KR20160141268A - Polycarbonate copolymer having improved scratch resistance and method for preparing the same - Google Patents
Polycarbonate copolymer having improved scratch resistance and method for preparing the same Download PDFInfo
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- KR20160141268A KR20160141268A KR1020150076351A KR20150076351A KR20160141268A KR 20160141268 A KR20160141268 A KR 20160141268A KR 1020150076351 A KR1020150076351 A KR 1020150076351A KR 20150076351 A KR20150076351 A KR 20150076351A KR 20160141268 A KR20160141268 A KR 20160141268A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
- C08G64/045—Aromatic polycarbonates containing aliphatic unsaturation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/38—General preparatory processes using other monomers
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- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
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Abstract
Description
The present invention relates to a polycarbonate copolymer having improved scratch resistance and a process for producing the same. More particularly, the present invention relates to a polycarbonate copolymer having (A) a hydroxy-terminal monocyclic, polycyclic or fused A cyclic compound-derived unit, and (B) a carbonate unit, and to a process for producing the polycarbonate copolymer and a polycarbonate copolymer having improved scratch resistance and anti-fogging properties compared to a linear polycarbonate.
Polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and is excellent in dimensional stability, heat resistance and optical transparency, and is widely used in industrial applications. Studies have been continuing on various copolymers to improve the physical properties of polycarbonate. For example, polysiloxane-polycarbonate copolymers have been proposed for improving low-temperature impact resistance (U.S. Patent Application Publication No. 2003/0105226).
The chemical structure of the polycarbonate prepared by using bisphenol A and phosgene has basically a hydroxyl group at the terminal end, and a new type of polymer can be produced by a method of activating hydroxyl groups at both terminal ends. In this case, the polymerization may be carried out in an aqueous solution, at an interface, or in a water-insoluble solution.
However, polycarbonates prepared from bisphenol A in particular have limited scratch resistance. Therefore, in order to prevent or minimize the scratch damage, it is necessary to apply a hard coat as a surface modification. This hard coat has a disadvantage in that it is accompanied by an additional process and a cost and is not durable.
Also, polycarbonates made from bisphenol A have low surface tensions, which can easily cause water vapor fogging due to condensation of water on cold surfaces, which reduces the optical advantage of the polycarbonate. Therefore, in order to reduce or eliminate such a water vapor streak phenomenon, it is necessary to apply a water vapor anti-reflection coating or introduce a hydrophilic functional group onto the molecule using a sulfonation method. However, all of these methods require complex processes and generate high additional costs. In addition, the water vapor stabilizer widely used in polyolefins is poor in thermal stability and poor in compatibility with polycarbonate.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a polycarbonate copolymer which exhibits improved scratch resistance and anti- And a manufacturing method thereof.
(A) a unit derived from a hydroxy-terminal monocyclic, polycyclic or fused cyclic compound having a (meth) acrylate group and (B) a carbonate unit as a repeating unit And a polycarbonate copolymer.
According to another aspect of the present invention there is provided a process for preparing a precursor solution comprising the steps of (1) preparing a carbonate precursor solution, (2) adding to the carbonate precursor solution a hydroxy-terminal monocyclic, polycyclic or fused cyclic (meth) (3) a step of polymerizing the resultant mixture of the step (2). The present invention also provides a method for producing a polycarbonate copolymer, comprising the steps of:
According to another aspect of the present invention, there is provided a processed resin article produced using the polycarbonate copolymer.
According to still another aspect of the present invention, there is provided a compound having a structure represented by the following Formula 1-1:
[Formula 1-1]
HO- [A (-CH 2 CH 2 C (= O) OR)] - OH
In Formula 1-1,
R represents a substituted or unsubstituted alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group;
A is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group, or a substituted or unsubstituted divalent monoheteroaryl group containing at least one atom selected from N, O and S Is a cyclic, polyheterocyclic or fused heterocyclic group and may contain two or more bonds selected from an ether bond, a thioether bond, an ester bond, a ketone bond and a urethane bond.
The polycarbonate copolymers according to the present invention are useful for optical applications and material lightweight substitutes in various industries because they exhibit the effects of improved scratch resistance and anti-fogging while maintaining good transparency.
Hereinafter, the present invention will be described in more detail.
The present invention provides a polycarbonate copolymer comprising (A) a unit derived from a hydroxy-terminal monocyclic, polycyclic or fused cyclic compound having a (meth) acrylate group and (B) a carbonate unit do.
