KR20210142104A - Terminal (meth)acrylate polycarbonate oligomer - Google Patents

Abstract

The present invention is a raw material for an ultraviolet curable (meth)acrylic resin used in an ultraviolet curable hard coat agent, etc., and has good compatibility and solvent solubility with a polyfunctional (meth)acrylic monomer, and also has excellent abrasion resistance when cured (meth) An object is to provide an acrylate polycarbonate oligomer.
In order to solve the above problems, the present invention is a terminal (meth)acrylate polycarbonate oligomer represented by Formula 1 and/or Formula 2, and having a weight average molecular weight (Mw) in the range of 300 or more and 10,000 or less. provides

Description

Terminal (meth)acrylate polycarbonate oligomer

The present invention relates to a terminal (meth)acrylate polycarbonate oligomer having good solvent solubility and excellent abrasion resistance upon curing.

Resin materials are widely used as engineering plastics due to their advantages such as light weight, low cost, and excellent workability. . In order to improve these drawbacks of the resin material, a resin thin film of a material different from the resin of the base material is formed on the surface of the resin, the resin of the base material is protected from external factors, and a hard coat treatment for surface modification is generally performed. is losing For the formation of the hard coat layer, a system in which a hard coat agent is applied to the resin surface of the substrate and dried, and then irradiated with radiation such as an electron beam or ultraviolet (UV), if necessary, and cured (for example, a patented patent) Literature 1, 2). Among these, the ultraviolet curable hard coat agent using an ultraviolet curable resin is developed for various uses with high productivity, since a process is possible in a short time at low temperature compared with the conventional hard coat agent.

Since this ultraviolet curable hard coat agent uses polyfunctional (meth)acrylic monomers, such as pentaerythritol-type (meth)acrylate, as a main component, the component to mix|blend has high compatibility with these polyfunctional (meth)acryl monomers. that is being demanded

Japanese Patent Laid-Open No. 2010-024255 Japanese Patent Laid-Open No. 2016-011365

The present invention has been made against the background of the above circumstances, and as a raw material for an ultraviolet curable (meth)acrylic resin used in an ultraviolet curable hard coat agent, etc., compatibility with a polyfunctional (meth)acrylic monomer and solvent solubility are good, and An object of the present invention is to provide a terminal (meth)acrylate polycarbonate oligomer having excellent abrasion resistance when cured.

As a result of intensive studies for solving the above-described problems, the present inventors have, in the terminal (meth)acrylate polycarbonate represented by the following Chemical Formula 1 and/or the following Chemical Formula 2, an oligomer having a weight average molecular weight (Mw) in a specific range, Compatibility with a polyfunctional (meth)acryl monomer and solvent solubility were favorable, and it discovered that it was excellent in abrasion resistance when hardened|cured, and completed this invention.

The present invention is as follows.

1. A terminal (meth)acrylate polycarbonate oligomer represented by Formula 1 and/or Formula 2 below, and having a weight average molecular weight (Mw) in the range of 300 or more and 10,000 or less.

(In Formulas 1 and 2, R ₁ each independently represents a hydrogen atom or a methyl group, R ₂ , R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, and n is an integer of 1 or more. , R ₂ and the sum of the number of carbon atoms of _{R 3 is 14 or less.)}

The terminal (meth)acrylate polycarbonate oligomer according to the present invention has a weight average molecular weight (Mw) in the range of 300 to 10,000, polyfunctional (meth)acrylic monomers such as pentaerythritol (meth)acrylate and UV curing is possible because of good compatibility and solvent solubility, and the obtained cured film is excellent in abrasion resistance. have an adversely beneficial effect.

^{1 is a 1} H-NMR spectrum chart of the terminal acrylate polycarbonate oligomer (1a) synthesized in Example 1. FIG.
^{2 is a 1} H-NMR spectrum chart of the terminal acrylate polycarbonate oligomer (1b) synthesized in Example 2. FIG.

The terminal (meth)acrylate polycarbonate oligomer of the present invention will be described in detail below.

The terminal (meth)acrylate polycarbonate oligomer of the present invention, as illustrated in the following reaction scheme, by the reaction of the polycarbonate oligomer represented by Formula A-1 with a (meth)acrylate agent such as (meth)acrylic acid chloride It is a compound represented by the following general formula (1) and/or the following general formula (2), which is the range of the weight average molecular weight (Mw) of 300 or more and 10,000 or less obtained.

(In the reaction scheme _{, the integers of R 1 to R 3} , n are the same as in Formulas 1 and 2 described above.)

<About the polycarbonate oligomer represented by the formula A-1>

With respect to the chemical structure of the terminal (meth)acrylate polycarbonate oligomer of the present invention, the polycarbonate oligomer represented by the following formula (A-1), which is a raw material for synthesis thereof, will be described in detail. That is, specific examples of n in the formula (A-1), preferred chemical groups and substituents thereof, etc. are the same as n in the formulas (1) and/or (2) representing the terminal (meth)acrylate polycarbonate oligomer of the present invention.

[Formula A-1]

(In Formula A-1 _{, the integers of R 2} , R ₃ , and n are the same as in Formulas 1 and 2 described above.)

