JPWO2020008879A1 - Terminal (meth) acrylate polycarbonate oligomer - Google Patents

Abstract

Provided as a raw material for a UV curable (meth) acrylic resin used for a UV curable hard coat agent or the like, a terminal (meth) acrylate polycarbonate oligomer having excellent compatibility with a polyfunctional (meth) acrylic monomer and solvent solubility. The task is to do. As a solution, there is provided a terminal (meth) acrylate polycarbonate oligomer represented by the formulas (1) and / or (2) and having a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less. ..

Description

The present invention relates to a terminal (meth) acrylate polycarbonate oligomer having good solvent solubility.

Resin materials are widely used as engineering plastics because they are lightweight, inexpensive, and have excellent workability, but their surface hardness, scratch resistance, and chemical resistance are inferior to those of glass and metal. Therefore, it will not be used as a substitute material as it is. In order to improve these drawbacks of the resin material, a hard coat treatment is performed on the resin surface to form a resin thin film made of a material different from the resin of the base material, protect the resin of the base material from external factors, and modify the surface. 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 an electron beam or ultraviolet rays (UV) as necessary to cure the hard coat layer. (For example, Patent Documents 1 and 2). Among these, UV curable hard coating agents using UV curable resins are highly productive and have been developed for various purposes because they can be treated at a lower temperature and in a shorter time than conventional hard coating agents. There is.
Since this UV curable hard coat agent uses a polyfunctional (meth) acrylic monomer such as pentaerythritol-based (meth) acrylate as the main component, the component to be blended is the polyfunctional (meth) acrylic monomer. Highly compatible products are required.

JP-A-2010-024255 Japanese Unexamined Patent Publication No. 2016-011365

The present invention has been made against the background of the above circumstances, and is compatible with a polyfunctional (meth) acrylic monomer as a raw material for a UV curable (meth) acrylic resin used for a UV curable hard coat agent or the like. An object of the present invention is to provide a terminal (meth) acrylate polycarbonate oligomer having excellent solvent solubility.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have specified the weight average molecular weight (Mw) of the terminal (meth) acrylate polycarbonate represented by the following formulas (1) and / or (2). The present invention has been completed by finding that the oligomer in the range has excellent compatibility with a polyfunctional (meth) acrylic monomer and good solvent solubility.

（式（１）、（２）中、Ｒ_１〜Ｒ_４は、各々独立して水素原子、炭素原子数１〜８のアルキル基、炭素数５〜１２のシクロアルキル基、炭素原子数１〜８のアルコキシ基、又は、炭素原子数６〜１２の芳香族炭化水素基を表し、Ｒ_５は、各々独立して水素原子又はメチル基を表し、Ｒ_６、Ｒ_７は、各々独立して水素原子又は炭素原子数１〜１４のアルキル基を表し、Ｘは、炭素原子数２〜４のアルキレン基を表し、ｎは、１以上の整数である。ただし、Ｒ_６及びＲ_７の炭素原子数の合計は１４以下であり、Ｘに結合している２つの酸素原子は、Ｘの同一炭素原子には結合しない。）The present invention is as follows.
1. 1. A terminal (meth) acrylate polycarbonate oligomer represented by the following formulas (1) and / or (2), wherein the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.

In formulas (1) and (2), R _{1 to} R ₄ are independently hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 5 to 12 carbon atoms, and carbon atoms 1 to 1. Represents an alkoxy group of 8 or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ₅ independently represents a hydrogen atom or a methyl group, and R ₆ and R ₇ each independently represent hydrogen. It represents an atom or an alkyl group having 1 to 14 carbon atoms, X represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 or more, where R ₆ and R ₇ have carbon atoms. The total of is 14 or less, and the two oxygen atoms bonded to X do not bond to the same carbon atom of X.)

Since the terminal (meth) acrylate polycarbonate oligomer according to the present invention has a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less, it can be used with a polyfunctional (meth) acrylic monomer such as pentaerythritol-based (meth) acrylate. Since it has excellent compatibility and good solvent solubility, it is most suitable as a raw material for a UV-curable hard coating agent, and exhibits an industrially advantageous effect that a smooth coating film can be formed by UV curing.