(Meth) acrylate group having a (meth) acrylate group, a polycyclic or fused cyclic compound having a (meth) acrylate group which provides the repeating unit (A) to the polycarbonate copolymer of the present invention (Meth) acrylate group and two or more (for example, two to four) hydroxyl groups are linked to the monocyclic, polycyclic or fused cyclic central moiety As a compound of the structure, a hydroxy group exists at both terminals.
The (meth) acrylate group may be selected from, for example, an alkyl (meth) acrylate group, an aryl (meth) acrylate group, an arylalkyl (meth) acrylate group, an alkylaryl May be, for example, linear or branched alkyl of 1 to 10 carbon atoms (or 1 to 6 carbon atoms) or cycloalkyl of 3 to 12 carbon atoms, and "aryl" may be, for example, aryl of 6 to 12 carbon atoms However, the present invention is not limited thereto.
The content of the unit derived from the (meth) acrylate group-containing hydroxy-terminal cyclic compound (A) contained in the polycarbonate copolymer of the present invention is 1 to 100 moles %, Preferably 3 to 75 mol%, and more preferably 5 to 60 mol%. However, the present invention is not limited thereto. If the content of the unit derived from the (meth) acrylate group-containing hydroxy-terminal cyclic compound in the copolymer is too small, the scratch resistance and the anti-fogging effect of the copolymer may be lowered to a desired level. On the contrary, There is a problem in synthesis and heat resistance.
According to one embodiment of the present invention, the (meth) acrylate group-containing hydroxy-terminated cyclic compound may have a structure represented by the following Formula 1-1:
[Formula 1-1]
HO- [A (-CH 2 CH 2 C (= O) OR)] - OH
In Formula 1-1,
R represents a substituted or unsubstituted alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group;
A is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group, or a substituted or unsubstituted divalent monoheteroaryl group containing at least one atom selected from N, O and S Is a cyclic, polyheterocyclic or fused heterocyclic group which may contain two or more (for example, two to four) bonds selected from an ether bond, a thioether bond, an ester bond, a ketone bond and a urethane bond.
As used herein, the term "substituted" or "substituted" means that a hydrogen atom is replaced by a halogen atom (eg Cl or Br), a hydroxyl group, an alkyl group having 1 to 13 carbon atoms (eg, methyl, ethyl, (E.g., phenyl, chlorophenyl, tolyl, and the like), a combination of these, and the like, such as an alkoxy group having 1 to 13 carbon atoms (e.g., methoxy, ethoxy or propoxy) or an aryl group having 6 to 10 carbon atoms
More specifically, in Formula 1-1,
R is a substituted or unsubstituted C 1 -C 10 alkyl group, a C 6 -C 12 aryl group, a C 6 -C 12 aryl-C 1 -C 10 alkyl group, or a C 1 -C 10 alkyl-C 6 -C 12 aryl Lt; / RTI >
A is a substituted or unsubstituted divalent aliphatic group having 5 to 30 carbon atoms in total or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms in total, or an atom selected from N, O and S Substituted or unsubstituted divalent, monocyclic heterocyclic group having 5 to 30 total ring atoms, a polyheterocyclic or a fused heterocyclic group, and includes an ether bond, a thioether bond, an ester bond, a ketone bond and a And may contain two or more bonds selected from urethane bonds.
More specifically, in Formula 1-1,
R represents a substituted or unsubstituted C 1 -C 6 alkyl group or a C 6 aryl-C 1 -C 6 alkyl group;
A is a substituted or unsubstituted divalent group, an aromatic monocyclic group having 6 to 20 carbon atoms in total, a polycyclic or fused cyclic group, or a substituted or unsubstituted aryl group having at least one atom selected from N, O and S A bicyclic, monoheterocyclic, polyheterocyclic or fused heterocyclic group having a total of 5 to 20 ring atoms and having two bonds selected from an ether bond, a thioether bond, an ester bond, a ketone bond and a urethane bond Or more.
According to a more preferred embodiment of the present invention, the (meth) acrylate group-containing hydroxy-terminal cyclic compound may have a structure represented by the following formula (1-2)
[Formula 1-2]
In Formula 1-2,
R is the same as defined in Formula 1-1.