The substitution position of the methyl group in the formula (A-1) is preferably an ortho position with respect to the oxygen atom bonded to the benzene ring.

_{R 2} and R ₃ in the formula (A-1) each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, and the alkyl group is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. , More preferably, it is a C1-C8 linear, branched alkyl group, More preferably, it is a C1-C4 linear, branched alkyl group. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n - a nonyl group, n-decyl group, n-undecyl group, n-tridecyl group, etc. are mentioned. However, the total number of carbon atoms of _{R 2} and R _{3 must be 14 or less.}

The polycarbonate oligomer represented by the formula (A-1) may be prepared by any conventionally known production method. Specifically, interfacial polymerization method, melt transesterification method, pyridine method, ring-opening polymerization method of a cyclic carbonate compound, the solid-phase transesterification method of a prepolymer etc. are mentioned, for example. Among these, it is industrially advantageous to use the interfacial polymerization method, the melt transesterification method, and the solid-phase transesterification method of a prepolymer. Among these, the melt transesterification method which does not use phosgene, and the solid-phase transesterification method of the prepolymer by a melt transesterification method are especially preferable. The above production method is carried out using an aromatic dihydroxy compound represented by the following formula (B-1) and a carbonate ester forming agent.

[Formula B-1]

_{(The definitions of R 2} and R ₃ in Formula B-1 are the same as those of Formulas 1 and 2 described above.)

<About the aromatic dihydroxy compound represented by the general formula B-1>

Specific examples of the aromatic dihydroxy compound represented by the formula (B-1) include bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxy-3-methylphenyl)ethane, , 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)butane, 2,2-bis(4-hydroxy-3-methylphenyl) Pentane, 2,2-bis(4-hydroxy-3-methylphenyl)hexane, 2,2-bis(4-hydroxy-3-methylphenyl)heptane, 2,2-bis(4-hydroxy-3-methylphenyl) ) octane, 1,1-bis(4-hydroxy-3-methylphenyl)decane, 2,2-bis(4-hydroxy-3-methylphenyl)decane, 2,2-bis(4-hydroxy-3-methylphenyl)decane Methylphenyl)dodecane, bis(4-hydroxy-2-methylphenyl)methane, 1,1-bis(4-hydroxy-2-methylphenyl)ethane, 2,2-bis(4-hydroxy-2-methylphenyl) Propane etc. are mentioned.

In the case of a polymerization reaction, you may use these aromatic dihydroxy compounds individually or in mixture of 2 or more types in arbitrary ratios.

<About carbonate ester former>

Specific examples of the carbonate ester forming agent to be reacted with the aromatic dihydroxy compound represented by the formula (B-1) include diaryl carbonate such as diphenyl carbonate, ditolyl carbonate, and bis(m-cresyl) carbonate; Dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, dicyclohexyl carbonate, alkylaryl carbonate such as methylphenyl carbonate, ethylphenyl carbonate, cyclohexylphenyl carbonate, divinyl carbonate, diisopropenyl carbonate, dipropenyl carbonate, etc. and diester carbonates such as dialkenyl carbonate. Moreover, dihalogenated carbonyl compounds, such as phosgene, etc., and triphosgene are mentioned. Among these, diaryl carbonate is preferable, and diphenyl carbonate is particularly preferable.

<About melt transesterification method>

As a method for producing the polycarbonate oligomer represented by the general formula (A-1), a melt transesterification method will be described.

As a method of melt transesterification, when an aromatic dihydroxy compound represented by the formula (B-1) and diphenyl carbonate are used as a carbonate ester forming agent, heating is performed in the presence of a catalyst in an inert gas atmosphere at normal pressure or reduced pressure. It is carried out by stirring while distilling the produced phenol. Usually, by adjusting the mixing ratio of the aromatic dihydroxy compound represented by the formula (B-1) and the carbonate ester forming agent, and the degree of pressure reduction during the transesterification reaction, the desired molecular weight and the amount of terminal hydroxyl groups are adjusted. The indicated polycarbonate oligomer can be obtained.

In order to obtain the polycarbonate oligomer represented by the formula (A-1), the mixing ratio of the aromatic dihydroxy compound represented by the formula (B-1) and the carbonate ester forming agent is 1 mole of the aromatic dihydroxy compound represented by the formula (B-1) As a result, the amount of the carbonate ester forming agent is usually 0.2 to 1.0 moles, preferably 0.25 to 0.95 moles, and more preferably 0.3 to 0.90 moles.

In order to increase the reaction rate during the melt transesterification reaction, a transesterification catalyst is used if necessary. There is no restriction|limiting in particular as a transesterification catalyst, For example, alkali metals, such as inorganic alkali metal compounds, such as lithium, sodium, cesium hydroxide, carbonate, hydrogen carbonate compound, organic alkali metal compound, such as alcoholate and organic carboxylate. Compounds; Alkaline earth metal compounds such as hydroxides such as beryllium and magnesium, inorganic alkaline earth metal compounds such as carbonates, and organic alkaline earth metal compounds such as alcoholates and organic carboxylates; tetramethylboron, tetraethylboron, butyltriphenyl Basic boron compounds such as sodium salts such as boron, calcium salts, and magnesium salts; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine, or quaternary phosphonium salts derived from these compounds Phosphorus compounds; Basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and tetrabutylammonium hydroxide; Known amine compounds such as 4-aminopyridine, 2-dimethylaminoimidazole and aminoquinoline of transesterification catalysts can be used. Among them, alkali metal compounds are preferable, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferable.

