JP2014201691A - Acrylic polymer, method of producing acrylic polymer, and method of producing radical curable compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an acrylic polymer having excellent heat resistance.SOLUTION: An acrylic polymer is obtained by the reaction between a polymer (I) obtained by radical polymerization of a radical curable compound (A) represented by formula (1) or (2) [X-Xare an acryloyl group or a hydrogen atom, at least one of them is essential] and an aldehyde compound (B).

Description

  The present invention relates to an acrylic polymer having excellent heat resistance, a method for producing the acrylic polymer, and a radical curable compound used for producing the acrylic polymer.

  2. Description of the Related Art In recent years, technological progress in electronic devices has been remarkable, and the density and performance of integrated circuits are rapidly increasing. Corresponding to this, higher density, higher wiring, and surface mounting of components have progressed in response to this, and higher precision and higher performance than before have been demanded. In order to adapt to the higher density and higher performance of this integrated circuit, higher performance has been studied for the solder resist, which is the main material of the integrated circuit. There is a problem of causing a crack called a popcorn phenomenon at the interface with the sealing resin, and a solder resist having a high heat resistance is demanded.

  Along with the high integration of integrated circuits, the nanoimprint method is attracting attention as a technique for ultra fine patterning with a line width of 20 nm or less. This nanoimprint method is roughly classified into a thermal nanoimprint method and an optical nanoimprint method. The thermal nanoimprint method heats above the glass transition temperature, presses the mold onto a softened polymer resin, releases the mold after cooling, and transfers the microstructure to the resin on the substrate, making the nanopattern relatively inexpensive It is expected to be applied to various fields. However, in the thermal nanoimprint method, since it is necessary to soften the polymer resin by heating, it is difficult to use a polymer resin having a high glass transition temperature, and in recent years, the application to the electric / electronic field where higher heat resistance is required. Application was difficult.

  On the other hand, in the optical nanoimprint method in which the composition is photocured by light irradiation, it is not necessary to heat the mold material for pattern transfer during pressing, and imprinting at room temperature is possible. The photo-curable resin applied to photo-nanoimprint includes radical polymerization type and ion polymerization type, and hybrid type of these, and any type of curable composition can be used for nanoimprint applications. In general, radical polymerization type photocurable compositions have been widely studied.

  In addition to the above highly integrated integrated circuit by the nanoimprint method, it is necessary to obtain a permanent film for use in microfabrication of liquid crystal display thin film transistors, liquid crystal color filter protective films, spacers, and other liquid crystal display device members. Nanoimprint materials that can provide mechanical properties, transparency, light resistance, and heat resistance are required, and materials that can provide cured products that are particularly excellent in high heat resistance are required.

  A cured product having high heat resistance is obtained, and as a material useful as a solder resist, for example, an epoxy (meth) acrylate resin having a biphenyl skeleton is known (for example, see Patent Document 1). It did not have high heat resistance.

JP-A-9-157340

  The problem to be solved by the present invention is an acrylic system that is excellent in heat resistance and useful as a permanent film for use in fine processing of solder resists, thin film transistors, protective films for liquid crystal color filters, spacers, and other liquid crystal display device members. It is providing the polymer, the manufacturing method of this acrylic polymer, and the radical curable compound used for manufacture of this acrylic polymer.

  As a result of extensive research, the present inventors have, for example, a polymer of a radical curable compound having a structure in which a part of the hydroxyl group of a pentafunctional phenol having a specific structure is substituted with a radical polymerizable unsaturated group, and an aldehyde compound. A cured product obtained by dehydrating and condensing, and a cured product obtained by radical polymerizing a polymer obtained by dehydrating and condensing the radical curable compound and the aldehyde compound have very high heat resistance, etc. The headline and the present invention were completed.

  That is, the present invention provides the following general formula (1) or general formula (2).

〔式中、Ｒ^１〜Ｒ^５は、それぞれ独立して炭素原子数１〜８のアルキル基である。X_１〜Ｘ_４はそれぞれ独立して下記式（ａ）

[In formula, R < ¹ > -R < ⁵ > is a C1-C8 alkyl group each independently. X _{1 to} X ₄ each independently represent the following formula (a)

で表される基または水素原子であるが、少なくとも一つは式（ａ）で表される基であり、また、少なくとも一つは水素原子である。ｍ、ｎ、ｏ、ｐおよびｑは、それぞれ独立して１〜４の整数である。〕で表されるラジカル硬化性化合物（Ａ）をラジカル重合させて得られる重合体（Ｉ）と、アルデヒド化合物（Ｂ）とを反応させて得られることを特徴とするアクリル系重合体を提供するものである。

Or at least one is a group represented by the formula (a), and at least one is a hydrogen atom. m, n, o, p, and q are each independently an integer of 1 to 4. An acrylic polymer obtained by reacting a polymer (I) obtained by radical polymerization of a radical curable compound (A) represented by formula (B) with an aldehyde compound (B) is provided. Is.