There is no particular limitation on the method for producing the (meth) acrylate group-containing hydroxy-terminal cyclic compound. According to one embodiment of the invention, the (meth) acrylic acid group [i.e., -CH 2 CH 2 C (= O) OH] having a hydroxy-terminated compound with a cyclic alkyl alcohol, an aryl alcohol, aryl alcohol or alkyl The aryl alcohol can be produced by ester-reacting an aryl alcohol in the presence of an acid or a base catalyst (for example, a base such as an inorganic acid or an organic acid such as sulfuric acid, or an alkali metal hydroxide), but is not limited thereto.
The polycarbonate copolymer of the present invention may further comprise a unit (A ') derived from an aromatic dihydroxy compound different from the above (A) as a repeating unit. According to one embodiment, the entire diol compound-derived unit present in the polycarbonate copolymer of the present invention is composed of the repeating units (A) and (A ').
The aromatic dihydroxy compound different from the above (A), which provides the polycarbonate copolymer of the present invention with the repeating unit (A '), may have, for example, a structure represented by the following formula (2).
(2)
In Formula 2,
X is an alkylene group, a linear, branched or cyclic alkylene group having no functional group, or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, Lt; / RTI > Preferably, X is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and 3 to 6 carbon atoms.
R 6 independently represents a hydrogen atom, a halogen atom, or an alkyl group, for example, a straight, branched or cyclic alkyl group of 3 to 20 carbon atoms (preferably 3 to 6 carbon atoms) having 1 to 20 carbon atoms.
a and b independently represent an integer of 0 to 4;
The compound of Formula 2 may be, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis ) - (4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1- Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, Bis (4-hydroxyphenyl) propane, bis (3-methyl-4-hydroxyphenyl) propane, 2,2- , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Resorcinol, Hydroquine, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-di Dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro- Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, Dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5- (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1- Bis (4-hydroxyphenyl) propane, 1,4-bis (4- (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis -Bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis , Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, ', 5,5'-tetramethyl-4,4'-dihydroxybenzophe , 4,4'-dihydroxy-diphenyl, methyl may be a hydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxy naphthalene, but is not limited thereto. Representative examples include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other functional dihydric phenols can be found in US Pat. Nos. US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used singly or in combination of two or more. Can be used.
The carbonate unit (B) contained as a repeating unit in the polycarbonate copolymer of the present invention may be derived from a carbonate precursor.
The carbonate precursors can be, for example, carbonyl chloride (i.e., phosgene), bis (trichloromethyl) carbonate (i.e., triphosgene), carbonyl bromide, bishaloformate, diphenyl carbonate, dimethyl carbonate, But is not limited thereto.
The copolymer of the present invention includes the same number of moles of carbonate units as the total of the repeating units (A) and (A ').
In addition to the repeating units (A), (A ') and (B) described above, the copolymer of the present invention may further contain one or more additional copolymer units within the scope of achieving the object of the present invention, There is no particular limitation on the kind of such additional copolymerization unit.
According to another aspect of the present invention there is provided a process for preparing a precursor solution comprising the steps of (1) preparing a carbonate precursor solution, (2) adding to the carbonate precursor solution a hydroxy-terminal monocyclic, polycyclic or fused cyclic (meth) (3) a step of polymerizing the resultant mixture of the step (2). The present invention also provides a method for producing a polycarbonate copolymer, comprising the steps of:
The method and conditions for preparing the carbonate precursor solution are not particularly limited and conventionally known methods or conditions can be used. According to one embodiment of the present invention, a carbonate precursor solution can be prepared by dissolving a carbonate precursor (e.g., phosgene) in an appropriate solvent (e.g., a non-aqueous organic solvent such as chloromethane, dichloromethane, trichloromethane, etc.) But is not limited thereto.
According to one embodiment of the process for producing a polycarbonate copolymer of the present invention, the hydroxy-terminal monocyclic, polycyclic or fused cyclic compound having the (meth) acrylate group (for example, Formula 1-1) terminal monocyclic, poly cyclic or fused cyclic compound and an alkyl alcohol, an aryl alcohol, aryl alkyl or alkyl alcohol (meth) acrylic acid group [i.e., -CH 2 CH 2 C (= O) OH] having a hydroxy Can be produced by subjecting an aryl alcohol to an ester reaction in the presence of an acid or a base catalyst (for example, a base such as an inorganic acid or an organic acid such as sulfuric acid, or an alkali metal hydroxide).
Further, according to one embodiment of the process for producing a polycarbonate copolymer of the present invention, the diol component is an aromatic group having a (meth) acrylate group and a hydroxy-terminal monocyclic, polycyclic or fused cyclic compound having different A dihydroxy compound (for example, the above formula (2)).