The amount of the catalyst to be used is within the range where the catalyst residue does not cause any problems in terms of the quality of the oligomer produced, and since the appropriate amount to be added varies depending on the type of catalyst, it can be said uniformly, but it is roughly, for example, It is usually 0.05 to 100 μmol, preferably 0.08 to 50 μmol, more preferably 0.1 to 20 μmol, still more preferably 0.1 to 5 μmol with respect to 1 mol of the indicated aromatic dihydroxy compound. The catalyst may be added as it is, or may be added by dissolving in a solvent. As the solvent, for example, water, phenol, etc., those which do not affect the reaction are preferable.

The reaction conditions for the melt transesterification reaction are usually in the range of 120 to 360°C, preferably in the range of 150 to 280°C, and more preferably in the range of 180 to 260°C. When the reaction temperature is too low, the transesterification reaction does not proceed, and when the reaction temperature is high, side reactions such as decomposition reaction proceed, which is not preferable. The reaction is preferably carried out under reduced pressure. The reaction pressure is preferably a pressure at which the carbonic acid ester forming agent, which is a raw material, does not flow out of the system at the reaction temperature and can flow out by-products such as phenol. Under these reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.

<About (meth)acrylation>

As illustrated in the above scheme, the terminal (meth)acrylate polycarbonate oligomer represented by Formula 1 and/or Formula 2 of the present invention is a polycarbonate oligomer represented by Formula A-1, and (meth)acrylic acid chloride It is obtained by the reaction of a (meth)acrylate agent such as

Specific examples of the (meth)acrylate agent include acrylic acid chloride, methacrylic acid chloride, acrylic acid, and methacrylic acid.

The usage-amount of (meth)acrylation agent is (meth)acryl with respect to all terminal hydroxyl groups of the polycarbonate oligomer represented by Formula (A-1), when obtaining the both terminal (meth)acrylate polycarbonate oligomer represented by Formula (1). The amount of the agent is usually 1.0 to 2.5 moles, preferably 1.1 to 2.0 moles, and more preferably 1.15 to 1.5 moles. In the case of obtaining the one-terminal (meth)acrylate polycarbonate oligomer represented by the formula (2), the (meth)acrylate agent is usually 0.5 to 1.5 times mole, with respect to all terminal hydroxyl groups of the polycarbonate oligomer represented by the formula (A-1); Preferably 0.55-1.25 times mole, More preferably, 0.6-1.0 times mole is used.

For example, when using (meth)acrylic acid chloride to acrylate the polycarbonate oligomer represented by the formula (A-1), since chloride ions are generated in the form of hydrogen chloride, it is preferable to use a hydrogen chloride scavenger together. As a hydrogen chloride scavenger, if it is a basic substance, it can be used. As the inorganic basic substance, alkali metal carbonate, hydrogen carbonate, or the like can be used. As an organic basic substance, tertiary amines can be used. As the tertiary amines, for example, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl -aliphatic amines such as diamylamine, N,N-diisopropylethylamine, N,N-dimethyl-cyclohexylamine, and N,N-diethyl-cyclohexylamine; N,N-dimethylaniline, N,N -Aromatic amines such as diethylaniline; Heterocyclic amines such as pyridine, picoline, and N,N-dimethylaminopyridine; 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5- and alicyclic amines such as diazabicyclo[4.3.0]non-5-ene.

The amount of the hydrogen chloride scavenger to be used is usually 0.8 to 10 moles, preferably 0.9 to 8 moles, and particularly preferably about 1.0 to 7 moles relative to the number of moles of the (meth)acrylate agent used. When the hydrogen chloride scavenger is less than 0.8 times the number of moles of the (meth) acrylate agent, the generated hydrogen chloride cannot be completely captured, and the polycarbonate oligomer represented by the formula A-1 as the raw material, or the target product, the formula 1 and/or The terminal (meth)acrylate polycarbonate oligomer represented by the general formula (2) is decomposed, and there is a possibility that the purity of the target product is reduced. Moreover, when the hydrogen chloride scavenger exceeds 10 moles with respect to the number of moles of the (meth)acrylate agent, it is not preferable because removal of the hydrogen chloride scavenger becomes complicated and not economical.

In this (meth)acrylation reaction, the solvent used may be any solvent capable of uniformly mixing the raw materials used, etc., specifically, halogenated hydrocarbons such as methylene chloride, tetrahydrofuran, dioxane, chlorobenzene, etc. can be heard The amount of the solvent used is not particularly limited, but is usually 0.5 to 100 times the weight of the polycarbonate oligomer represented by the formula (A-1), preferably 1 to 50 times the weight, and particularly preferably 2 to 10 times the weight.

