JP7387973B2 - Terminal (meth)acrylate polycarbonate oligomer - Google Patents

Description

The present invention relates to terminal (meth)acrylate polycarbonate oligomers that have good solvent solubility and excellent wear resistance when cured.

Resin materials are widely used as engineering plastics because they are lightweight, inexpensive, and have excellent processability, but they are inferior in surface hardness, scratch resistance, and chemical resistance compared to glass and metal. Therefore, it cannot be used as an alternative material. In order to improve these drawbacks of resin materials, a hard coat treatment is used to form a thin resin film made of a material different from the base resin on the resin surface to protect the base resin from external factors and improve the surface. This is commonly done. To form this hard coat layer, a system is adopted in which a hard coat agent is applied to the resin surface of the base material, dried, and then irradiated with radiation such as electron beams or ultraviolet (UV) as necessary to cure the resin. (For example, Patent Documents 1 and 2). Among these, UV-curable hard coating agents that use UV-curable resins can be processed at lower temperatures and in a shorter time than conventional hard coating agents, so they are highly productive and are being used in a variety of applications. There is.
This ultraviolet curable hard coating agent uses polyfunctional (meth)acrylic monomers such as pentaerythritol (meth)acrylate as the main component, so the components to be blended are the same as these polyfunctional (meth)acrylic monomers. High compatibility is required.

Japanese Patent Application Publication No. 2010-024255 Japanese Patent Application Publication No. 2016-011365

The present invention has been made against the background of the above-mentioned circumstances, and is intended to be used as a raw material for ultraviolet curable (meth)acrylic resin used in ultraviolet curable hard coating agents, etc. An object of the present invention is to provide a terminal (meth)acrylate polycarbonate oligomer that has good solvent solubility and excellent wear resistance when cured.

As a result of intensive studies to solve the above-mentioned problems, the present inventors found that in the terminal (meth)acrylate polycarbonate represented by the following formula (1) and/or the following formula (2), the weight average molecular weight (Mw) is The present invention was completed based on the discovery that oligomers in a specific range have good compatibility with polyfunctional (meth)acrylic monomers and solvent solubility, and exhibit excellent wear resistance when cured.

The invention is as follows.
1. A terminal (meth)acrylate polycarbonate oligomer represented by the following formula (1) and/or the following formula (2) 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, and R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. (n is an integer of 1 or more. However, the total number of carbon atoms in R ₂ and R ₃ is 14 or less.)

Since 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, it is compatible with polyfunctional (meth)acrylic monomers such as pentaerythritol-based (meth)acrylate. UV curing is possible due to good compatibility and solvent solubility, and the resulting cured film has excellent abrasion resistance, making it ideal as a raw material for UV curable hard coating agents. It exhibits an industrially advantageous effect of being able to form a coating film.

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

Hereinafter, the terminal (meth)acrylate polycarbonate oligomer of the present invention will be explained in detail.
The terminal (meth)acrylate polycarbonate oligomer of the present invention, as illustrated in the reaction formula below, comprises a polycarbonate oligomer represented by formula (A-1) and a (meth)acrylating agent such as (meth)acrylic acid chloride. It is a compound represented by the following formula (1) and/or the following formula (2), which is obtained by reaction with the following formula (1) and has a weight average molecular weight (Mw) in the range of 300 or more and 10,000 or less.
(The definitions of R ₁ to R ₃ and n in the reaction formula are the same as in formulas (1) and (2) above.)

<About the polycarbonate oligomer represented by formula (A-1)>
The chemical structure of the terminal (meth)acrylate polycarbonate oligomer of the present invention will be explained by explaining in detail the polycarbonate oligomer represented by the following formula (A-1), which is a raw material for its synthesis. That is, regarding specific examples of n in formula (A-1), preferred chemical groups and substituents thereof, formula (1) and/or formula (2) representing the terminal (meth)acrylate polycarbonate oligomer of the present invention It is the same as n in the middle.
(The definitions of R ₂ , R ₃ , and n in formula (A-1) are the same as in formulas (1) and (2) above.)
The substitution position of the methyl group in the above formula (A-1) is preferably the ortho position with respect to the oxygen atom bonded to the benzene ring.