There are no particular restrictions on the method or condition of the polymerization, and any known method or condition may be used. According to one embodiment of the present invention, the polymerization reaction may be carried out at room temperature in the presence of a catalyst (e.g., a basic catalyst such as an alkali metal hydroxide, an alkylammonium salt, an alkylamine or the like), but is not limited thereto.
Since the polycarbonate copolymer of the present invention exhibits the effects of improved scratch resistance and prevention of water vapor stains while maintaining excellent transparency, the resin processed products (such as films, sheets, lenses, cover glasses, interior / exterior materials, etc.) And can be used for optical applications and material lightweight alternatives.
Thus, according to another aspect of the present invention, there is provided a resin finished product made using the polycarbonate copolymer of the present invention.
The method for producing a resin-finished product by using the polycarbonate copolymer of the present invention is not particularly limited, and a method generally used for processing a copolymer resin can be used as it is or modified appropriately.
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited to these examples.
[ Example ]
Synthetic example One: Acrylate group Containing hydroxy-terminal Cyclic Preparation of compounds
A condenser was placed in a 500 mL three-necked flask and 10 g of 4,4-bis (4-hydroxyphenyl) valeric acid (Sigma Aldrich) was dissolved in methanol (Sigma Aldrich ). 10 mL of 0.1 mol% sulfuric acid (Sigma Aldrich) relative to methanol was added slowly while refluxing the prepared solution, and then the solution was refluxed at 60 DEG C for 12 hours. After the reaction, the solvent was removed and dried in a vacuum oven to prepare a monomer represented by the following formula (a).
(A)
Example 1: Preparation of Polycarbonate Copolymer
In a 500 mL two-necked flask, 4.84 g of triphosgene (Sigma Aldrich) was dissolved in 25 mL of dichloromethane (Sigma Aldrich). 5 g of bisphenol A (BPA, Sigma Aldrich), 0.2 g of monomer of formula (a) and 8 g of sodium hydroxide (Sigma Aldrich) were dissolved in 100 mL of distilled water and tetrabutylammonium chloride (PTC, Sigma Aldrich) was added thereto, followed by stirring for about 30 minutes. Then, 0.12 mL of triethylamine (TEA, Sigma Aldrich) was slowly added thereto using a funnel, and the reaction was allowed to proceed at room temperature for 24 hours. After stopping the reaction, the organic layer was collected from the water layer and the organic layer, and the polymer was assembled in a mixed solution of water and acetone. The assembled polymer granules were dried in an oven at 100 ° C. for 24 hours to obtain polycarbonate aerials containing 97 mol% of BPA-derived units and 3 mol% of monomer-derived units of formula (a) based on 100 mol% (Having a structure represented by the following formula A). The physical properties of the prepared copolymer were measured and are shown in Table 1 below.
(A)
Synthetic example 2: Acrylate group Containing hydroxy-terminal Cyclic Preparation of compounds
A monomer of the following formula (b) was prepared in the same manner as in Synthesis Example 1 except that ethanol (Sigma Aldrich) was used instead of methanol.
[Formula b]
Example 2: Preparation of polycarbonate copolymer
A polycarbonate copolymer (having the structure of the following Formula B) was prepared in the same manner as in Example 1, except that 97 mol% of BPA and 3 mol% of the monomer of Formula (b) were used based on 100 mol% of the total diol compound. The physical properties of the prepared copolymer were measured and are shown in Table 1 below.
[Chemical Formula B]
Synthetic example 3: Acrylate group Containing hydroxy-terminal Cyclic Preparation of compounds
A monomer of the following formula (c) was prepared in the same manner as in Synthesis Example 1, except that t-butyl alcohol (Sigma Aldrich) was used instead of methanol.
(C)
Example 3: Preparation of Polycarbonate Copolymer
A polycarbonate copolymer was prepared in the same manner as in Example 1, except that 97 mol% of BPA and 3 mol% of the monomer of the formula (c) were used based on 100 mol% of the total diol compound. The physical properties of the prepared copolymer were measured and are shown in Table 1 below.
Synthetic example 4: Acrylate group Containing hydroxy-terminal Cyclic Preparation of compounds
A monomer of the following formula (d) was prepared in the same manner as in Synthesis Example 1, except that benzyl alcohol (Sigma Aldrich) was used instead of methanol.