  The present invention also provides an acrylic polymer obtained by radical polymerization of the polymer (II) obtained by reacting the radical curable compound (A) with the aldehyde compound (B). To do.

  Further, the present invention provides an acrylic characterized by reacting the polymer (I) with an aldehyde compound (B) after radical polymerization of the radical curable compound (A) to obtain a polymer (I). A method for producing a polymer is provided.

  Furthermore, the present invention provides an acrylic characterized in that after the radical curable compound (A) and the aldehyde compound (B) are reacted to obtain a polymer (II), the polymer (II) is radically polymerized. A method for producing a polymer is provided.

  The acrylic polymer of the present invention has a very high level of heat resistance. In addition, the solubility in a solvent is also good. Therefore, the acrylic polymer of the present invention can be used as a material for solder resist and a material for nanoimprint, which require high heat resistance. In addition, the polymer used for obtaining the acrylic polymer of the present invention has photocurability and thermosetting, and can be used as a mold material for the thermal nanoimprint method because it can be photo-molded or thermo-molded. Can do. Here, as a thermoplastic resin used for a resist in the thermal nanoimprint method, when an engineering plastic for electrical / electronic materials having a glass transition temperature (Tg) exceeding 200 ° C. such as polyphenylene ether (PPE) having high heat resistance is used. The softening temperature of the plastic is 300 ° C. or higher, but the cured product of the radical curable compound of the present invention has very high heat resistance. Therefore, it can be used as a mold material.

  Further, since the acrylic polymer of the present invention has a high density of benzene rings, it becomes a more rigid skeleton, and its cured product has high heat resistance. Furthermore, due to its rigid skeleton, the cured product also has high mechanical properties (impact resistance), high water resistance, especially high hardness. Therefore, the acrylic polymer of the present invention is a film hard such as triacetyl cellulose (TAC) used for a polarizing plate of a liquid crystal display such as a television, a video camera, a computer, a mobile phone and the like that requires a high surface hardness. Coating material; Hard coating material for transparent protective film that protects the surface of various displays such as liquid crystal display, plasma display, organic EL display, etc .; Hard coating material for optical lens; Moreover, the acrylic polymer of the present invention can be easily produced by the production method of the present invention.

  The acrylic polymer of the present invention has the following general formula (1) or general formula (2).

〔式中、Ｒ^１〜Ｒ^５は、それぞれ独立して炭素原子数１〜８のアルキル基である。X_１〜Ｘ_４はそれぞれ独立して下記式（ａ）

[In formula, R < ¹ > -R < ⁵ > is a C1-C8 alkyl group each independently. X _{1 to} X ₄ each independently represent the following formula (a)

で表される基または水素原子であるが、少なくとも一つは式（ａ）で表される基であり、また、少なくとも一つは水素原子である。ｍ、ｎ、ｏ、ｐおよびｑは、それぞれ独立して１〜４の整数である。〕で表されるラジカル硬化性化合物（Ａ）をラジカル重合させて得られる重合体（Ｉ）と、アルデヒド化合物（Ｂ）とを反応させて得られる〔以下、これをアクリル系重合体（Ｉ）と略記することがある。〕。

Or at least one is a group represented by the formula (a), and at least one is a hydrogen atom. m, n, o, p, and q are each independently an integer of 1 to 4. ] It can be obtained by reacting a polymer (I) obtained by radical polymerization of a radical curable compound (A) represented by formula (B) with an aldehyde compound (B). May be abbreviated. ].

  Another acrylic polymer of the present invention is obtained by radical polymerization of the polymer (II) obtained by reacting the radical curable compound (A) with the aldehyde compound (B) [hereinafter, This may be abbreviated as acrylic polymer (II). ].

R ^{1 to} R ⁵ in the general formula (1) and the general formula (2) used when obtaining the acrylic polymer (I) and the acrylic polymer (II) of the present invention are each independently carbon. It is an alkyl group having 1 to 8 atoms. These alkyl groups give high heat resistance to the acrylic polymer (I) and the acrylic polymer (II). Among these alkyl groups, high rigidity is given to the molecule by suppressing molecular motion, high heat resistance can be given to the cured product, electron donating property to the phenolic benzene nucleus can be given, and industrial availability is easy. Therefore, a methyl group is preferable.

X _{1 to} X ₂ in the general formula (1) and the general formula (2) are each a group represented by the general formula (a) or a hydrogen atom, and at least one of them is represented by the formula (a). And at least one is a hydrogen atom. In this invention, it is preferable to have 2.2 to 3.8 groups represented by the group represented by the formula (a) on average. By having 2.2 to 3.8, the polymer (I) and the polymer (II) can be successfully prepared, and the acrylic polymer (I) having excellent heat resistance can be easily obtained. In addition, it is easy to obtain a polymer (I) having good solubility in a solvent, and since the residual solvent is reduced when the acrylic polymer of the present invention is formed into a coating film, the coating film characteristics do not deteriorate. I can expect. Among the radical curable compounds (A) used in the present invention, compounds having 2.4 to 3.6 groups represented by (a) are more preferable.