^{6 is a 1} H-NMR spectrum chart of the terminal (meth) acrylate polycarbonate oligomer (1c) synthesized in Example 1. ^{6 is a 1} H-NMR spectrum chart of the terminal (meth) acrylate polycarbonate oligomer (1d) synthesized in Example 2.

（反応式中のＲ_１〜Ｒ_７、Ｘ、ｎの定義は、上述の式（１）、（２）と同じである。）Hereinafter, the terminal (meth) acrylate polycarbonate oligomer of the present invention will be described in detail.
As illustrated in the reaction formula below, the terminal (meth) acrylate polycarbonate oligomer of the present invention comprises a polycarbonate oligomer represented by the formula (A) and a (meth) acrylicizing 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 the reaction and has a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less.

(The definitions of R _{1 to} R ₇ , X, and n in the reaction formula are the same as those in the above formulas (1) and (2).)

（式（Ａ）中のＲ_１〜Ｒ_７、Ｘ、ｎの定義は、上述の式（１）、（２）と同じである。）
上記式（Ａ）において、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４のいずれかが、炭素原子数１〜８のアルキル基である場合、アルキル基としては、好ましくは炭素原子数１〜４の直鎖状、分岐鎖状のアルキル基であり、具体的には、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、イソブチル基等が挙げられる。このようなアルキル基には、本発明の効果を損なわない範囲で例えばフェニル基、炭素原子数１〜４のアルコキシ基等の置換基を有していてもよい。
Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４のいずれかが、炭素原子数５〜１２のシクロアルキル基である場合、シクロアルキル基としては、好ましくは炭素原子数５〜７のシクロアルキル基であり、具体的には、例えば、シクロヘキシル基、シクロペンチル基、シクロへプチル基等が挙げられる。このようなシクロアルキル基には、本発明の効果を損なわない範囲で、例えば、直鎖又は分岐鎖状の炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、フェニル基等の置換基を有していてもよい。
また、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４のいずれかが、炭素原子数１〜８のアルコキシ基である場合、アルコキシ基としては、好ましくは炭素原子数１〜４の直鎖状、分岐鎖状のアルコキシ基であり、具体的には、例えば、メトキシ基、エトキシ基等が挙げられる。このようなアルコキシ基には本願の効果を損なわない範囲で、例えば、フェニル基、炭素原子数１〜４のアルコキシ基等の置換基を有していてもよい。
さらに、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４のいずれかが、炭素原子数６〜１２の芳香族炭化水素基である場合、芳香族炭化水素基としては、具体的には、例えば、フェニル基、ナフチル基等が挙げられる。このような芳香族炭化水素基には、本発明の効果を損なわない範囲で、例えば、炭素原子数１〜４のアルキル基及び／又は、炭素原子数１〜４のアルコキシ基が１〜３程度置換していてもよい。
Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４の置換基が結合する位置は、そのベンゼン環に結合する酸素原子に対してオルト位が好ましい。
上記式（Ａ）において、Ｒ_６及びＲ_７のいずれかが、炭素原子数１〜１４のアルキル基である場合、アルキル基としては、好ましくは炭素原子数１〜１２の直鎖状、分岐鎖状のアルキル基であり、具体的には、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基等が挙げられる。ただし、Ｒ_６及びＲ_７の炭素原子数の合計は１４以下でなければならない。
上記式（Ａ）において、Ｘは、具体的には、エチレン基、ｎ−プロピレン基、プロパン−１，２−ジイル基、ｎ−ブチレン基、ブタン−１，３−ジイル基、ブタン−１，２−ジイル基、ブタン−２，３−ジイル基を表し、中でも、エチレン基、ｎ−プロピレン基、プロパン−１，２−ジイル基、ｎ−ブチレン基が好ましく、エチレン基、プロパン−１，２−ジイル基、がより好ましく、エチレン基が特に好ましい。<About the polycarbonate oligomer represented by the formula (A)>
The chemical structure of the terminal (meth) acrylate polycarbonate oligomer of the present invention will be described by explaining in detail the polycarbonate oligomer represented by the following formula (A), which is a synthetic raw material thereof. _{That is, specific examples of R 1 to} R ₄ , R ₆ , R ₇ , X, n in the formula (A), preferable chemical groups and substituents thereof, etc. represent the terminal (meth) acrylate polycarbonate oligomer of the present invention. _{, R 1 to} R ₇ , X, n in the formula (1) or (2).