R ₂ and R ₃ in the above 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 chain having 1 to 12 carbon atoms. A straight-chain or branched alkyl group, more preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms, and even more preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms. It is an alkyl group with a shape. 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- -nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. However, the total number of carbon atoms of R ₂ and R ₃ must be 14 or less.

The polycarbonate oligomer represented by formula (A-1) can be produced by any conventionally known production method. Specifically, examples thereof include interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of cyclic carbonate compounds, and solid phase transesterification of prepolymers. Among these, it is industrially advantageous to use interfacial polymerization, melt transesterification, and prepolymer solid phase transesterification. Among these, a melt transesterification method that does not use phosgene and a solid-phase transesterification method of a prepolymer using a melt transesterification method are particularly preferred. 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.
(The definitions of R ₂ and R ₃ in formula (B-1) are the same as in formulas (1) and (2) above.)

<About the aromatic dihydroxy compound represented by formula (B-1)>
Specific examples of the aromatic dihydroxy compound represented by formula (B-1) include bis(4-hydroxy-3-methylphenyl)methane, 1,1-bis(4-hydroxy-3-methyl phenyl)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)dodecane, bis(4-hydroxy-2-methylphenyl)methane, 1,1-bis(4-hydroxy-2-methylphenyl)ethane, 2,2-bis(4-hydroxy-2-methyl) phenyl)propane, etc.
In the polymerization reaction, such aromatic dihydroxy compounds may be used alone or in a mixture of two or more kinds in any ratio.

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

<About melt transesterification method>
A melt transesterification method will be described as a method for producing the polycarbonate oligomer represented by formula (A-1).
When using the aromatic dihydroxy compound represented by formula (B-1) and diphenyl carbonate as the carbonate ester forming agent, the melt transesterification reaction is carried out under normal pressure or reduced pressure in the presence of a catalyst. This is done by stirring while heating in an active gas atmosphere and distilling out the produced phenol. Usually, the desired molecular weight and amount of terminal hydroxyl groups are adjusted by adjusting the mixing ratio of the aromatic dihydroxy compound represented by formula (B-1) and the carbonate ester forming agent and the degree of reduced pressure during the transesterification reaction. A polycarbonate oligomer represented by (A-1) can be obtained.
In order to obtain the polycarbonate oligomer represented by formula (A-1), the mixing ratio of the aromatic dihydroxy compound represented by formula (B-1) and the carbonate ester forming agent is as shown in formula (B-1). The amount of the carbonate ester forming agent is usually 0.2 to 1.0 times the mole, preferably 0.25 to 0.95 times, more preferably 0.3 to 0.90 times the mole of the aromatic dihydroxy compound to be used. Use twice the molar amount.
During the melt transesterification reaction, a transesterification catalyst is used as necessary to increase the reaction rate. There are no particular restrictions on the transesterification catalyst, and examples include inorganic alkali metal compounds such as hydroxides, carbonates, and hydrogen carbonates of lithium, sodium, and cesium, and organic alkali metal compounds such as alcoholates and organic carboxylates. Alkali metal compounds; inorganic alkaline earth metal compounds such as hydroxides and carbonates such as beryllium and magnesium; alkaline earth metal compounds such as organic alkaline earth metal compounds such as alcoholates and organic carboxylates; tetramethylboron; Basic boron compounds such as sodium salts, calcium salts, and magnesium salts such as tetraethylboron and butyltriphenylboron; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine, or derivatives from these compounds Basic phosphorus compounds such as quaternary phosphonium salts; Basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; Amine-based compounds such as 4-aminopyridine, 2-dimethylaminoimidazole, and aminoquinoline Known transesterification catalysts such as compounds can be used. Among these, alkali metal compounds are preferred, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferred.
The amount of the catalyst to be used is within a range where the catalyst residue does not cause any quality problems with the produced oligomer, and since the suitable addition amount differs depending on the type of catalyst, it cannot be stated unconditionally, but roughly, for example, the formula (B- Usually 0.05 to 100 μmol, preferably 0.08 to 50 μmol, more preferably 0.1 to 20 μmol, and even more preferably 0.1 to 5μmol per mole of the aromatic dihydroxy compound represented by 1). It is a mole. The catalyst may be added as it is or dissolved in a solvent, and the solvent is preferably one that does not affect the reaction, such as water or phenol.
The reaction conditions for the melt transesterification reaction are such that the temperature is usually in the range of 120 to 360°C, preferably in the range of 150 to 280°C, more preferably in the range of 180 to 260°C. If the reaction temperature is too low, the transesterification reaction will not proceed, and if the reaction temperature is too high, side reactions such as decomposition reactions will proceed, which is not preferable. The reaction is preferably carried out under reduced pressure. The reaction pressure is preferably such that the carbonate ester forming agent, which is a raw material, does not distill out of the system at the reaction temperature, and by-products such as phenol can distill out. Under such reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.