  Here, the “average” is an average of the number of groups represented by (a) of each radical curable compound (A). For example, acrylic polymer (I) or acrylic The radical curable compound (mixture) used as a raw material for the preparation of the polymer (II) does not have a group represented by (a) (0) a radical curable compound or a group represented by (a) It may contain four radically curable compounds.

_Here, if X 1 to X ₄ is formula (a), ^{R 6} in the general formula (a) may be the same or different.

In the formula (a), when R ⁶ is a hydrogen atom, a radical curable compound is obtained from which a cured product having a high curing rate and high adhesion to the substrate can be obtained. Further, when R ⁶ is a methyl group in the formula (a), a radical curable compound is obtained that has a cured shrinkage and a cured product having high adhesion to the substrate.

  It is preferable that m, n, p, and q in the general formula (1) and the general formula (2) are each independently an integer of 1 to 3, and o is 1.

  Examples of the radical curable compound (A) used in the present invention include the following general formula (1-1) to general formula (1-3) and general formula (2-1) to general formula (2-3). Illustrative examples include the radical curable compounds represented.

In said formula, R < ¹ > -R < ⁵ > is a C1-C8 alkyl group each independently. X _{1 to} X ₄ are each independently a group represented by the formula (a) or a hydrogen atom, at least one of which is a group represented by the formula (a). m, n, o, p, and q are each independently an integer of 1 to 4.

  Specific examples of the radical curable compounds represented by the following general formulas (1-1) to (1-3) and general formulas (2-1) to (2-3) include, for example, And radical curable compounds represented by the following general formulas (3) to (8).

  Furthermore, specific examples of the radical curable compounds represented by the general formulas (3) to (8) include the following compounds.

  The radically polymerizable compound used in the present invention may contain the compounds exemplified below as long as the effects of the present invention are not impaired.

  The radical curable compound (A) used in the present invention is obtained by, for example, polycondensation of an alkyl-substituted phenol (a1) and an aromatic dialdehyde (a2), thereby the following general formula (11) or general formula (12).

〔式中、Ｒ^１〜Ｒ^５は、それぞれ独立して炭素原子数１〜８のアルキル基である。ｍ、ｎ、ｏ、ｐおよびｑは、それぞれ独立して１〜４の整数である。〕で表される重縮合物（α）を得た後、該重縮合物に（メタ）アクリル酸ハライド（β）とを反応させる方法により得ることができる。

[In formula, R < ¹ > -R < ⁵ > is a C1-C8 alkyl group each independently. m, n, o, p, and q are each independently an integer of 1 to 4. The polycondensate (α) represented by the following formula can be obtained by reacting the polycondensate with (meth) acrylic acid halide (β).

  Examples of the polycondensate (α) represented by the general formula (11) or the general formula (12) include the polycondensates shown below.

[In formula, R < ¹ > -R < ⁵ > is a C1-C8 alkyl group each independently. m, n, o, p, and q are each independently an integer of 1 to 4. ]

  In the present invention, “(meth) acrylic acid” means one or both of “acrylic acid” and “methacrylic acid”.

  The alkyl-substituted phenol (a1) is a compound in which part or all of the hydrogen atoms bonded to the aromatic ring of the phenol are substituted with an alkyl group. Examples of the alkyl group include an alkyl group having 1 to 8 carbon atoms, and a methyl group is particularly preferable. Examples of the alkyl-substituted phenol (a1) include o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, pt-butylphenol, o -Monoalkylphenols such as cyclohexylphenol, m-cyclohexylphenol and p-cyclohexylphenol; dialkyl such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, 2,6-xylenol Examples include alkylphenols; trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol. Among these alkyl-substituted phenols, those having 2 substitutions of alkyl groups on the aromatic ring of the phenol are preferable because of their excellent heat resistance, and 2,5-xylenol and 2,6-xylenol are particularly preferable. These alkyl-substituted phenols (a1) can be used alone or in combination of two or more.

  As the aromatic dialdehyde (a2), for example, terephthalaldehyde, orthophthalaldehyde, isophthalaldehyde, 4-methylphthalaldehyde and the like can be preferably used. These aromatic dialdehydes (a2) can be used alone or in combination of two or more.

  Examples of the halide of the (meth) acrylic acid halide (β) include fluorine, chlorine, bromine, iodine, and astatine. Specific examples of the (meth) acrylic acid halide include (meth) acrylic acid chloride, (meth) acrylic acid bromide, and (meth) acrylic acid iodide. Among these (meth) acrylic acid halides, (meth) acrylic acid chloride is preferable because of its high reactivity and easy availability.

  Specific examples of the above production method for producing the radical curable compound (A) used in the present invention include a method comprising the following three steps.

(Step 1-1)
Alkyl-substituted phenol (a1) and aromatic dialdehyde (a2) having a hydroxyl group on the benzene ring are subjected to polycondensation in the presence of an acid catalyst, whereby the above general formulas (13) to (18) are added to the reaction solution. A crude product containing a polycondensate (α) represented by the above is obtained.