_{(The definitions of R 1 to} R ₇ , X, and n in the formula (A) are the same as those in the above formulas (1) and (2).)
In the above formula (A), when _{any one of R 1} , R ₂ , R ₃ and R ₄ is an alkyl group having 1 to 8 carbon atoms, the alkyl group preferably has 1 to 4 carbon atoms. It is a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an isobutyl group. Such an alkyl group may have a substituent such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms as long as the effect of the present invention is not impaired.
When _{any one of R 1} , R ₂ , R ₃ and R ₄ is a cycloalkyl group having 5 to 12 carbon atoms, the cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms. Specifically, for example, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group and the like can be mentioned. Such cycloalkyl groups include, for example, linear or branched alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, and phenyl groups as long as the effects of the present invention are not impaired. It may have a substituent such as.
When _{any one of R 1} , R ₂ , R ₃ and R ₄ is an alkoxy group having 1 to 8 carbon atoms, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. It is a chain alkoxy group, and specific examples thereof include a methoxy group and an ethoxy group. Such an alkoxy group may have a substituent such as a phenyl group or an alkoxy group having 1 to 4 carbon atoms as long as the effect of the present application is not impaired.
Further, when _{any one of R 1} , R ₂ , R ₃ and R ₄ is an aromatic hydrocarbon group having 6 to 12 carbon atoms, the aromatic hydrocarbon group is specifically, for example, phenyl. Groups, naphthyl groups and the like can be mentioned. Such an aromatic hydrocarbon group contains, for example, an alkyl group having 1 to 4 carbon atoms and / or an alkoxy group having 1 to 4 carbon atoms as long as the effect of the present invention is not impaired. It may be replaced.
The _{position where the substituents of R 1} , R ₂ , R ₃ and R ₄ are bonded is preferably the ortho position with respect to the oxygen atom bonded to the benzene ring.
In the above formula (A), when _{any of R 6} and R ₇ is an alkyl group having 1 to 14 carbon atoms, the alkyl group is preferably a linear or branched chain having 1 to 12 carbon atoms. 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-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. However, the total number of carbon atoms of _{R 6} and R _{7 must be 14 or less.}
In the above formula (A), X is specifically an ethylene group, an n-propylene group, a propane-1,2-diyl group, an n-butylene group, a butane-1,3-diyl group, butane-1, It represents a 2-diyl group and a butane-2,3-diyl group, and among them, an ethylene group, an n-propylene group, a propane-1,2-diyl group and an n-butylene group are preferable, and an ethylene group and a propane-1,2 group are used. -The diyl group is more preferable, and the ethylene group is particularly preferable.

（式（Ｂ）中のＲ_１〜Ｒ_４、Ｒ_６、Ｒ_７、Ｘの定義は、上述の式（１）、（２）と同じである。）As the polycarbonate oligomer represented by the formula (A), those produced by any conventionally known production method can be used. Specific examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Above all, it is industrially advantageous to use the interfacial polymerization method, the molten transesterification method, and the solid phase transesterification method of the prepolymer. Among these, a melt transesterification method that does not use phosgene and a prepolymer solid phase transesterification method by a melt transesterification method are particularly preferable. The above production method is carried out using a dihydroxy compound represented by the following formula (B) and a carbonic acid ester forming agent.

_{(The definitions of R 1 to} R ₄ , R ₆ , R ₇ , and X in the formula (B) are the same as those in the above formulas (1) and (2).)

<About the dihydroxy compound represented by the formula (B)>
Specific examples of the dihydroxy compound represented by the formula (B) include bis (4- (2-hydroxyethoxy) phenyl) methane and 2,2-bis (4- (2-hydroxyethoxy) phenyl). Propane, 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) propane, 1,1-bis (4- (2-hydroxyethoxy) phenyl) ethane, 2,2-bis (4-) (2-Hydroxyethoxy) phenyl) -4-methylpentane, 2,2-bis (4- (2-hydroxyethoxy) phenyl) butane, 1,1-bis (4- (2-hydroxyethoxy) phenyl) dodecane, etc. Can be mentioned.
In the polymerization reaction, such a dihydroxy compound may be used alone or in admixture of two or more at an arbitrary ratio.