<About (meth)acrylation>
As exemplified in the above reaction formula, 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), Obtained by reaction with a (meth)acrylating agent such as (meth)acrylic acid chloride.
Specific examples of the (meth)acrylating agent include acrylic acid chloride, methacrylic acid chloride, acrylic acid, and methacrylic acid.
When obtaining a (meth)acrylate polycarbonate oligomer at both ends represented by formula (1), the amount of the (meth)acrylating agent to be used is determined so that all the terminal hydroxy groups of the polycarbonate oligomer represented by formula (A-1) are The (meth)acrylating agent is usually used in an amount of 1.0 to 2.5 times in mole, preferably 1.1 to 2.0 times in mole, and more preferably 1.15 to 1.5 times in mole. When obtaining a one-end (meth)acrylate polycarbonate oligomer represented by formula (2), a (meth)acrylating agent is added to all terminal hydroxy groups of the polycarbonate oligomer represented by formula (A-1). , usually 0.5 to 1.5 times the mole, preferably 0.55 to 1.25 times the mole, and more preferably 0.6 to 1.0 times the mole.
For example, when (meth)acrylic acid chloride is used to acrylate the polycarbonate oligomer represented by formula (A-1), chloride ions are generated in the form of hydrogen chloride, so a hydrogen chloride scavenger must be used in combination. is preferred. As the hydrogen chloride scavenger, any basic substance can be used. As the inorganic basic substance, alkali metal carbonates, hydrogen carbonates, etc. can be used. Tertiary amines can be used as the organic basic substance. Examples of tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl-diamylamine, N,N- Aliphatic amines such as diisopropylethylamine, N,N-dimethyl-cyclohexylamine, N,N-diethyl-cyclohexylamine; Aromatic amines such as N,N-dimethylaniline, N,N-diethylaniline; pyridine, picoline, N , N-dimethylaminopyridine; and fats such as 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[4.3.0]non-5-ene. Examples include cyclic amines.
The amount of the hydrogen chloride scavenger used is usually 0.8 to 10 times the mole of the (meth)acrylating agent used, preferably 0.9 to 8 times the mole, particularly preferably is about 1.0 to 7 times the mole. If the hydrogen chloride scavenger is less than 0.8 times the number of moles of the (meth)acrylating agent, the generated hydrogen chloride cannot be captured completely, and the polycarbonate oligomer represented by the raw material formula (A-1) or the purpose There is a risk that the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or formula (2), which is a product, will be decomposed, resulting in a decrease in the purity of the target product. Moreover, if the hydrogen chloride scavenger exceeds 10 times the mole number of the (meth)acrylating agent, it is not preferable because the removal of the hydrogen chloride scavenger not only becomes complicated but also uneconomical.