(Step 1-2)
The polycondensate (α) obtained in step 1-1 is recovered (isolated) from the reaction solution.

(Step 1-3)
The polycondensate (α) isolated in Step 1-2 is reacted with (meth) acrylic acid halide (β) in the presence of a base.

  Examples of the acid catalyst used in Step 1-1 include acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts can be used alone or in combination of two or more. Of these acid catalysts, sulfuric acid and paratoluenesulfonic acid are preferred because of their excellent activity. The acid catalyst may be added before the reaction or during the reaction.

  In step 1-1, a polycondensate may be obtained in the presence of a solvent, if necessary. Examples of the solvent include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Polyols such as hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerol; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol Glycol ethers such as ruethyl methyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like Examples include ketones. These solvents can be used alone or in combination of two or more. Of these solvents, 2-ethoxyethanol is preferable because the resulting compound has excellent solubility.

  In step 1-1, the reaction temperature for polycondensing the alkyl-substituted phenol (a1) and the aromatic dialdehyde (a2) is, for example, 60 to 140 ° C. Moreover, reaction time is 0.5 to 100 hours, for example.

  The charge ratio [(a1) / (a2)] of the alkyl-substituted phenol (a1) to the aromatic dialdehyde (a2) in the step 1-1 is that the unreacted alkyl-substituted phenol can be easily removed, and the product In this case, a molar ratio of 1 / 0.2 to 1 / 0.5 is preferable, and 1 / 0.25 to 1 / 0.45 is preferable. More preferred.

  Examples of the polycondensate (α) obtained as a result of the polycondensation in Step 1-1 include compounds represented by the following general formulas (19-1) to (19-8).

  In the reaction solution obtained in the step 1-1, unreacted substances such as (a1) and (a2) may remain together with the polycondensate (α). In addition, an unfavorable condensate other than the condensate having the structure represented by the general formula (5) or the general formula (6) may be generated. When such a reaction solution is subjected to a reprecipitation operation with water to obtain a recovered product for reaction with (meth) acryloyl halide (β), the recovered polycondensate (A) is contained in the recovered product. In addition, there is a possibility that a large amount of unreacted substances such as (a1) and (a2) or the undesired polycondensate is included.

  Therefore, it is preferable to further recover the polycondensate (α) from the recovered product recovered from the reaction solution in Step 1-2, and to increase the purity of the polycondensate (α) as much as possible.

  The purity of the polycondensate (α) to be reacted with the (meth) acryloyl halide (β) is preferably 85% or more, more preferably 90% or more, still more preferably 94% or more, particularly preferably 98% or more, 100 % Is most preferred. The purity of the polycondensate (α) can be determined from the area ratio in a chart of gel permeation chromatography (GPC).

  In the present invention, GPC measurement conditions are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: “Shodex KF802” manufactured by Showa Denko KK (8.0 mm （× 300 mm)
+ Showa Denko “Shodex KF802” (8.0 mmФ × 300 mm)
+ Showa Denko Co., Ltd. “Shodex KF803” (8.0 mmФ × 300 mm)
+ Showa Denko Co., Ltd. “Shodex KF804” (8.0 mmФ × 300 mm)
Column temperature: 40 ° C
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.30” manufactured by Tosoh Corporation
Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Sample: 0.5% by mass tetrahydrofuran solution in terms of resin solids filtered through a microfilter Injection volume: 0.1 ml
Standard sample: Monodispersed polystyrene below

(Standard sample: monodisperse polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation

  In the step 1-2, by removing impurities such as unreacted substances such as (a1) and (a2) from the polycondensate (α), the crystallinity of the resulting radically curable compound (A) is high. Become. Therefore, the radically curable compound (A) is easily packed finely. The radical curable compound of the present invention is cured while being packed finely. As a result, the molecular motion of the cured product is suppressed, and the glass transition temperature is 400 ° C. or higher, which can express heat resistance that is twice or more that of the conventional one.

  As a method for recovering the polycondensate (α) in the reaction solution in Step 1-2, for example, the reaction solution was obtained by introducing the reaction solution into a poor solvent (S1) in which the reaction product is insoluble or hardly soluble. A method in which a precipitate is filtered, and then the reaction product is dissolved in a solvent (S2) that is also mixed with the poor solvent (S1), and again added to the poor solvent (S1), and the resulting precipitate is filtered off. Is mentioned. Examples of the poor solvent (S1) used in this case include water; monoalcohols such as methanol, ethanol, propanol, and ethoxyethanol; Aromatic hydrocarbons such as toluene and xylene are listed. Among these poor solvents (S1), water, methanol, and ethoxyethanol are preferable because the acid catalyst can be efficiently removed at the same time.

  On the other hand, examples of the solvent (S2) include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5- Polyols such as pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerin; 2-ethoxyethanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether Glycol ethers such as ethylene glycol ethyl methyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane and 1,4-dioxane; glycol esters such as ethylene glycol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like Examples include ketones. The (S2) is preferably acetone when water or monoalcohol is used as the poor solvent (S1). The poor solvent (S1) and the solvent (S2) can be used alone or in combination of two or more.