<About carbonic acid ester forming agent>
Specific examples of the carbonic acid ester forming agent to react with the dihydroxy compound represented by the formula (B) include diaryl carbonate such as diphenyl carbonate, ditril carbonate and bis (m-credyl) carbonate, dimethyl carbonate and diethyl. Examples thereof include dialkyl carbonates such as carbonates and dicyclohexyl carbonates, alkylaryl carbonates such as methylphenyl carbonates, ethylphenyl carbonates and cyclohexylphenyl carbonates, or carbonic acid diesters such as dialkenyl carbonates such as diisopropenyl carbonates and dipropenyl carbonates. Further, dihalogenated carbonyl compounds such as phosgene and triphosgene can also be mentioned. Of these, diaryl carbonate is preferred, and diphenyl carbonate is particularly preferred.

<About the molten transesterification method>
A melt transesterification method will be described as a method for producing the polycarbonate oligomer represented by the formula (A).
As a method of the melt transesterification reaction, when the dihydroxy compound represented by the formula (B) and diphenyl carbonate are used as the carbonate ester forming agent, in the presence of a catalyst, in an inert gas atmosphere at normal pressure or reduced pressure. It is carried out by stirring while heating to distill off the produced phenol. Usually, the desired molecular weight and the amount of terminal hydroxyl groups are adjusted by adjusting the mixing ratio of the dihydroxy compound represented by the formula (B) and the carbonic acid ester forming agent and the degree of reduced pressure during the transesterification reaction, according to the formula (A). The represented polycarbonate oligomer can be obtained.
In order to obtain the polycarbonate oligomer represented by the formula (A), the mixing ratio of the dihydroxy compound represented by the formula (B) and the carbonic acid ester forming agent is based on 1 mol of the dihydroxy compound represented by the formula (B). The carbonic acid ester forming agent is usually 0.2 to 1.0 mol times, preferably 0.25 to 0.95 mol times, and more preferably 0.3 to 0.90 mol times.
In the transesterification reaction, a transesterification catalyst is used as needed in order to increase the reaction rate. The ester exchange catalyst is not particularly limited, and examples thereof include inorganic alkali metal compounds such as lithium, sodium and cesium hydroxides, carbonates and hydrogen carbonate compounds, and organic alkali metal compounds such as alcoholates and organic carboxylates. Alkali metal compounds; hydroxides such as beryllium and magnesium, inorganic alkaline earth metal compounds such as carbonates, alkaline earth metal compounds such as organic alkaline earth metal compounds such as alcoholates and organic carboxylates; tetramethylboron, Sodium salts such as tetraethylboron and butyltriphenylboron, basic boron compounds such as calcium salt and magnesium salt; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine, or derived from these compounds. Basic phosphorus compounds such as quaternary phosphonium salts; Basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide; amines such as 4-aminopyridine, 2-dimethylaminoimidazole, and aminoquinolin. A known ester exchange catalyst such as a compound can be used. Of these, alkali metal compounds are preferable, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferable.
The amount of the catalyst used cannot be unequivocally determined because it is used within a range that does not cause a quality problem of the produced oligomer due to the catalyst residue, and the suitable addition amount differs depending on the type of catalyst. ) 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 dihydroxy compound. .. The catalyst may be added as it is, or may be added by dissolving it in a solvent, and the solvent is preferably one that does not affect the reaction of, for example, water or phenol.
The reaction conditions of 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, and 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 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 a pressure at which the carbonic acid 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 be distilled off. Under such reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.

