of the prepared No. 10 hard bead was measured by gel permeation chromatography, and the weight average molecular weight was 30,500 g / mol.
[Comparative Production Example 5]
(11) was prepared in the same manner as in Production Example 1, except that 66% by weight of methyl methacrylate, 33% by weight of phenyl methacrylate and 1% by weight of methyl acrylate were used in Production Example 1, Respectively.
The weight average molecular weight of the prepared No. 11 hard bead was measured by gel permeation chromatography and the weight average molecular weight was 10,000 g / mol.
II. Manufacture of plaster and measurement of physical properties
[Example 1]
60 wt% of a polycarbonate resin having a melt viscosity (MI) of 3 g / 10 min as measured at 40 캜 of hardness improver No. 1 (1) prepared in Preparation Example 1 and a load of 1.2 ㎏ at 300 캜 was extruded using a twin screw extruder Kneaded to prepare a resin in the form of a pellet, and the produced pellet was produced by a sheet extruder with a 2 mm thick press.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Example 2]
Except that 30% by weight of the hardness improver No. 1 in Example 1 and 70% by weight of a polycarbonate resin having a melt viscosity (MI) of 3 g / 10 min were used in the same manner as in Example 1, .
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Example 3]
Except that 40% by weight of the hardness improver No. 1 in Example 1 and 60% by weight of a polycarbonate resin having a melt viscosity (MI) of 5 g / 10 min were used in the same manner as in Example 1, .
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Comparative Example 1]
Except that 10 weight% of the hardness improver No. 1 and 90 weight% of a polycarbonate resin having a melt viscosity (MI) of 3 g / 10 min were used in Example 1, .
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Comparative Example 2]
Except that 60% by weight of the hardness improver No. 1 in Example 1 and 40% by weight of polycarbonate resin having a melt viscosity (MI) of 3 g / 10 min were used. .
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Comparative Example 3]
40% by weight of the hardness improver No. 1 in Example 1 and 60% by weight of a polycarbonate resin having a melt viscosity (MI) of 22 g / 10 min
, A pressure-pressing was produced in the same manner as in Example 1.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Example 4]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. 2 in Example 1 was used.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Example 5]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. (3) was used in Example 1.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Example 6]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. 4 in Example 1 was used.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Example 7]
A pressure-pressing was produced in the same manner as in Example 1 except that the hardness improver No. 5 in Example 1 was used.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Example 8]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. 6 in Example 1 was used.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Comparative Example 4]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. 7 in Example 1 was used.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Comparative Example 5]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. 8 in Example 1 was used.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Comparative Example 6]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. 9 was used in Example 1.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Comparative Example 7]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. 10 was used in Example 1.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
[Comparative Example 8]
A pressure-pressing was produced in the same manner as in Example 1, except that the hardness improver No. 11 was used in Example 1.
After the preparation, the press-formed product was measured for physical properties and is shown in Table 1 below.
As described in the above Table 1, it was found that the press-presses of Examples 1 to 8 were transparent and could produce pressure-presses having excellent surface hardness and impact strength.
On the other hand, in Comparative Example 1, the content of the hardness improver is low and the effect of improving the surface hardness is low.
It was found that the impact strength of the impact resistance was not sufficiently ensured in Comparative Example 2, and the impact strength of the impact resistance was not sufficiently secured due to the decrease in molecular weight due to the increase of the melting point of the polycarbonate resin in Comparative Example 3. [
Further, in Comparative Example 4, it was found that the lower the content of phenyl methacrylate, the lower the compatibility of the hardness improver and the polycarbonate resin, and the optical characteristics were lowered. In Comparative Example 5, it was found that the effect of the hardness improver was not sufficient due to the increase of the phenyl methacrylate content of the hardness improver.
In Comparative Example 6, the methylmethacrylate content was low and the surface hardness improvement effect was low. In Comparative Example 7, the content of methyl methacrylate was high, so that the impact strength of the dropout was not sufficiently secured.
Further, in Comparative Example 8, it was confirmed that the impact strength was not sufficiently secured due to a low molecular weight without using a crosslinking agent.
Therefore, the composition of the present invention is excellent in transparency, surface hardness and impact resistance, and can be suitably applied to products requiring transparency, surface hardness and impact resistance.
Although the present invention has been described with respect to a transparent hardness extruded plate having excellent impact strength in terms of impact resistance through specified matters and limited embodiments, the present invention is provided only for better understanding of the present invention. And various modifications and changes may be made thereto by those skilled in the art to which the present invention pertains.
Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .
Claims (9)
And 60 to 70% by weight of a polycarbonate having a melt viscosity (MI) of 3 to 5 g / 10 min as measured at a load of 1.2 kg at 300 占 폚.
The aromatic (meth) acrylate monomers include phenyl methacrylate, phenyl acrylate, benzyl methacrylate, benzyl acrylate. Phenoxy methacrylate, 2-ethylphenoxy methacrylate, 2-ethylthio phenyl methacrylate, 2-hydroxy-3-phenoxy propyl acrylate, 2-hydroxy- , Phenoxyethyl acrylate, and phenoxyethyl methacrylate, and which has excellent impact strength at low dropout.
The acrylate monomer may be at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, heptyl acrylate, octyl acrylate, , 2-methylhexyl acrylate, 2-methyl octyl acrylate, 2-tert-butyl heptyl acrylate, 3-isopropyl heptyl acrylate, decyl acrylate, undecyl acrylate, 5-methylundecyl acrylate, dodecyl acrylate , Methyldodecyl acrylate, tridecyl acrylate, 5-methyltridecyl acrylate, tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, 2-methylhexadecyl acrylate, heptadecyl acrylate, 5-ethylheptadecyl acrylate, 5-ethyl octadecyl acrylate, octadecyl acrylate, nonadecyl acrylate And eicosyl acrylate, which are excellent in the strength of the impact resistance.
Wherein the polycarbonate comprises any one or two or more selected from the group consisting of a linear polycarbonate resin, a branched polycarbonate resin and a polyester carbonate copolymer resin.
The crosslinking agent may be at least one selected from the group consisting of ethylene glycol dimethacrylate, bis (4-methacryloxyethoxyphenyl) propane, urethane dimethyrate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, Butanediol diacrylate, 1,4-butanediol dimethacrylate, allyl acrylate, allyl methacrylate, trimethylol propane, triacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate and divinylbenzene And a transparent high hardness pressure printing having excellent impact strength of the impact resistance.
The pressing is a pencil hardness F or more,
The impact strength of the volumetric impact strength of specimens was not broken when specimens with a thickness of 2 ㎜, 20 ㎝ and 20 ㎝ were dropped from a 500 -
A light transmittance of 89% or more,
Haze A haze of 1.0 or less.
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