[Chemical formula d]
Example 4: Preparation of Polycarbonate Copolymer
A polycarbonate copolymer was prepared in the same manner as in Example 1, except that 97 mol% of BPA and 3 mol% of the monomer of the formula (d) were used based on 100 mol% of the total diol compound. The physical properties of the prepared copolymer were measured and are shown in Table 1 below.
Example 5: Preparation of polycarbonate copolymer
A polycarbonate copolymer was prepared in the same manner as in Example 1, using 94 mol% of BPA and 6 mol% of the monomer of the formula (a) based on 100 mol% of the total diol compound. The physical properties of the prepared copolymer were measured and are shown in Table 1 below.
Example 6: Preparation of polycarbonate copolymer
A polycarbonate copolymer was prepared in the same manner as in Example 1, except that 50 mole% of BPA and 50 mole% of monomer of Formula (a) were used based on 100 mole% of the total diol compound. The physical properties of the prepared copolymer were measured and are shown in Table 1 below.
Example 7: Preparation of Polycarbonate Copolymer
A polycarbonate copolymer was prepared in the same manner as in Example 1, using 100 mol% of the monomer of the formula (a) based on 100 mol% of the total diol compound. The physical properties of the prepared copolymer were measured and are shown in Table 1 below.
Comparative Example
The physical properties of a linear polycarbonate having a viscosity average molecular weight of 21,000 (Samyang 3022IR) were measured and described in Table 1 below.
≪ Measurement of physical properties &
(a) One H-NMR (nuclear magnetic resonance spectroscopy) analysis
And measured using an Avance DRX 300 from Bruker. The synthesis and content of the copolymer were confirmed by methylene peak of acrylate observed at about 3.8 ppm by 1 H-NMR and alkylene peak between two acrylates and phenyl groups appearing between 2.1 and 2.7 ppm.
(b) viscosity average molecular weight ( Mv )
The viscosity of the dichloromethane solution was measured at 20 degrees using an Atlantic viscometer (Atlantic) and the intrinsic viscosity [?] Was calculated from the following formula.
[ŋ] = 1.23 X 10 -5 Mv 0 .83
(c) Pencil hardness
No. of YASUDA SEIKI Co., Ltd. 553-M1 pencil hardness tester. The pencil hardness value of the hardest pencil concentration just before the scratching of the coating by rubbing the drawing at an angle of 45 ° and causing scratches is shown by pencil hardness value. The hardness of the pencil is lowered in the order of 9H-8H-7H-6H-5H-4H-3H-2H-H-F-HB-B-3B-4B-5B-6B-7B-8B-9B.
(d) Contact angle (°)
And measured using a Phoenix 300 manufactured by SEO. The surface properties were evaluated by measuring the contact angle formed between the surface of the sample and the droplet by dropping liquid (water) on the sample. The lower the numerical value, the higher the surface tension and the higher the hydrophilicity, and the better the effect of preventing the water vapor.
As shown in Table 1, the polycarbonate copolymers of the Examples all exhibited superior pencil hardness and lower water contact angle than the commercialized linear polycarbonate Comparative Example, whereby the polycarbonate copolymer according to the present invention was commercialized It shows that the polycarbonate exhibits improved scratch resistance and anti-fogging effect as compared with the linear polycarbonate.
Claims (19)
[Formula 1-1]
HO- [A (-CH 2 CH 2 C (= O) OR)] - OH
In Formula 1-1,
R represents a substituted or unsubstituted alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group;
A is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group, or a substituted or unsubstituted divalent monoheteroaryl group containing at least one atom selected from N, O and S Is a cyclic, polyheterocyclic or fused heterocyclic group and may contain two or more bonds selected from an ether bond, a thioether bond, an ester bond, a ketone bond and a urethane bond.
R is a substituted or unsubstituted C 1 -C 10 alkyl group, a C 6 -C 12 aryl group, a C 6 -C 12 aryl-C 1 -C 10 alkyl group, or a C 1 -C 10 alkyl-C 6 -C 12 aryl Lt; / RTI >
A is a substituted or unsubstituted divalent aliphatic group having 5 to 30 carbon atoms in total or an aromatic monocyclic, polycyclic or fused cyclic group having 6 to 30 carbon atoms in total, or an atom selected from N, O and S Substituted or unsubstituted divalent, monocyclic heterocyclic group having 5 to 30 total ring atoms, a polyheterocyclic or a fused heterocyclic group, and includes an ether bond, a thioether bond, an ester bond, a ketone bond and a ≪ RTI ID = 0.0 > and / or < / RTI >
Polycarbonate copolymer.