<About (meth) acrylicization>
As illustrated in the above reaction formula, the terminal (meth) acrylate polycarbonate oligomer represented by the formulas (1) and / or (2) of the present invention includes the polycarbonate oligomer represented by the formula (A) and (meth). It is obtained by reaction with a (meth) acrylicizing agent such as acrylate chloride.
Specific examples of the (meth) acrylicizing agent include acrylate chloride, methacrylic acid chloride, acrylic acid, and methacrylic acid.
The amount of the (meth) acrylicizing agent used is based on the all-terminal hydroxyl groups of the polycarbonate oligomer represented by the formula (A) when both terminal (meth) acrylate polycarbonate oligomers represented by the formula (1) are obtained. The (meth) acrylicizing agent is usually used 1.0 to 2.5 mol times, preferably 1.1 to 2.0 mol times, and more preferably 1.15 to 1.5 mol times.
In the case of obtaining the one-terminal (meth) acrylate polycarbonate oligomer represented by the formula (2), a (meth) acrylicizing agent is usually applied to all the terminal hydroxyl groups of the polycarbonate oligomer represented by the formula (A). It is used 0.5 to 1.5 mol times, preferably 0.5 to 1.25 mol times, and more preferably 0.6 to 1.0 mol times.
For example, when the polycarbonate oligomer represented by the formula (A) is acrylicized using (meth) acrylic acid chloride, chloride ions are generated in the form of hydrogen chloride, so it is preferable to use a hydrogen chloride supplement in combination. .. As the hydrogen chloride supplement, any basic substance can be used. As the inorganic basic substance, alkali metal carbonates, hydrogen carbonates and the like can be used. As the organic basic substance, tertiary amines can be used. Examples of tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl-diamilamine, 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, picolin, N , N-Dimethylaminopyridine and other heterocyclic amines; 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene and other fats Cyclic amines and the like can be mentioned.
The amount of the hydrogen chloride supplement used is 0.8 to 10 times by mole, preferably 0.9 to 8 times by mole, particularly preferably 0.9 to 8 times the number of moles of the (meth) acrylicizing agent normally used. Is about 1.0 to 7 times the molar amount. If the hydrogen chloride supplement is less than 0.8 times the number of moles of the (meth) acrylicizing agent, the generated hydrogen chloride cannot be completely captured, and the polycarbonate oligomer represented by the formula (A) of the raw material or the target substance can be used. There is a risk that the terminal (meth) acrylate polycarbonate oligomer represented by a certain formula (1) or (2) will be decomposed, causing a decrease in the purity of the target substance. Further, if the amount of the hydrogen chloride supplement exceeds 10 times the number of moles of the (meth) acrylicizing agent, it is not preferable because the removal of the hydrogen chloride supplement is not only complicated but also uneconomical.

In this (meth) acrylicization 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, etc. Examples include chlorobenzene and the like. The amount of the solvent used is not particularly limited, but is usually 0.5 to 100 times by weight, preferably 1 to 50 times by weight, particularly preferably 2 to 10 times the weight of the polycarbonate oligomer represented by the formula (A). It is double the weight.
The (meth) acrylicization 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. If the reaction temperature exceeds 100 ° C, a side reaction will occur, leading to a decrease in the yield of the target product. Further, if the temperature is lower than −50 ° C., the reaction rate becomes slow and the required time is too long, which is not economical.
As a reaction procedure, a method in which a polycarbonate oligomer represented by the formula (A) and a (meth) acrylicizing agent are mixed in a solvent in advance and a hydrogen chloride supplement is added thereto, or a method of first formulating (A). ) Is mixed in a solvent with a polycarbonate oligomer represented by) and a hydrogen chloride supplement, and a (meth) acrylicizing agent is added thereto. In these methods, the hydrogen chloride supplement or (meth) acrylicizing agent to be added later may be used in a state of being diluted with a solvent.
Further, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-di-tert-butyl-4-methylphenol (BHT) and the like may be added as a polymerization inhibitor during the reaction.

<Post-treatment and purification of (meth) acrylicization>
In the (meth) acrylicization reaction, a basic substance that is a hydrogen chloride supplement is often added in excess, and in particular, an organic basic substance is the target product according to the formulas (1) and / or (2). Since it remains in the organic solvent together with the represented terminal (meth) acrylate polycarbonate oligomer and tends to cause an unfavorable phenomenon such as coloring and decomposition, it is preferable to remove it by 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 the inorganic acidic substance includes, for example, hydrochloric acid, sulfuric acid, nitric acid and the like, and the organic acidic substance includes, for example, formic acid, acetic acid, propionic acid, and the like. Carboxylic acids such as butyric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and the like. Of these, organic acidic substances having low acidity are more preferable. After removing the hydrogen chloride supplement, it is preferable to carry out a subsequent washing with water.
The obtained terminal (meth) acrylate polycarbonate oligomer represented by the formulas (1) and / or (2) is preferably obtained as a precipitate by adding a poor solvent to the dissolved solution. Specific examples of the poor solvent include an aliphatic alcohol solvent having 1 to 6 carbon atoms such as methanol, ethanol and propanol, or a mixture of the above aliphatic alcohol solvent and water.