In this (meth)acrylation reaction, the solvent used may be any solvent that can uniformly mix the raw materials used, and specifically, halogenated hydrocarbons such as methylene chloride, tetrahydrofuran, dioxane, Examples include chlorobenzene. 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 formula (A-1), preferably 1 to 50 times the weight, particularly preferably 2 ~10 times the weight.
The (meth)acrylation reaction is carried out at a relatively low temperature, usually -50 to 100°C, preferably -30 to 80°C, particularly preferably -15 to 60°C. When the reaction temperature exceeds 100°C, side reactions occur, leading to a decrease in the yield of the target product. Further, if it is lower than -50°C, the reaction rate is slow and the time required is uneconomical.
The reaction procedure includes a method in which a polycarbonate oligomer represented by formula (A-1) and a (meth)acrylating agent are mixed in advance in a solvent, and a hydrogen chloride scavenger is added thereto; There is a method in which a polycarbonate oligomer represented by (A-1) and a hydrogen chloride scavenger are mixed in a solvent, and a (meth)acrylating agent is added thereto. In these methods, the hydrogen chloride scavenger and (meth)acrylating agent that are added later may be used in a diluted state in a solvent.
Further, during the reaction, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-di-tert-butyl-4-methylphenol (BHT), etc. may be added.

<About post-treatment and purification of (meth)acrylation>
In the (meth)acrylation reaction, a basic substance that is a hydrogen chloride scavenger is often added in excess, and in particular, an organic basic substance is Since it remains in the organic solvent together with the terminal (meth)acrylate polycarbonate oligomer represented by and tends to cause undesirable phenomena such as coloring and decomposition, it is preferable to remove it in a washing operation after the reaction. In order to wash and remove the organic basic substance, it is preferable to wash with an aqueous solution of an acidic substance. The acidic substance to be used is not particularly limited, but examples of inorganic acidic substances include hydrochloric acid, sulfuric acid, nitric acid, etc., and examples of organic acidic substances include formic acid, acetic acid, propionic acid, Examples include carboxylic acids such as butyric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid. Among these, organic acidic substances with low acidity are more preferred. After removing the hydrogen chloride scavenger, it is preferable to subsequently perform washing with water.
The obtained terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or formula (2) is preferably formed into a precipitate by adding a poor solvent to the solution in which it is dissolved. . Specific examples of the poor solvent include aliphatic alcohol solvents having 1 to 6 carbon atoms such as methanol, ethanol, and propanol, or mixtures of the aliphatic alcohol solvents and water.

<About terminal (meth)acrylate polycarbonate oligomer>
Specific examples of preferred compounds of the terminal (meth)acrylate polycarbonate oligomers represented by formula (1) and/or formula (2) of the present invention are shown below.
Preferred compounds of the (meth)acrylate polycarbonate oligomer at both ends 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.

Preferred compounds of the one-end (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.

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 to 10,000, particularly 500 to 9 ,000 or less, more preferably 800 or more and 8,500 or less, even more preferably 1,000 or more and 8,000 or less. It is preferable that the weight average molecular weight (Mw) is within this range because good solubility in organic solvents can be obtained.
In addition, when the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or formula (2) of the present invention is used as a component of an ultraviolet curable hard coating agent, pentaerythritol, which is the main component, Because it has excellent compatibility with polyfunctional (meth)acrylic monomers such as (meth)acrylates, it exhibits the industrially advantageous effect of being able to form smooth coating films by ultraviolet curing. Furthermore, the terminal (meth)acrylate polycarbonate oligomer of the present invention exhibits a remarkable effect in that a cured film obtained by ultraviolet curing has excellent abrasion resistance.
From the above, the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or formula (2) of the present invention can be used as a raw material for modeling materials for 3D printers in addition to raw materials for ultraviolet curable hard coating agents. It is very useful as a modifier for thermosetting resins such as and epoxy resins.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to examples, but it is not limited to these examples.
In addition, the weight average molecular weight (Mw) in the following examples was measured by gel permeation chromatography. The methods for analysis etc. are as follows.
<Analysis method>
1. Gel permeation chromatography measurement (oligomer analysis)
Equipment: Tosoh Corporation HLC-8320GPC
Flow rate: 0.35ml/min, mobile phase: tetrahydrofuran, injection amount: 10μl
Column: TSKgel guardcolumn SuperMP(HZ)-N, TSKgel SuperMultiporeHZ-N x 3 Detector: RI
Analysis method: Relative molecular weight in terms of polystyrene. The polystyrene samples used are A-500, A-2500, A-5000, F-1, F-2, and F-4 manufactured by Tosoh Corporation.
(Polymer analysis)
Equipment: Tosoh Corporation HLC-8320GPC
Flow rate: 1.0ml/min, mobile phase: tetrahydrofuran, injection amount: 100μl
Column: TSKgel guardcolumn HXL-L TSKgel G2000HXL x 2 + TSKgel G3000HXL + TSKgel G4000HXL
Detector: RI
Analysis method: Relative molecular weight in terms of polystyrene. Polystyrene standard products are manufactured by Tosoh Corporation PStQuick E,F (E: F-40, F-4, A-5000, A-1000, F: F-20, F-2, A-2500, A-500) use.
2. Measurement of terminal hydroxyl concentration
Using ¹ H-NMR, a calibration curve of the weight ratio with TCE was created using TCE (1,1,1,2-tetrachloroethane) as an internal standard and bisphenol A and bisphenol C as standards. Quantification was performed by determining the weight of the phenol end from this calibration curve.
Equipment: BRUKER AscendTM 400
Measurement conditions: room temperature, 120 accumulations 3. Identification of chemical structure Identification was carried out by ¹ H-NMR measurement using the same equipment as in "2." above.
4. Evaluation of abrasion property Using a Taber abrasion tester (“MODEL174” manufactured by Taber Industries), the abrasion wheel CS-10 was rotated 50 times under the condition of a load of 2.45N (250gf).
The degree of abrasion in the above abrasion test was evaluated as haze using an ultraviolet-visible near-infrared spectrophotometer (V-780, manufactured by JASCO Corporation).