The (meth)acrylation reaction is carried out at a relatively low temperature, and is usually -50 to 100°C, preferably -30 to 80°C, particularly preferably -15 to 60°C. When the reaction temperature exceeds 100° C., a side reaction occurs, leading to a decrease in the yield of the target product. In addition, if the temperature is less than -50°C, the reaction rate is slowed and the required time is too long, which is not economical.

As a reaction procedure, the polycarbonate oligomer and (meth)acrylation agent represented by Formula (A-1) are mixed beforehand in a solvent, and a method of adding a hydrogen chloride scavenger thereto, First, the polycarbonate represented by Formula (A-1) There is a method in which an oligomer and a hydrogen chloride scavenger are mixed in a solvent and a (meth)acrylation agent is added thereto. These methods WHEREIN: You may use the hydrogen chloride trapping agent and (meth)acrylation agent added later in the state diluted with a solvent.

Moreover, you may add hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6- di-tert- butyl-4-methylphenol (BHT) etc. as a polymerization inhibitor at the time of reaction, for example.

<About post-treatment and purification of (meth)acrylation>

In the (meth)acrylation reaction, the basic substance as a hydrogen chloride scavenger is often added in excess, and in particular, the organic basic substance is the target product, the terminal (meth)acrylate polycarbonate oligomer represented by the general formula (1) and/or general formula (2) together with Since it remains in an organic solvent and tends to produce undesirable phenomena, such as coloring and decomposition, it is preferable to remove in the washing|cleaning operation after reaction. In order to wash off an organic basic substance, it is preferable to wash|clean with the aqueous solution of an acidic substance. Although it does not specifically limit as an acidic substance to be used, For example, there exist hydrochloric acid, sulfuric acid, nitric acid etc. as an inorganic acidic substance, For example, As an organic acidic substance, For example, carboxylic acid, such as formic acid, acetic acid, propionic acid, butyric acid ; and sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Especially, an organic type acidic substance with low acidity is more preferable. After removing the hydrogen chloride scavenger, it is preferable to continue washing with water.

The method of obtaining the terminal (meth)acrylate polycarbonate oligomer represented by the obtained general formula (1) and/or general formula (2) as a precipitate by adding a poor solvent to the solution in which it is melt|dissolved, etc. are preferable. As said poor solvent, a C1-C6 aliphatic alcohol solvent, such as methanol, ethanol, and a propanol, or the mixture of the said aliphatic alcohol solvent and water is mentioned specifically, for example.

<About the terminal (meth)acrylate polycarbonate oligomer>

Specific examples of the preferred compound of the terminal (meth)acrylate polycarbonate oligomer represented by the general formula (1) and/or general formula (2) of the present invention are shown below.

Preferred compounds of the both-terminal (meth)acrylate polycarbonate oligomer represented by Formula 1 are as follows. In Formulas 1a and 1b, n is an integer of 1 or more, and the weight average molecular weight (Mw) is in the range of 300 or more and 10,000 or less.

[Formula 1a]

[Formula 1b]

Preferred compounds of the one-terminal (meth)acrylate polycarbonate oligomer represented by Formula 2 are as follows. In Formulas 2a and 2b, n is an integer of 1 or more, and the weight average molecular weight (Mw) is in the range of 300 or more and 10,000 or less.

[Formula 2a]

[Formula 2b]

The terminal (meth)acrylate polycarbonate oligomer represented by Formula 1 and/or Formula 2 of the present invention has a weight average molecular weight (Mw) in the range of 300 or more and 10,000 or less, and among them, preferably 500 or more and 9,000 or less, , the range of 800 or more and 8,500 or less is more preferable, and the range of 1,000 or more and 8,000 or less is still more preferable. If the weight average molecular weight (Mw) is within this range, it is preferable because good solubility in the organic solvent is obtained.

In addition, when the terminal (meth)acrylate polycarbonate oligomer represented by the general formula (1) and/or general formula (2) of the present invention is used as a component of an ultraviolet curable hard coat agent, pentaerythritol-based (meth)acrylate, etc. Since it is excellent in compatibility with the polyfunctional (meth)acryl monomer of, it exhibits the industrially advantageous effect that smooth coating film formation is possible by ultraviolet curing. Moreover, the terminal (meth)acrylate polycarbonate oligomer of this invention shows the remarkable effect that the cured film obtained by ultraviolet curing is excellent in abrasion resistance.

From the above facts, the terminal (meth)acrylate polycarbonate oligomer represented by the general formula (1) and/or general formula (2) of the present invention, in addition to the raw material for the ultraviolet curable hard coat agent, is a raw material for modeling of a 3D printer or thermosetting such as an epoxy resin. It is very useful as a modifier for resins.

Example

The present invention will be specifically described below by way of examples, but is not limited to these examples.

In addition, the weight average molecular weight (Mw) in the following example was measured by gel permeation chromatography. The method for analysis, etc. is as follows.