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

Preferred compounds of both terminal (meth) acrylate polycarbonate oligomers represented by the formula (1) are as follows. N in the formulas (1a) to (1d) is an integer of 1 or more, but the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.

Preferred compounds of the one-terminal (meth) acrylate polycarbonate oligomer represented by the formula (2) are as follows. N in the formulas (2a) to (2d) is an integer of 1 or more, but the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.

The terminal (meth) acrylate polycarbonate oligomer represented by the formulas (1) and / or (2) of the present invention has a weight average molecular weight (Mw) in the range of 500 or more and 10,000 or less, and among them, 1,000 or more. The range of 8,000 or less is preferable, and the range of 2,000 or more and 6,000 or less is more preferable. When the weight average molecular weight (Mw) is within this range, good solubility in an organic solvent can be obtained, which is preferable.
Further, when the terminal (meth) acrylate polycarbonate oligomer represented by the formulas (1) and / or (2) of the present invention is used as a component of the UV curable hard coat agent, the pentaerythritol system which is the main component is used. Since it has excellent compatibility with polyfunctional (meth) acrylic monomers such as (meth) acrylate, it exhibits an industrially advantageous effect that a smooth coating film can be formed by UV curing.
The terminal (meth) acrylate polycarbonate oligomer represented by the formulas (1) and / or (2) of the present invention is not only a raw material for a UV curable hard coat agent, but also a raw material for modeling of a 3D printer and heat of an epoxy resin or the like. It is useful as a modifier for cured resins.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
The weight average molecular weight (Mw) in the following examples was measured by gel permeation chromatography. The analysis method is as follows.
<Analysis method>
1. 1. Gel permeation chromatography measurement (analysis of oligomers)
Equipment: HLC-8320GPC manufactured by Tosoh Corporation
Flow rate: 0.35 ml / min, mobile phase: tetrahydrofuran, driving amount: 10 μl
Column: TSKgel guardcolumn SuperMP (HZ) -N, TSKgel SuperMultipore HZ-N x 3 Detectors: RI,
Analysis method: Relative molecular weight in terms of polystyrene.
Polystyrene standard: Tosoh Corporation A-500, A-2500, A-5000, F-1, F-2, F-4
(Polymer analysis)
Equipment: HLC-8320GPC manufactured by Tosoh Corporation
Flow rate: 1.0 ml / min, mobile phase: tetrahydrofuran, driving amount: 100 μl
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: 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
2. Measurement of terminal hydroxyl concentration
¹ 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 preparations to prepare a calibration curve of the weight ratio with TCE. It was quantified by a method of determining the phenol terminal weight from this calibration curve.
Equipment: Bruker AscendTM 400
Measurement conditions: Room temperature, 120 times of integration 3. Identification of chemical structure Using the same equipment as in "2." above, ¹ H-NMR measurement was performed.

温度計、撹拌機、冷却器を備えた４つ口フラスコに２，２−ビス（４−（２−ヒドロキシエトキシ）−３−メチルフェニル）プロパン３８８．６ｇ（１．１モル）、ジフェニルカーボネート１６９．２ｇ（０．８モル）を仕込み、反応容器を窒素置換した後、１１０℃で０．０９％炭酸セシウム水溶液０．８２ｇを加えた。２００℃まで昇温した後、減圧度を０．３ｋＰａに調整し、２時間、生成したフェノールを留出させながら反応し、反応終了液３８３．４ｇを得た。
次いで、得られた反応終了液３７２．６ｇを温度計、撹拌機、冷却器を備えた４つ口フラスコに仕込み、トルエン７４５．２ｇに溶解させ、さらにメタノール２２３５．６ｇを添加し、室温で３０分撹拌した。３０分静置して分離した上層の溶液を抜き取り、得られた下層溶液にトルエン５５８．９ｇ、メタノール２２３５．６ｇを添加し、同様に撹拌、静置、上層溶液の抜き取り作業を２回行った。その後、溶剤を濃縮することで、ポリカーボネートオリゴマー（Ａ−ａ）１９３．５ｇを得た。得られたポリカーボネートオリゴマーの重量平均分子量は４６３０（ゲル浸透クロマトグラフィー）、末端ヒドロキシル濃度は０．６７ｍｍｏｌ／ｇであった。<Reference Example 1> Synthesis of Polycarbonate Oligomer (Aa)