<Reference Example 1> Synthesis of polycarbonate oligomer (A-1-a)
In a four-necked flask equipped with a thermometer, stirrer, and condenser, 690.0 g (2.7 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane and 403.8 g (1 mol) of diphenyl carbonate were added. After the reaction vessel was purged with nitrogen, 3.1 g of a 0.06% cesium carbonate aqueous solution was added at 110°C. After raising the temperature to 200° C., the degree of vacuum was adjusted to 1.3 kPa, and the reaction was carried out for 8 hours while distilling the produced phenol, to obtain 737.1 g of a reaction-completed liquid.
Next, a solution in which 540 g of the obtained reaction-completed liquid was dissolved in 1086 g of toluene was added dropwise to 6492 g of methanol in a 4-necked flask over 2 hours while maintaining the temperature at 15° C. to precipitate the target product. After stirring overnight, the precipitate was filtered off and the resulting wet cake was subjected to one wash step of redispersing it in methanol. The precipitate was filtered and dried to obtain 255 g of powdered 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)
207.0 g of the polycarbonate oligomer (A-1-a) obtained in Reference Example 1 was placed in a four-necked flask equipped with a thermometer, stirrer, and condenser, and after purging the reaction vessel with nitrogen, acrylic acid chloride was added. 53.9 g (0.60 mol), 455 g of dichloromethane, and 14.5 mg of methoquinone were added under a nitrogen stream. At 15° C., a mixed solution of 53.5 g (0.53 mol) of triethylamine and 205 g of dichloromethane was added over 2 hours. After further stirring at 15° C. for 3 hours, 400 g of water and 1,300 g of methanol were added, and after stirring for 1 hour, the solution was left to stand and the separated upper layer was taken out, followed by further addition of 900 g of methanol and stirring. After repeating the process of standing still and removing the separated upper layer solution, 900 g of water was added and the resulting precipitate was filtered by stirring for 2 hours, and the resulting wet cake was poured into 750 g of methanol. A washing step for redispersion was performed. Thereafter, the precipitate was filtered and dried to obtain 177 g of terminal acrylate polycarbonate oligomer (1a) in the form of a 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 results of ¹ H-NMR analysis, it was confirmed that the obtained oligomer was a double-terminated acrylate polycarbonate oligomer represented by the above formula (1a).
2.0 g of the obtained terminal acrylate polycarbonate oligomer (1a), 8.0 g of pentaerythritol tetraacrylate which is a polyfunctional acrylate, 10.0 g of cyclohexanone, and 0.5 g of Irgacure (184) were all mixed together to form a transparent solution. It was confirmed that a transparent hard coat film was formed on the PC board by UV irradiation.
From this result, it is clear that the obtained terminal acrylate polycarbonate oligomer (1a) shows good solubility in organic solvents such as cyclohexanone, and also has excellent compatibility with pentaerythritol tetraacrylate, which is a polyfunctional acrylate. became.
Subsequently, the obtained solution was applied onto a commercially available polycarbonate sheet using a bar coater, dried at 80° C. for 1 minute, and then cured by irradiation with an illuminance of 850 mW/cm ² using a high-pressure mercury lamp. . The obtained cured film was abraded by rotating it 50 times using a Taber abrasion tester ("MODEL174" manufactured by Taber Industries) using an abrasion wheel CS-10 and a load of 2.45N (250gf). The haze around 50 rotations was measured using an ultraviolet-visible-near-infrared spectrophotometer (V-780 manufactured by JASCO Corporation) equipped with an integrating sphere unit, and the haze was 5.5%.