<Analysis method>

1. Gel Permeation Chromatography Measurements

(Analysis of oligomers)

Apparatus: Manufactured by Tosoh Corporation 　HLC-8320GPC

Flow rate: 0.35 ml/min, mobile phase: tetrahydrofuran, injection amount: 10 µl

Column: TSKgel guardcolumn SuperMP(HZ)-N, TSKgel SuperMultiporeHZ-N×3

Detector: RI

Analysis method: Let it be the relative molecular weight in terms of polystyrene. For polystyrene standards, A-500, A-2500, A-5000, F-1, F-2, F-4 manufactured by Tosoh Corporation are used.

(Analysis of Polymer)

Apparatus: Manufactured by Tosoh Corporation 　HLC-8320GPC

Flow rate: 1.0 ml/min, mobile phase: tetrahydrofuran, injection amount: 100 µl

Column: TSKgel guardcolumn HXL-L TSKgel G2000HXL x 2 + TSKgel G3000HXL + TSKgel G4000HXL

Detector: RI

Analysis method: Let it be the relative molecular weight in terms of polystyrene. For polystyrene standards, PStQuick E, F (E: F-40, F-4, A-5000, A-1000, F: F-20, F-2, A-2500, A-500) manufactured by Tosoh Corporation is used.

2. Determination of terminal hydroxy concentrations

^{Using 1} H-NMR, TCE (1,1,1,2-tetrachloroethane) was used as an internal standard, and bisphenol A and bisphenol C were used as samples to prepare a calibration curve for weight ratio with TCE. It was quantified by the method of calculating|requiring the phenol terminal weight from this calibration curve.

Apparatus: AscendTM 400 manufactured by BRUKER

Measurement conditions: room temperature, integration count 120 times

3. Identification of chemical structure

^{It carried out by 1} H-NMR measurement using the same apparatus as said "2.".

4. Evaluation of abrasion

Using a Taber abrasion tester ("MODEL174" manufactured by Taber Industries), the wear wheel was worn by 50 rotations under the conditions of a wear wheel CS-10 and a load of 2.45 N (250 gf).

The degree of wear by the abrasion test was evaluated as soaking (haze) using an ultraviolet-visible near-infrared spectrophotometer (V-780 manufactured by Nippon Spectroscopy Co., Ltd.).

<Reference Example 1> Synthesis of polycarbonate oligomer (A-1-a)

[Formula A-1-a]

In a four-neck flask equipped with a thermometer, a stirrer and a cooler, 690.0 g (2.7 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane and 403.8 g (1.9 mol) of diphenyl carbonate were placed in a reaction vessel After nitrogen substitution, 3.1 g of a 0.06% cesium carbonate aqueous solution was added at 110°C. After heating up to 200 degreeC, the pressure reduction degree was adjusted to 1.3 kPa, and it reacted, distilling the produced|generated phenol for 8 hours, and 737.1 g of reaction completion liquids were obtained.

Then, a solution obtained by dissolving 540 g of the obtained reaction solution in 1086 g of toluene was added dropwise to 6492 g of methanol in a four-neck flask over 2 hours while maintaining 15° C. to precipitate the target product. After stirring overnight, the precipitate was separated by filtration, and a washing step of redispersing the obtained wet cake in methanol was performed once. The precipitate was separated by filtration and dried to obtain 255 g of a powdery polycarbonate oligomer (A-1-a).

The weight average molecular weight of the obtained polycarbonate oligomer (A-1-a) was 3,373 (gel permeation chromatography), and the terminal hydroxyl concentration was 1.0 mmol/g.

<Example 1> Synthesis of terminal acrylate polycarbonate oligomer (1a)

[Formula 1a]

In a four-neck flask equipped with a thermometer, a stirrer, and a cooler, 207.0 g of the polycarbonate oligomer (A-1-a) obtained in Reference Example 1 was put, and the reaction vessel was replaced with nitrogen, and then 53.9 g (0.60 mol) of acrylic acid chloride, 455 g of dichloromethane and 14.5 mg of metoquinone were added under a nitrogen stream. A mixed solution of 53.5 g (0.53 mol) of triethylamine and 205 g of dichloromethane was added at 15° C. over 2 hours. After continuing stirring at 15°C for 3 hours, 400 g of water and 1300 g of methanol were added, and after stirring for 1 hour, the solution of the upper layer separated by standing was taken out, and further 900 g of methanol was added and stirred. . After repeating the operation of extracting the solution of the upper layer separated by standing still, 900 g of water is added, a precipitate obtained by stirring for 2 hours is filtered off, and the wet cake thus obtained is redispersed in 750 g of methanol. was carried out. Thereafter, the precipitate was separated by filtration and dried to obtain 177 g of the terminal acrylate polycarbonate oligomer (1a) in the form of pale yellowish white powder.

The weight average molecular weight of the obtained terminal acrylate polycarbonate oligomer (1a) was 4,024 (gel permeation chromatography). ^From the analysis result of 1 H-NMR, it was confirmed that the obtained oligomer was the both-terminal acrylate polycarbonate oligomer represented by the said Formula (1a).