2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) propane 388.6 g (1.1 mol), diphenyl carbonate 169 in a four-necked flask equipped with a thermometer, stirrer and cooler After charging 2 g (0.8 mol) and substituting the reaction vessel with nitrogen, 0.82 g of a 0.09% cesium carbonate aqueous solution was added at 110 ° C. After raising the temperature to 200 ° C., the degree of decompression was adjusted to 0.3 kPa, and the reaction was carried out for 2 hours while distilling off the produced phenol to obtain 383.4 g of a reaction completion solution.
Next, 372.6 g of the obtained reaction termination liquid was charged into a four-necked flask equipped with a thermometer, a stirrer, and a cooler, dissolved in 745.2 g of toluene, and 2235.6 g of methanol was further added, and 30 at room temperature. Stir for minutes. After allowing to stand for 30 minutes, the separated upper layer solution was withdrawn, 558.9 g of toluene and 2235.6 g of methanol were added to the obtained lower layer solution, and the same stirring, standing, and withdrawal of the upper layer solution were performed twice. .. Then, the solvent was concentrated to obtain 193.5 g of the polycarbonate oligomer (Aa). The weight average molecular weight of the obtained polycarbonate oligomer was 4630 (gel permeation chromatography), and the terminal hydroxyl concentration was 0.67 mmol / g.

<Example 1> Synthesis of terminal acrylate polycarbonate oligomer (1c) 80.3 g of the polycarbonate oligomer (Aa) obtained in Reference Example 1 was placed in a four-necked flask equipped with a thermometer, a stirrer, and a cooler. After replacing the reaction vessel with nitrogen, 7.3 g (0.08 mol) of acrylate chloride, 120.5 g of dichloromethane, and 4.0 mg of methquinone were added under a nitrogen stream. A mixed solution of 10.9 g (0.11 mol) of triethylamine and 40.2 g of dichloromethane was added at 10 ° C. over 2 hours. After further stirring at 10 ° C. for 1 hour, 825 g of water and 960 g of methanol were added, and after stirring for 1 hour, the solution in the upper layer separated by allowing to stand was extracted, and 960 g of methanol was further added and stirred. After stirring for 1 hour, the solution of the upper layer separated by allowing to stand was withdrawn, and 320 g of methanol was further added and stirred. After stirring for 2 hours, the precipitate was filtered off and dried to obtain 79.3 g of a powdered terminal acrylate polycarbonate oligomer (1c).
The weight average molecular weight of the obtained terminal acrylate polycarbonate oligomer (1c) was 5,211 (gel permeation chromatography). ^{From the 1} H-NMR analysis result, it was confirmed that it was a double-ended acrylate polycarbonate oligomer represented by the above formula (1c). ^{FIG. 1 shows a 1} H-NMR spectrum chart of the obtained terminal acrylate polycarbonate oligomer (1c).
When 2.0 g of the obtained terminal acrylate polycarbonate oligomer (1c) and 10.0 g of cyclohexanone were mixed, a transparent solution was obtained. Further, when 8.0 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 0.5 g of Irgacure (184) were mixed, a transparent solution was obtained.
It was clarified that the obtained terminal acrylate polycarbonate oligomer (1c) showed good solubility in an organic solvent such as cyclohexanone, and also had excellent compatibility with pentaerythritol tetraacrylate, which is a polyfunctional acrylate.