R represents a substituted or unsubstituted C 1 -C 6 alkyl group or a C 6 aryl-C 1 -C 6 alkyl group;
A is a substituted or unsubstituted divalent group, an aromatic monocyclic group having 6 to 20 carbon atoms in total, a polycyclic or fused cyclic group, or a substituted or unsubstituted aryl group having at least one atom selected from N, O and S A bicyclic, monoheterocyclic, polyheterocyclic or fused heterocyclic group having a total of 5 to 20 ring atoms and having two bonds selected from an ether bond, a thioether bond, an ester bond, a ketone bond and a urethane bond Or more,
Polycarbonate copolymer.
[Formula 1-2]
In Formula 1-2,
R represents a substituted or unsubstituted alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group.
(2)
In Formula 2,
X is an alkylene group, a linear, branched or cyclic alkylene group having no functional group, or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, Lt; / RTI >
R 6 independently represents a hydrogen atom, a halogen atom, or an alkyl group,
a and b independently represent an integer of 0 to 4;
(2) adding and mixing a diol component comprising a hydroxy-terminal monocyclic, polycyclic or fused cyclic compound having a (meth) acrylate group into the carbonate precursor solution, and
(3) polymerizing the resultant mixture of step (2)
A method for producing a polycarbonate copolymer.
[Formula 1-1]
HO- [A (-CH 2 CH 2 C (= O) OR)] - OH
In Formula 1-1,
R represents a substituted or unsubstituted alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group;
A is a substituted or unsubstituted divalent aliphatic or aromatic monocyclic, polycyclic or fused cyclic group, or a substituted or unsubstituted divalent monoheteroaryl group containing at least one atom selected from N, O and S Is a cyclic, polyheterocyclic or fused heterocyclic group and may contain two or more bonds selected from an ether bond, a thioether bond, an ester bond, a ketone bond and a urethane bond.
[Formula 1-2]
In Formula 1-2,
R represents a substituted or unsubstituted alkyl group, an aryl group, an arylalkyl group, or an alkylaryl group.
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| KR1020150076351A KR101815930B1 (en) | 2015-05-29 | 2015-05-29 | Polycarbonate copolymer having improved scratch resistance and method for preparing the same |
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| KR (1) | KR101815930B1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020158590A1 (en) * | 2019-01-30 | 2020-08-06 | 出光興産株式会社 | Carbonate-olefin based copolymer and composition thereof |
| KR20210028763A (en) * | 2019-09-04 | 2021-03-15 | 주식회사 삼양사 | Polyester-polycarbonate block copolymer having improved scratch resistance and method for preparing the same |
| KR20220094265A (en) * | 2020-12-28 | 2022-07-06 | 주식회사 삼양사 | Copolymer with improved scratch resistance and good impact resistance and method for preparing the same |
| KR20220094247A (en) * | 2020-12-28 | 2022-07-06 | 주식회사 삼양사 | Polyester oligomer and method for preparing the same, and polyester-polycarbonate block copolymer comprising the oligomer with well-balanced impact resistance and scratch resistance and method for preparing the same |
| KR20240090213A (en) | 2021-10-29 | 2024-06-21 | 이데미쓰 고산 가부시키가이샤 | Aromatic polycarbonate-based resin, polycarbonate-based resin compositions and molded products |
-
2015
- 2015-05-29 KR KR1020150076351A patent/KR101815930B1/en active IP Right Grant
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020158590A1 (en) * | 2019-01-30 | 2020-08-06 | 出光興産株式会社 | Carbonate-olefin based copolymer and composition thereof |
| KR20210028763A (en) * | 2019-09-04 | 2021-03-15 | 주식회사 삼양사 | Polyester-polycarbonate block copolymer having improved scratch resistance and method for preparing the same |
| KR20220094265A (en) * | 2020-12-28 | 2022-07-06 | 주식회사 삼양사 | Copolymer with improved scratch resistance and good impact resistance and method for preparing the same |
| KR20220094247A (en) * | 2020-12-28 | 2022-07-06 | 주식회사 삼양사 | Polyester oligomer and method for preparing the same, and polyester-polycarbonate block copolymer comprising the oligomer with well-balanced impact resistance and scratch resistance and method for preparing the same |
| KR20240090213A (en) | 2021-10-29 | 2024-06-21 | 이데미쓰 고산 가부시키가이샤 | Aromatic polycarbonate-based resin, polycarbonate-based resin compositions and molded products |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101815930B1 (en) | 2018-01-09 |
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