As a result of mixing all of the obtained terminal acrylate polycarbonate oligomer (1a) 2.0 g, polyfunctional acrylate pentaerythritol tetraacrylate 8.0 g, cyclohexanone 10.0 g, and Irgacure (184) 0.5 g, a transparent solution was obtained It was confirmed that a transparent hard coat film was formed on the PC substrate by ultraviolet irradiation.

From this result, it became clear that the obtained terminal acrylate polycarbonate oligomer (1a) showed favorable solubility in organic solvents, such as cyclohexanone, and was excellent in compatibility with pentaerythritol tetraacrylate which is a polyfunctional acrylate.

Subsequently, the obtained solution was applied onto a commercially available polycarbonate sheet using a bar coater, dried at 80° C. for 1 minute, and cured by irradiating with an illuminance of 850 mW/cm 2 using a high-pressure mercury lamp. Using the obtained cured film, using a Taber abrasion tester ("MODEL174" by Taber Industries), it was abraded by 50 rotations under the conditions of a wear wheel CS-10 and a load of 2.45 N (250 gf). The haze before and after 50 rotations was measured using an ultraviolet visible near-infrared spectrophotometer (V-780 manufactured by Nippon Spectroscopy Co., Ltd.) equipped with an integrating sphere unit. As a result, the haze was 5.5%.

<Example 2> Synthesis of terminal methacrylate polycarbonate oligomer (1b)

[Formula 1b]

130.0 g of the polycarbonate oligomer (A-1-a) synthesized in the same manner as in Reference Example 1 was put into a four-neck flask equipped with a thermometer, a stirrer, and a cooler, and the reaction vessel was replaced with nitrogen, followed by methacrylic acid chloride 19.9 g (0.19 mol), 286.2 g of dichloromethane, and 10.0 mg of metoquinone were added under a nitrogen stream. At 15° C. 25.4 g (0.25 mole) of triethylamine were added over 45 minutes. Furthermore, after continuing stirring at 15 degreeC for 2 hours, 390 g of 0.1 mol/L hydrochloric acid water was added, and it stirred for 20 minutes, and liquid-separated, and obtained the organic solvent layer. Then, water washing and analysis were performed once with 260 g of water, 1040 g of methanol was added, and the target substance was precipitated. Then, the operation|work of extracting the upper layer solution which was left still and isolate|separated was performed, and 780 g of methanol was further added, and it stirred. A washing step was performed in which the precipitate was separated by filtration, and the obtained wet cake was redispersed in 780 g of methanol. Thereafter, the precipitate was separated by filtration and dried to obtain 120 g of white powdery terminal methacrylate polycarbonate oligomer (1b).

The weight average molecular weight of the obtained terminal methacrylate polycarbonate oligomer (1b) was 3,134 (gel permeation chromatography). ^From the analysis result of 1 H-NMR, it was confirmed that the obtained oligomer was the both terminal methacrylate polycarbonate oligomer represented by the said Formula (1b).

When 2.0 g of the obtained terminal methacrylate polycarbonate oligomer (1b), 8.0 g of polyfunctional acrylate pentaerythritol tetraacrylate, 10.0 g of cyclohexanone, and 0.5 g of Irgacure (184) were mixed, a transparent solution was obtained It was confirmed that a transparent hard coat film was formed on the PC substrate by ultraviolet irradiation.

From this result, it became clear that the obtained terminal methacrylate polycarbonate oligomer (1b) showed good solubility in organic solvents, such as cyclohexanone, and was excellent in compatibility with pentaerythritol tetraacrylate which is a polyfunctional acrylate. .

Then, about the obtained said solution, when the cured film was produced by the method similar to Example 1, and the haze after abrasion test was measured, haze was 5.1 %.

<Comparative Example 1> Synthesis of diacrylate polycarbonate-1

In a four-neck flask equipped with a thermometer, a stirrer and a condenser, 246.1 g (1.08 mol) of 2,2-bis(4-hydroxyphenyl)propane and 237.1 g (1.12 mol) of diphenyl carbonate were placed, and the reaction vessel was purged with nitrogen. After that, 0.9 g of a 0.08% cesium carbonate aqueous solution was added at 110°C. After raising the temperature to 220 ° C., the reaction was carried out at normal pressure for 40 minutes, and while the produced phenol was discharged, the pressure reduction degree was set to 13.3 kPa over 80 minutes, and after raising the temperature to 240 ° C., the pressure reduction degree was 0.8 kPa over 40 minutes. . Furthermore, it heated up to 285 degreeC, and it reacted at 0.7 kPa for 7 hours, and 250 g of reaction completion liquids were obtained.

Next, a solution obtained by dissolving 150.0 g of the obtained reaction end solution in 530.0 g of dichloromethane was added dropwise into 1850 g of methanol to precipitate the target product. After stirring for 1 hour, the precipitate was separated by filtration and dried to obtain a powdery polycarbonate.

The weight average molecular weight of the obtained polycarbonate was 31,240 (gel permeation chromatography), and the terminal hydroxyl concentration was 0.13 mmol/g.