<Example 2> Synthesis of terminal methacrylate polycarbonate oligomer (1d) 96 g of the polycarbonate oligomer (Aa) obtained in Reference Example 1 was charged into a four-necked flask equipped with a thermometer, a stirrer, and a cooler, and reacted. After replacing the container with nitrogen, 8.5 g (0.08 mol) of methacrylic acid chloride, 120.4 g of dichloromethane, and 4.6 mg of methquinone were added under a nitrogen stream. At 10 ° C., 10.9 g (0.11 mol) of triethylamine was added over 30 minutes. After further stirring at 10 ° C. for 2 hours, 825 g of water and 960 g of methanol were added, and after stirring for 1 hour, the solution in the upper layer separated by allowing to stand was extracted, and 960 g of methanol was further added and stirred. After stirring for 2 hours, the precipitate was filtered off, and the obtained wet cake was redispersed in 960 g of methanol to carry out a washing step. Then, the precipitate was separated by filtration and dried to obtain 56.1 g of powdered terminal methacrylate-polycarbonate oligomer (1d).
The weight average molecular weight of the obtained terminal methacrylate polycarbonate oligomer (1d) was 4,734 (gel permeation chromatography). ^{From the 1} H-NMR analysis result, it was confirmed that it was a double-ended methacrylate polycarbonate oligomer represented by the above formula (1d). ^{FIG. 2 shows a 1} H-NMR spectrum chart of the obtained terminal methacrylate polycarbonate oligomer (1d).
When 2.0 g of the obtained terminal methacrylate polycarbonate oligomer (1d) and 10.0 g of cyclohexanone were mixed, a transparent solution was obtained. Further, when 8.0 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 0.5 g of Irgacure (184) were mixed, a transparent solution was obtained.
It was clarified that the obtained terminal methacrylate polycarbonate oligomer (1d) showed good solubility in an organic solvent such as cyclohexanone, and also had excellent compatibility with pentaerythritol tetraacrylate, which is a polyfunctional acrylate.

<Comparative Example 1> Synthesis of terminal diacrylic polycarbonate In a four-necked flask equipped with a thermometer, a stirrer, and a cooler, 246.1 g (1.08 mol) of 2,2-bis (4-hydroxyphenyl) propane, 237.1 g (1.12 mol) of diphenyl carbonate was added, the reaction vessel was replaced with nitrogen, and then 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 is carried out at normal pressure for 40 minutes, and while distilling the produced phenol, the degree of decompression is adjusted to 13.3 kPa over 80 minutes. Was set to 0.8 kPa. The temperature was further raised to 285 ° C., and the reaction was carried out at 0.7 kPa for 7 hours. 250 g of the reaction completion solution was obtained.
Next, a solution prepared by dissolving 150.0 g of the obtained reaction termination solution in 530.0 g of dichloromethane was added dropwise to 1850 g of methanol to precipitate the desired product. After stirring for 1 hour, the precipitate was filtered off and dried to obtain a 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 cooler, and the reaction vessel was replaced with nitrogen. 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 desired product. Then, the precipitate was separated by filtration 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 precipitate. Then, the precipitate was filtered off and dried to obtain 13 g of a white powdery compound.
^{From the 1} H-NMR analysis result of the obtained compound, it was confirmed that it was a terminal diacrylic polycarbonate.
Cyclohexanone 8.0 g was used with respect to 0.4 g of the terminal diacrylic polycarbonate, but it did not dissolve. In addition, a mixture of 0.6 g of terminal diacrylic polycarbonate, 2.4 g of pentaerythritol tetraacrylate, which is a polyfunctional acrylate, and 3.0 g of dichloromethane, using dichloromethane instead of cyclohexanone, is in a cloudy state, and a transparent solution is prepared. I couldn't get it.

From the above results, the terminal (meth) acrylate polycarbonate oligomer represented by the formulas (1) and / or (2) of the present invention is organic by setting the weight average molecular weight (Mw) to be within a specific range. It was clarified that it showed good solubility in a solvent and also had excellent compatibility with polyfunctional acrylates and the like.

Claims (1)

A terminal (meth) acrylate polycarbonate oligomer represented by the following formulas (1) and / or (2), wherein the weight average molecular weight (Mw) is in the range of 500 or more and 10,000 or less.

In formulas (1) and (2), R _{1 to} R ₄ are independently hydrogen atoms, alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 5 to 12 carbon atoms, and carbon atoms 1 to 1. Represents an alkoxy group of 8 or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ₅ independently represents a hydrogen atom or a methyl group, and R ₆ and R ₇ each independently represent hydrogen. It represents an atom or an alkyl group having 1 to 14 carbon atoms, X represents an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 or more, where R ₆ and R ₇ have carbon atoms. The total of is 14 or less, and the two oxygen atoms bonded to X do not bond to the same carbon atom of X.)

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