  Examples of the base used in Step 1-3 include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; tertiary such as triethylamine and trimethylamine. Amine; pyridine and the like. Among bases, potassium carbonate and tertiary amine are preferred because they can be easily removed from the reaction system after the reaction of polycondensate (A) with (meth) acrylic acid halide (β). Among them, potassium carbonate and triethylamine are preferred. Is more preferable.

  In the step 1-3, a solvent may be used as necessary. Examples of the solvent include monoalcohols such as methanol, ethanol, and propanol; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Polyols such as hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, glycerol; 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol Glycol ethers such as ruethyl methyl ether and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane and tetrahydrofuran; glycol esters such as ethylene glycol acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone and the like Examples include ketones. These solvents can be used alone or in combination of two or more. Of these solvents, tetrahydrofuran, methyl ethyl ketone, and methyl isobutyl ketone are preferred because the resulting compound has excellent solubility.

  In step 1-3, the reaction temperature for reacting the polycondensate (α) with the (meth) acrylic acid halide (β) is, for example, 20 to 80 ° C. Moreover, reaction time is 1 to 30 hours, for example.

  The charging ratio of the polycondensate (α) and the (meth) acrylic acid halide (β) in step 1-3 is such that the target radical curable compound (A) has high purity and is obtained in good yield. When the mole number of the phenolic hydroxyl group contained in the polycondensate (α) is α ′, [(α ′) / (β)] is preferably in the range of 1 / 0.5 to 1/3 in terms of molar ratio. A range of 1/1 to 1/2 is more preferable.

  The acrylic polymer of the present invention is obtained by reacting the polymer (I) obtained by radical polymerization of the radical curable compound (A) with the aldehyde compound (B). The polymer (I) can be obtained, for example, by adding a polymerization initiator and irradiating with active energy rays or by applying heat to cure.

  When the radical curable compound (A) is irradiated with active energy rays and cured by radical polymerization, an intramolecular cleavage type photopolymerization initiator or a hydrogen abstraction type photopolymerization initiator is used as the polymerization initiator.

  Examples of the intramolecular cleavage type photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thio Acetophenone-based compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenylphos Acylphosphine oxide compounds such as fin oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; 1,1′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2 -Azo compounds such as cyano-2-propylazoformamide; benzyl, methylphenylglyoxyester and the like.

  Examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4- Thioxanthone compounds such as dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler-ketone and 4,4′-diethylaminobenzophenone; 10-butyl 2-chloro-acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

  Among the above photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- Acetophenone compounds such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone and benzophenone are preferred, and 1-hydroxycyclohexyl phenyl ketone is particularly preferred. These photopolymerization initiators can be used alone or in combination of two or more.

  0.01-20 mass parts is preferable with respect to 100 mass parts of radical curable compounds (A), and, as for the usage-amount of the said photoinitiator, 0.1-15 mass% is more preferable, 0.5-10 masses Part is more preferred. In addition, when using the electron beam mentioned later as an active energy ray, a photoinitiator is unnecessary.

  Examples of active energy rays used for curing the radical curable compound (A) include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of energy sources or curing devices that generate these active energy rays include germicidal lamps, ultraviolet lamps (black lights), carbon arcs, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, Examples thereof include an electrode lamp, a metal halide lamp, an ArF excimer laser, an ultraviolet LED, an ultraviolet ray using natural light as a light source, or an electron beam by a scanning type or curtain type electron beam accelerator.

  When the radical curable compound (A) is cured by thermal radical polymerization, a thermal radical polymerization initiator is used. Examples of the thermal radical polymerization initiator include benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 3,3,5-trimethylhexanoyl peroxide, di-2-ethylhexyl peroxydicarbonate, and methyl ethyl ketone. Peroxide, t-butyl peroxyphthalate, t-butyl peroxybenzoate, di-t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-hexanoate, t-butyl peroxy Organic peroxides such as 3,3,5-trimethylhexanoate; 1,1′-azobisisobutyronitrile, 1,1′-azobiscyclohexanecarbonitrile, 2-cyano-2-propylazoformamide And azo compounds. Among these thermal radical polymerization initiators, benzoyl peroxide and 1,1'-azobisisobutyronitrile are preferable. Moreover, these thermal radical polymerization initiators can be used alone or in combination of two or more.

  0.01-20 mass parts is preferable with respect to 100 mass parts of radical curable compounds (A), and, as for the usage-amount of the said thermal radical polymerization initiator, 0.1-15 mass% is more preferable, 0.5-10 Part by mass is more preferable.

  The weight average molecular weight (Mw) of the polymer (I) is preferably from 2,000 to 60,000, preferably from 5,000 to 50,000 because it is easily dissolved in a solvent when reacted (addition condensation) with the aldehyde compound (B). 30,000 is more preferable.