Next, in a four-neck flask equipped with a thermometer, a stirrer, and a cooler, 13.6 g of the obtained polycarbonate was put, the reaction vessel was substituted with nitrogen, and 0.3 g (0.003 mol) of acrylic acid chloride and 47.6 g of dichloromethane were added under a nitrogen stream. Then, 0.4 g (0.004 mol) of triethylamine was added at 15°C. After stirring for 2 hours, the reaction solution was added to 163 g of methanol to precipitate the target product. Then, the deposit was separated by filtration and dried, 14.1 g of the obtained wet cake was dissolved in 47.6 g of dichloromethane, the solution was added to 163 g of methanol, and it was made to precipitate. Thereafter, the precipitate was separated by filtration and dried to obtain 13 g of a white powdery compound.

^{From the analysis result of <1>} H-NMR of the obtained compound, it confirmed that it was a terminal diacrylate polycarbonate.

The synthesized diacrylate polycarbonate did not dissolve in cyclohexanone.

In addition, a mixture of using dichloromethane instead of cyclohexanone, 0.6 g of diacrylate polycarbonate, 2.4 g of polyfunctional acrylate pentaerythritol tetraacrylate, and 3.0 g of dichloromethane is in a cloudy state, and the hard coat film is It was impossible to form.

<Comparative Example 2> Synthesis of diacrylate polycarbonate-2

In a four-neck flask equipped with a thermometer, a stirrer and a cooler, 276.9 g (1.08 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane and 237.1 g (1.12 mol) of diphenyl carbonate were placed in a reaction vessel After nitrogen substitution, 0.9 g of a 0.08% cesium carbonate aqueous solution was added at 110°C. After raising the temperature to 220 ° C., the reaction was carried out at normal pressure for 40 minutes, and while the produced phenol was discharged, the pressure reduction degree was set to 13.3 kPa over 80 minutes, and after raising the temperature to 240 ° C., the pressure reduction degree was 0.8 kPa over 40 minutes. . Furthermore, it heated up to 285 degreeC, and it reacted at 0.7 kPa for 7 hours, and 250 g of reaction completion liquids were obtained.

Next, a solution obtained by dissolving 150.0 g of the obtained reaction completion solution in 530.0 g of dichloromethane was added dropwise to 1850 g of methanol to precipitate the target product. After stirring for 1 hour, the precipitate was separated by filtration and dried to obtain a powdery polycarbonate.

The weight average molecular weight of the obtained polycarbonate was 30,760 (gel permeation chromatography), and the terminal hydroxyl concentration was 0.13 mmol/g.

Next, 13.6 g of the obtained polycarbonate was put into a four-neck flask equipped with a thermometer, a stirrer, and a cooler, and the reaction vessel was purged with nitrogen, and then 0.3 g (0.003 mol) of acrylic acid chloride and 47.6 g of dichloromethane were added under a nitrogen stream. After that, 0.4 g (0.004 mol) of triethylamine was added at 15°C. After stirring for 2 hours, the reaction solution was added to 163 g of methanol to precipitate the target product. Then, the deposit was separated by filtration and dried, 14.1 g of the obtained wet cake was dissolved in 47.6 g of dichloromethane, the solution was added to 163 g of methanol, and it was made to precipitate. Thereafter, the precipitate was separated by filtration and dried to obtain 13 g of a white powdery compound.

^{From the analysis result of <1>} H-NMR of the obtained compound, it confirmed that it was a terminal diacrylate polycarbonate.

The synthesized diacrylate polycarbonate did not dissolve in cyclohexanone.

In addition, a mixture of using dichloromethane instead of cyclohexanone, 0.6 g of diacrylate polycarbonate, 2.4 g of polyfunctional acrylate pentaerythritol tetraacrylate, and 3.0 g of dichloromethane is in a cloudy state, and the hard coat film is It was impossible to form.

From the results of Comparative Examples 1 and 2, the terminal (meth)acrylate polycarbonate oligomer represented by Chemical Formulas 1 and 2 has good solubility in organic solvents by setting the weight average molecular weight (Mw) within a specific range. It became clear that compatibility with polyfunctional acrylate etc. was excellent.

<Comparative Reference Example 1> Synthesis of polycarbonate oligomer (X)

[Formula X]

In a four-neck flask equipped with a thermometer, a stirrer, and a cooler, 616.4 g (2.7 mol) of 2,2-bis(4-hydroxyphenyl)propane and 404.8 g (1.9 mol) of diphenyl carbonate were placed, and the reaction vessel was purged with nitrogen. After that, 2.9 g of a 0.06% cesium carbonate aqueous solution was added at 110°C. After heating up to 210 degreeC, the pressure reduction degree was adjusted to 0.6 kPa, and reaction was carried out, distilling the produced|generated phenol for 8 hours, and 646.9 g of reaction completion liquids were obtained.

Next, a solution obtained by dissolving 140.0 g of the obtained reaction completion solution in 252.0 g of toluene was added dropwise to 1680 g of methanol in a four-neck flask over 2 hours while maintaining 15° C. to precipitate the target product. After stirring overnight, the precipitate was separated by filtration, and a washing step of redispersing 2533 g of the obtained wet cake in methanol was performed twice. The precipitate was separated by filtration and dried to obtain a powdery polycarbonate oligomer (X).