<Example 2> Synthesis of terminal methacrylate polycarbonate oligomer (1b)
130.0 g of polycarbonate oligomer (A-1-a) synthesized in the same manner as Reference Example 1 was placed in a four-necked flask equipped with a thermometer, stirrer, and condenser, and after purging the reaction vessel with nitrogen, 19.9 g (0.19 mol) of methacrylic acid chloride, 286.2 g of dichloromethane, and 10.0 mg of methoquinone were added under a nitrogen stream. At 15° C., 25.4 g (0.25 mol) of triethylamine were added over 45 minutes. After further stirring at 15° C. for 2 hours, 390 g of 0.1 mol/L hydrochloric acid water was added, stirred for 20 minutes, and separated to obtain an organic solvent layer. Thereafter, washing and analysis were performed once with 260 g of water, and 1040 g of methanol was added to precipitate the target product. Thereafter, the solution was allowed to stand still and the separated upper layer was extracted, and 780 g of methanol was further added and stirred. A washing step was performed in which the precipitate was filtered off and the resulting wet cake was redispersed in 780 g of methanol. Thereafter, the precipitate was filtered and dried to obtain 120 g of terminal methacrylate polycarbonate oligomer (1b) in the form of a white powder.
The weight average molecular weight of the obtained terminal methacrylate polycarbonate oligomer (1b) was 3,134 (gel permeation chromatography). From the results of ¹ H-NMR analysis, it was confirmed that the obtained oligomer was a double-ended methacrylate polycarbonate oligomer represented by the above formula (1b).
When 2.0 g of the obtained terminal methacrylate polycarbonate oligomer (1b), 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 transparent solution was obtained. It was confirmed that a transparent hard coat film was formed on the PC board by UV irradiation.
From these results, it is clear that the obtained terminal methacrylate polycarbonate oligomer (1b) shows good solubility in organic solvents such as cyclohexanone, and also has excellent compatibility with pentaerythritol tetraacrylate, which is a polyfunctional acrylate. It became.
Subsequently, a cured film was prepared using the obtained solution in the same manner as in Example 1, and the haze after the abrasion test was measured. As a result, the haze was 5.1%.

<Comparative Example 1> Synthesis of diacrylate polycarbonate-1
In a four-necked flask equipped with a thermometer, stirrer, and 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 added. After the reaction vessel was purged with nitrogen, 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 the degree of vacuum was reduced to 13.3 kPa over 80 minutes while distilling the generated phenol. was set to 0.8 kPa. The temperature was further increased to 285°C, and the reaction was carried out at 0.7 kPa for 7 hours. 250 g of reaction-completed liquid was obtained.
Next, a solution in which 150.0 g of the obtained reaction-completed liquid was dissolved in 530.0 g of dichloromethane was dropped into 1850 g of methanol to precipitate the target product. After stirring for 1 hour, the precipitate was filtered and dried to obtain powdered 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, 13.6 g of the obtained polycarbonate was placed in a four-necked flask equipped with a thermometer, a stirrer, and a condenser, and after purging the reaction vessel with nitrogen, 0.3 g (0.003 mol) of acrylic acid chloride, After adding 47.6 g of dichloromethane under a nitrogen stream, 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. Thereafter, the precipitate was filtered and dried, and 14.1 g of the obtained wet cake was dissolved in 47.6 g of dichloromethane, and the solution was added to 163 g of methanol to cause precipitation. Thereafter, the precipitate was filtered and dried to obtain 13 g of a white powdery compound.
From the results of ¹ H-NMR analysis of the obtained compound, it was confirmed that it was a terminal diacrylate polycarbonate.
The synthesized diacrylate polycarbonate did not dissolve in cyclohexanone.
In addition, a mixture obtained by using dichloromethane instead of cyclohexanone and mixing 0.6 g of diacrylate polycarbonate, 2.4 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 3.0 g of dichloromethane, was cloudy and formed a hard coat film. I couldn't let it go.