  Examples of the aldehyde compound (B) used in the present invention include aromatic aldehydes and aliphatic aldehydes. Examples of aromatic aldehydes include benzaldehyde, o-tolualdehyde, salicylaldehyde, cinnamic aldehyde, α-naphthaldehyde and the like. Examples of the aliphatic aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovalerinaldehyde, pivalinaldehyde, capronaldehyde, heptaldehyde, caprylaldehyde, pelargonaldehyde, caprinaldehyde, Examples include undecyl aldehyde, lauric aldehyde, tridecyl aldehyde, stearaldehyde, glyoxal, succindialdehyde, glutardialdehyde and the like. As the aldehyde compound (B), an aliphatic aldehyde is preferable and formaldehyde is more preferable because reactivity with the polymer (I) is good and the acrylic polymer of the present invention is easily obtained.

  The reaction between the polymer (I) and the aldehyde compound (B) may be performed, for example, at 60 to 100 ° C. for 2 to 20 hours, whereby the acrylic polymer of the present invention is obtained.

  The acrylic polymer of the present invention obtains a polymer (I) obtained by radical polymerization of the radical curable compound (A), and then quickly reacts the polymer (I) with the aldehyde compound (B). After obtaining the polymer (I), it may be temporarily stored and reacted with the aldehyde compound (B) at a later date.

  Another acrylic polymer of the present invention is obtained by radical polymerization of a polymer (II) obtained by reacting a radical curable compound (A) with an aldehyde compound (B). The reaction between the radical curable compound (A) and the aldehyde compound (B) may be performed, for example, at 60 to 100 ° C. for 2 to 20 hours. The weight average molecular weight (Mw) of the polymer (II) obtained at this time is preferably from 2,000 to 60,000, more preferably from 5,000 to 20,000, since the radical polymerization reaction proceeds well.

  In order to radically polymerize the polymer (II), for example, as in the preparation of the polymer (I), it is performed by adding a polymerization initiator and irradiating active energy rays or applying heat to cure. be able to.

  The acrylic polymer of the present invention obtains a polymer (II) obtained by reacting a radical curable compound (A) with an aldehyde compound (B), and then rapidly radically polymerizes the polymer (II). After obtaining the polymer (II), it may be temporarily stored, and may be obtained by radical polymerization at a later date.

  Hereinafter, the present invention will be described in more detail with specific examples. In addition, the measuring method of the NMR spectrum used for the identification of a compound is as follows.

^[1 H-NMR spectrum measurement method]
Structural analysis was performed using “JNM-GSX500 (500 MHz, DMSO-d6, TMS)” manufactured by JEOL Ltd.

Synthesis Example 1 [Synthesis of radical curable compound (A)]
In a 100 ml two-necked flask equipped with a condenser tube, 7.32 g (60 mmol) of 2,5-xylenol and 2.01 g (15 mmol) of terephthalaldehyde were charged and dissolved in 30 ml of 2-ethoxyethanol. 2 ml of sulfuric acid was added while cooling in an ice bath, and then the mixture was heated and stirred in an oil bath at 80 ° C. for 2 hours for reaction. After the reaction, the resulting solution was reprecipitated with water to obtain a crude product. The crude product was redissolved in acetone, and further reprecipitated with water. The obtained product was filtered and dried in vacuum, and a tetrafunctional phenol compound (a1-1) shown below as a pale red powder was obtained. ) 6.23 g was obtained. Formation of the target compound was confirmed by GPC and 1H-NMR.

  A tetrafunctional phenol compound (a1-1) 2.93 g (5 mmol), potassium carbonate 4.15 g (30 mmol), and tetrahydrofuran 30 ml were charged into a 100 ml two-necked flask equipped with a nitrogen condenser, and stirring was started. While cooling in an ice bath, 1.35 g (15 mmol) of acrylic acid chloride was added dropwise over 30 minutes, and then the reaction was carried out by heating and stirring in an oil bath at 70 ° C. for 16 hours. After the reaction, the solid content was filtered off from the resulting solution, and the filtrate was mixed with 60 ml of chloroform and washed three times with 50 ml of water. The organic substance as the lower layer was collected and dried over sodium sulfate, and then the solution was distilled off under reduced pressure to obtain 1.98 g of a white needle crystal radical curing compound (A1). It identified from each peak of 1H NMR, and it confirmed that the target compound of the average substitution number 2.4 was obtained.

Synthesis example 2 (same as above)
The same operation as in Synthesis Example 1 was performed except that 1.80 g (20 mmol) of acrylic acid chloride was used, to obtain 1.67 g of a white needle crystal radical curing compound (A2). It identified from each peak of 1H NMR, and it confirmed that the target compound whose average substitution number is 3.0 respectively was obtained.

Synthesis example 3 (same as above)
The same operation as in Synthesis Example 1 was performed except that 2.70 g (30 mmol) of acrylic acid chloride was used, to obtain 1.72 g of a radical curing compound (A3) of white needle crystals. It identified from each peak of 1H NMR, and it confirmed that the target compound whose average substitution number is 3.6 respectively was obtained.