The weight average molecular weight of the obtained polycarbonate oligomer was 2,944 (gel permeation chromatography), and the terminal hydroxyl concentration was 1.2 mmol/g.

<Comparative Example 3> Synthesis of terminal acrylate polycarbonate oligomer (x-1)

[Formula x-1]

130.0 g of the polycarbonate oligomer (X) obtained in Comparative Reference Example 1 was put into a four-neck flask equipped with a thermometer, a stirrer, and a cooler, and the reaction vessel was substituted with nitrogen, and then acrylic acid chloride 35.3 g (0.39 mol), dichloromethane 285.7 g, 17.4 mg of metoquinone was added under a stream of nitrogen. A mixed solution of 47.1 g (0.47 mol) of triethylamine and 65 g of dichloromethane was added at 15° C. over 2 hours. Furthermore, after continuing stirring at 15 degreeC for 3 hours, 1300 g of methanol was added, and the target substance was precipitated. Thereafter, the precipitate was separated by filtration, and a washing step of redispersing the obtained wet cake twice with 900 g of water and twice with 900 g of methanol was performed. Thereafter, the precipitate was separated by filtration and dried to obtain 138 g of a terminal acrylate polycarbonate oligomer (x-1) in the form of an off-white powder.

The weight average molecular weight of the obtained terminal acrylate polycarbonate oligomer (x-1) was 3,453 (gel permeation chromatography). ^From the analysis result of 1 H-NMR, it was confirmed that the obtained oligomer was the both terminal acrylate polycarbonate oligomer represented by the said Formula (x-1).

When 2.0 g of the obtained terminal acrylate polycarbonate oligomer (x-1), 8.0 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, 10.0 g of cyclohexanone, and 0.5 g of Irgacure (184) were mixed, a clear solution was obtained. It was obtained and confirmed that the transparent hard-coat film was formed on a PC board by ultraviolet irradiation.

Then, about the obtained said solution, when the cured film was produced similarly to Example 1 and the haze after abrasion test was measured, haze was 9.4 %.

<Comparative Example 4> Synthesis of terminal methacrylate polycarbonate oligomer (x-2)

[Formula x-2]

In a four-neck flask equipped with a thermometer, a stirrer, and a cooler, 120.0 g of polycarbonate oligomer (X) synthesized in the same manner as in Comparative Reference Example 1 was put, and the reaction vessel was replaced with nitrogen, and then 18.3 g (0.18) of methacrylic acid chloride mol), dichloromethane 265 g, and metoquinone 9.3 mg were added under a nitrogen stream. A mixed solution of 23.4 g (0.47 mol) of triethylamine and 60 g of dichloromethane was added at 15° C. over 45 minutes. Furthermore, after continuing stirring at 15 degreeC for 2 hours, 0.1 mol/L hydrochloric acid water 360g was added, and it stirred for 20 minutes, it liquid-separated and obtained the organic solvent layer. Then, water washing and analysis were performed once with 240 g of water, 960 g of methanol was added, and the target substance was precipitated. Then, the operation|work of extracting the upper layer solution which was left still and wasolate|separated was performed, further, 720 g of methanol was added, and it stirred. A washing step was performed in which the precipitate was separated by filtration and the obtained wet cake was redispersed in 900 g of methanol. Thereafter, the precipitate was separated by filtration and dried to obtain 123 g of white powdery terminal methacrylate polycarbonate oligomer (x-2).

The weight average molecular weight of the obtained terminal methacrylate polycarbonate oligomer (x-2) was 3,147 (gel permeation chromatography). ^From the analysis result of 1 H-NMR, it was confirmed that the obtained oligomer was the methacrylate polycarbonate oligomer of both terminals represented by the said Formula (x-2).

1.0 g of the obtained terminal methacrylate polycarbonate oligomer (x-2), 9.0 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, 10.0 g of cyclohexanone, and 0.5 g of Irgacure (184) were mixed, a clear solution This was obtained and it confirmed that the transparent hard-coat film was formed on a PC board|substrate by ultraviolet irradiation.

The cured film was produced by the method similar to Example 1, and when the haze after abrasion test was measured, haze was 12.8 %.

From these results, the terminal methacrylate polycarbonate oligomer represented by the general formula (1) and/or general formula (2) of the present invention exhibits good solubility in organic solvents such as cyclohexanone, and is a polyfunctional acrylate pentaerythritol tetraacrylate It became clear that it was excellent in compatibility with. Moreover, it was confirmed that the terminal methacrylate polycarbonate oligomer of this invention was excellent in abrasion resistance when it was set as a cured film.

Claims (1)

A terminal (meth)acrylate polycarbonate oligomer represented by Formula 1 and/or Formula 2 below, and having a weight average molecular weight (Mw) in the range of 300 or more and 10,000 or less.
[Formula 1]

[Formula 2]

(In Formulas 1 and 2, R ₁ each independently represents a hydrogen atom or a methyl group, R ₂ , R ₃ each independently represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, and n is an integer of 1 or more. , R ₂ and the sum of the number of carbon atoms of _{R 3 is 14 or less.)}

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