<Comparative Example 2> Synthesis of diacrylate polycarbonate-2
Into a four-necked flask equipped with a thermometer, stirrer, and condenser, 276.9 g (1.08 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane and 237.1 g (1.08 mol) of diphenyl carbonate were added. After the reaction vessel was purged with nitrogen, 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 the degree of vacuum was reduced to 13.3 kPa over 80 minutes while distilling the generated phenol. was set to 0.8 kPa. The temperature was further increased to 285°C, and the reaction was carried out at 0.7 kPa for 7 hours. 250 g of reaction-completed liquid was obtained.
Next, a solution in which 150.0 g of the obtained reaction-completed liquid was dissolved in 530.0 g of dichloromethane was dropped into 1850 g of methanol to precipitate the target product. After stirring for 1 hour, the precipitate was filtered and dried to obtain powdered 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 placed in a four-necked flask equipped with a thermometer, a stirrer, and a condenser, and after purging the reaction vessel with nitrogen, 0.3 g (0.003 mol) of acrylic acid chloride, After adding 47.6 g of dichloromethane under a nitrogen stream, 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. Thereafter, the precipitate was filtered and dried, and 14.1 g of the obtained wet cake was dissolved in 47.6 g of dichloromethane, and the solution was added to 163 g of methanol to cause precipitation. Thereafter, the precipitate was filtered and dried to obtain 13 g of a white powdery compound.
From the results of ¹ H-NMR analysis of the obtained compound, it was confirmed that it was a terminal diacrylate polycarbonate.
The synthesized diacrylate polycarbonate did not dissolve in cyclohexanone.
In addition, a mixture obtained by using dichloromethane instead of cyclohexanone and mixing 0.6 g of diacrylate polycarbonate, 2.4 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 3.0 g of dichloromethane, was cloudy and formed a hard coat film. I couldn't let it go.

From the results of Comparative Example 1 and Comparative Example 2 above, the terminal (meth)acrylate polycarbonate oligomer represented by formula (1) and/or (2) has a weight average molecular weight (Mw) within a specific range. As a result, it has been revealed that it shows good solubility in organic solvents and has excellent compatibility with polyfunctional acrylates and the like.