Synthesis Example 4 [Synthesis of radical curable compound (a ′) for comparison]
The same operation as in Synthesis Example 1 was carried out except that 5.40 g (60 mmol) of acrylic acid chloride was used, respectively, to obtain 2.03 g of a white needle crystal radical curing compound (a′1). It identified from each peak of 1H NMR, and it confirmed that the target compound whose average substitution number is 4.0 was obtained.

Synthesis example 5 (same as above)
150 g of phenol novolac epoxy resin (epoxy equivalent 190 g / eq), 30 g of acrylic acid and 80 g of propylene glycol monomethyl acetate as a solvent were charged in a reaction vessel and reacted at 100 ° C. for 5 hours to give phenol novolac epoxy acrylate [hereinafter, radical curable compound ( a'2). 174 g was obtained.

Example 1
0.5 g of radical curable compound (A1), 0.05 g of Irgacure 184 (manufactured by Ciba Specialty) and 0.5 g of tetrahydrofuran were placed in a Schlenk tube and freeze-dried in a nitrogen atmosphere. The Schlenk tube is sealed and the radical curable compound (A1) is radically polymerized by irradiating light with a high pressure mercury lamp equipped with a 340 nm bandpass filter for 3 hours to obtain a product containing the polymer (I-1). It was. This product was reprecipitated with methanol, and the resulting precipitate was filtered and vacuum dried to obtain 0.32 g of polymer (I-1). A 100 ml two-necked flask equipped with a condenser was charged with 0.30 g of polymer (I-1), 0.05 g of paraformaldehyde, and 10 ml of 2-ethoxyethanol, and stirring was started. While adding 0.1 ml of sulfuric acid while cooling in an ice bath, the mixture was heated and stirred in an oil bath at 70 ° C. for 4 hours for reaction. The obtained solution was reprecipitated with water to obtain a crude product containing the acrylic polymer (1) of the present invention. The crude product was redissolved in acetone and further reprecipitated with water, and then the obtained product was filtered and vacuum dried to obtain an acrylic polymer (1).

  The solubility and heat resistance of the obtained acrylic polymer (1) in a solvent were evaluated as follows. The evaluation results are shown in Table 1.

<Method for evaluating solubility in solvent>
Charge 0.5 g of acrylic polymer (1) and 0.5 g of tetrahydrofuran into a 6 ml sample bottle with a screw cap containing a micromagnetic stirrer chip, and judge by the time until the acrylic polymer (1) dissolves visually. did. Those that melted within 1 minute were marked as ◎, those that melted within 5 minutes were marked with ○, those that melted within 1 hour were marked with Δ, and those that remained insoluble were marked with ×.

<Method for evaluating heat resistance>
The heat resistance was evaluated by measuring the glass transition temperature. The measurement is performed by using a differential scanning calorimeter (manufactured by TA Instruments Co., Ltd., DSC Q100) under a nitrogen atmosphere and scanning under conditions of a temperature range of 25 to 450 ° C. and a temperature rising temperature of 10 ° C./min. It was.

Example 2
A 100 ml two-necked flask equipped with a condenser was charged with 0.5 g of radical curable compound (A1), 0.1 g of paraformaldehyde, and 10 ml of 2-ethoxyethanol, and stirring was started. After adding 0.1 ml of sulfuric acid while cooling in an ice bath, the mixture was heated, stirred and reacted in an oil bath at 70 ° C. for 4 hours to obtain a product containing the polymer (II-1). This product was reprecipitated with water to obtain a crude product of polymer (II-1). The crude product was redissolved in acetone and further reprecipitated with water, and then the obtained product was filtered and vacuum dried to obtain 0.42 g of polymer (II-1). 0.4 g of the synthesized polymer (II-1), 0.04 g of Irgacure 184 (manufactured by Chiba Specialty Co., Ltd.) and 0.5 g of tetrahydrofuran were placed in a Schlenk tube and freeze-dried in a nitrogen atmosphere. The reactor was sealed and irradiated with light from a high-pressure mercury lamp equipped with a 340 nm bandpass filter for 3 hours to obtain a crude product containing the acrylic polymer (2) of the present invention. The crude product was reprecipitated with methanol, and the resulting precipitate was filtered and vacuum dried to obtain an acrylic polymer (2) g. In the same manner as in Example 1, the solubility of the acrylic polymer (2) in the solvent and the heat resistance were evaluated. The evaluation results are shown in Table 1.

Example 3
An acrylic polymer (3) was obtained in the same manner as in Example 1 except that the radical curable compound (A2) was used instead of the radical curable compound (A1). In the same manner as in Example 1, the solubility of the acrylic polymer (3) in the solvent and the heat resistance were evaluated. The evaluation results are shown in Table 1.

Example 4
An acrylic polymer (4) was obtained in the same manner as in Example 2 except that the radical curable compound (A2) was used instead of the radical curable compound (A1). In the same manner as in Example 1, the solubility of the acrylic polymer (4) in the solvent and the heat resistance were evaluated. The evaluation results are shown in Table 1.

Example 5
An acrylic polymer (5) was obtained in the same manner as in Example 1 except that the radical curable compound (A3) was used instead of the radical curable compound (A1). In the same manner as in Example 1, the solubility of the acrylic polymer (5) in the solvent and the heat resistance were evaluated. The evaluation results are shown in Table 1.

Example 4
An acrylic polymer (5) was obtained in the same manner as in Example 2 except that the radical curable compound (A3) was used instead of the radical curable compound (A1). In the same manner as in Example 1, the solubility of the acrylic polymer (6) in the solvent and the heat resistance were evaluated. The evaluation results are shown in Table 1.

Comparative Example 1
A comparative acrylic polymer (1 ′) was obtained in the same manner as in Example 1 except that the comparative radical curable compound (a′1) was used instead of the radical curable compound (A1). In the same manner as in Example 1, the solubility and heat resistance of the comparative acrylic polymer (1 ′) in the solvent were evaluated. The evaluation results are shown in Table 2.

Comparative Example 2
A comparative acrylic polymer (2 ′) was obtained in the same manner as in Example 2 except that the comparative radical curable compound (a′1) was used instead of the radical curable compound (A1). In the same manner as in Example 1, the solubility and heat resistance of the comparative acrylic polymer (2 ′) in the solvent were evaluated. The evaluation results are shown in Table 2.

Comparative Example 3
A comparative radical curable compound (a′2) 0.5 g, Irgacure 184 [manufactured by Chiba Specialty Co., Ltd.] 0.05 g and tetrahydrofuran 0.5 g were placed in a Schlenk tube and freeze-dried in a nitrogen atmosphere. The reactor was sealed and irradiated for 3 hours with a high pressure mercury lamp equipped with a 340 nm bandpass filter. The obtained content was reprecipitated with methanol, and the resulting precipitate was filtered and vacuum dried to obtain a comparative polymer (3 ′). In the same manner as in Example 1, the solubility and heat resistance of the comparative polymer (3 ′) in the solvent were evaluated. The evaluation results are shown in Table 2.

Claims (14)

The following general formula (1) or general formula (2)

[In formula, R < ¹ > -R < ⁵ > is a C1-C8 alkyl group each independently. X _{1 to} X ₄ each independently represent the following formula (a)

Or at least one is a group represented by the formula (a), and at least one is a hydrogen atom. m, n, o, p, and q are each independently an integer of 1 to 4. An acrylic polymer obtained by reacting a polymer (I) obtained by radical polymerization of a radical curable compound (A) represented by formula (B) with an aldehyde compound (B). The radical curable compound (A) represented by the general formula (1) or the general formula (2) is represented by the following general formula (1-1) or the general formula (2-1).

[In formula, R < ¹ > -R < ⁵ > is a C1-C8 alkyl group each independently. X _{1 to} X ₄ each independently represent the following formula (a)

Or at least one group represented by the formula (a). m, n, o, p, and q are each independently an integer of 1 to 4. The acrylic polymer according to claim 1, which is a radical curable compound represented by the formula: The radical curable compound (A) is represented by the general formula (3) or the general formula (4).

[In formula, R < ¹ > -R < ⁵ > is a C1-C8 alkyl group each independently. X _{1 to} X ₄ each independently represent the following formula (a)

Or at least one group represented by the formula (a). m, n, o, p, and q are each independently an integer of 1 to 4. The acrylic polymer according to claim 2, which is a radical curable compound represented by the formula:   The acrylic radical weight according to any one of claims 1 to 3, wherein the radical curable compound (A) is a radical curable compound having an average of 2.2 to 3.8 groups represented by (a). Coalescence. The acrylic polymer according to any one of claims 1 to 4, wherein each of R ^{1 to} R ⁵ is independently a methyl group.   The acrylic polymer according to claim 1 or 2, wherein m, n, p and q are each independently an integer of 1 to 3, and o is 1.   The acrylic polymer according to any one of claims 1 to 6, wherein the aldehyde compound (B) is formaldehyde.   An acrylic polymer obtained by radical polymerization of a polymer (II) obtained by reacting the radical curable compound (A) with an aldehyde compound (B).   The radical curable compound (A) is represented by the general formula (3) or the general formula (4), and is a radical curable compound having an average of 2.2 to 3.8 groups represented by the above (a). The acrylic polymer according to claim 8. The acrylic polymer according to claim 8 or 9, wherein R ^{1 to} R ⁵ are each independently a methyl group.   3. The acrylic polymer according to claim 1, wherein m, n, p and q are each independently an integer of 1 to 3, and o is 1.   The acrylic polymer according to any one of claims 8 to 11, wherein the aldehyde compound (B) is formaldehyde.   A method for producing an acrylic polymer, wherein the radical curable compound (A) is radically polymerized to obtain a polymer (I), and then the polymer (I) is reacted with an aldehyde compound (B). .   A method for producing an acrylic polymer, wherein the radical curable compound (A) and the aldehyde compound (B) are reacted to obtain a polymer (II), and then the polymer (II) is radically polymerized. .