<Comparative Reference Example 1> Synthesis of polycarbonate oligomer (X)
In a four-necked flask equipped with a thermometer, stirrer, and condenser, 616.4 g (2.7 mol) of 2,2-bis(4-hydroxyphenyl)propane and 404.8 g (1.9 mol) of diphenyl carbonate were added. After replacing the reaction vessel with nitrogen, 2.9 g of a 0.06% cesium carbonate aqueous solution was added at 110°C. After raising the temperature to 210° C., the degree of vacuum was adjusted to 0.6 kPa, and the reaction was carried out for 8 hours while distilling the produced phenol, to obtain 646.9 g of the reaction-completed liquid.
Next, a solution of 140.0 g of the obtained reaction-completed liquid dissolved in 252.0 g of toluene was added dropwise to 1680 g of methanol in a 4-necked flask over 2 hours while maintaining the temperature at 15°C to obtain the target product. precipitated. After stirring overnight, the precipitate was filtered off, and 2,533 g of the resulting wet cake was washed twice in which it was redispersed in methanol. The precipitate was filtered and dried to obtain a powdered 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)
130.0 g of the polycarbonate oligomer (X) obtained in Comparative Reference Example 1 was placed in a four-necked flask equipped with a thermometer, stirrer, and condenser, and after purging the reaction vessel with nitrogen, 35.3 g of acrylic acid chloride was added. (0.39 mol), 285.7 g of dichloromethane, and 17.4 mg of methoquinone were added under a nitrogen stream. At 15° C., a mixed solution of 47.1 g (0.47 mol) of triethylamine and 65 g of dichloromethane was added over 2 hours. After further stirring at 15° C. for 3 hours, 1300 g of methanol was added to precipitate the target product. Thereafter, a washing step was carried out in which the precipitate was filtered out and the resulting wet cake was redispersed twice with 900 g of water and twice with 900 g of methanol. Thereafter, the precipitate was filtered and dried to obtain 138 g of terminal acrylate polycarbonate oligomer (x-1) in the form of a yellowish white powder.
The weight average molecular weight of the obtained terminal acrylate polycarbonate oligomer (x-1) was 3,453 (gel permeation chromatography). From the results of ¹ H-NMR analysis, it was confirmed that the obtained oligomer was a double-terminated acrylate polycarbonate oligomer represented by the above formula (x-1).
When 2.0 g of the obtained terminal acrylate polycarbonate oligomer (x-1), 8.0 g of pentaerythritol tetraacrylate (a polyfunctional acrylate), 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 a PC board by irradiation with ultraviolet rays.
Subsequently, a cured film was prepared using the obtained solution in the same manner as in Example 1, and the haze after the abrasion test was measured. As a result, the haze was 9.4%.

<Comparative Example 4> Synthesis of terminal methacrylate polycarbonate oligomer (x-2)
120.0 g of polycarbonate oligomer (X) synthesized in the same manner as in Comparative Reference Example 1 was placed in a four-necked flask equipped with a thermometer, stirrer, and condenser, and after purging the reaction vessel with nitrogen, methacrylic acid chloride was added. 18.3 g (0.18 mol), 265 g of dichloromethane, and 9.3 mg of methoquinone were added under a nitrogen stream. At 15° C., a mixed solution of 23.4 g (0.47 mol) of triethylamine and 60 g of dichloromethane was added over 45 minutes. After further stirring at 15° C. for 2 hours, 360 g of 0.1 mol/L hydrochloric acid water was added, stirred for 20 minutes, and separated to obtain an organic solvent layer. Thereafter, washing and analysis were performed once with 240 g of water, and 960 g of methanol was added to precipitate the target product. Thereafter, the solution was allowed to stand still and the separated upper layer solution was extracted, and 720 g of methanol was further added and stirred. A washing step was performed in which the precipitate was filtered off and the resulting wet cake was redispersed in 900 g of methanol. Thereafter, the precipitate was filtered and dried to obtain 123 g of terminal methacrylate polycarbonate oligomer (x-2) in the form of a white powder.
The weight average molecular weight of the obtained terminal methacrylate polycarbonate oligomer (x-2) was 3,147 (gel permeation chromatography). From the results of ¹ H-NMR analysis, it was confirmed that the obtained oligomer was a double-ended methacrylate polycarbonate oligomer represented by the above formula (x-2).
When 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 transparent A solution was obtained, and it was confirmed that a transparent hard coat film was formed on the PC board by UV irradiation.
A cured film was created in the same manner as in Example 1, and the haze after the abrasion test was measured, and the haze was 12.8%.

From this result, the terminal methacrylate polycarbonate oligomer represented by formula (1) and/or formula (2) of the present invention shows good solubility in organic solvents such as cyclohexanone, and also has a high solubility in organic solvents such as cyclohexanone. It was revealed that it has excellent compatibility with erythritol tetraacrylate. Furthermore, it was confirmed that the terminal methacrylate polycarbonate oligomer of the present invention has excellent abrasion resistance when formed into a cured film.

Claims (1)

A terminal (meth)acrylate polycarbonate oligomer represented by the following formula (1) and/or the following formula (2) 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, and R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. (n is an integer of 1 or more. However, the total number of carbon atoms in R ₂ and R ₃ is 14 or less.)