JPH07252246A - Polyfunctional vinyl ether compound - Google Patents

Abstract

(57) [Abstract] [Purpose] When used as a photosensitive resin, it has good surface-hardening properties such as fast curing and no polymerization inhibition by oxygen. To provide a polyfunctional vinyl ether compound capable of imparting solubility in dilute alkaline water by adjusting the balance of vinyloxyalkyl groups (the latter is necessary especially when used in a negative photoresist). [Structure] General formula (I) [In formula, Q is a hydrogen atom or general formula -ROCH = CH
₂ (in the formula, R represents an alkylene group containing 1 to 12 carbon atoms), and R ₁ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, or a cycloalkyl group. Represents an aryl group having 15 or less carbon atoms or a halogen atom. R ₂ represents an alkyl group having 10 or less carbon atoms. n shows the integer of 0-3. Also Q
In, the ratio of hydrogen atom / vinyloxyalkyl group is
The average value is a value in the range of 0/100 to 90/10 (molar ratio). ] The polyfunctional vinyl ether compound represented by these.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyfunctional vinyl ether compound. This compound can be photocured by adding a photocationic polymerization initiator such as a Lewis acid or a protonic acid, and as an industrial field of application, for example, as a photosensitive resin such as a negative photoresist, a paint, or an ink. It can be used.

[0002]

2. Description of the Related Art Compounds that have been put into practical use as photosensitive resins include acrylate resins represented by epoxy acrylate and urethane acrylate.

However, in these conventional acrylate resins, polymerization inhibition by oxygen is unavoidable at the time of curing, the curability of the surface of the cured film is remarkably poor, and the cationic photopolymerization of the epoxy group in which the polymerization inhibition by oxygen is not observed. The photosensitive resin using the resin in the curing reaction has another problem that the curing speed is very slow, and none of them satisfy the required characteristics as the photosensitive resin.

[0004]

The object of the present invention, when used as a photosensitive resin, is that it has good surface-hardening properties such that it has fast-curing properties and does not inhibit polymerization by oxygen.
Furthermore, by adjusting the balance between the phenolic hydroxyl group and the vinyloxyalkyl group in the molecule, solubility in dilute alkaline water can also be imparted (the latter is necessary especially when used for negative photoresists). It is to provide a functional vinyl ether compound.

[0005]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a compound having a specific structure satisfies the above-mentioned object, and to complete the present invention. I arrived. That is, the present invention is as follows. General formula (I)

[0006]

[Chemical 2] [In formula, Q is a hydrogen atom or general formula -ROCH = CH
₂ (in the formula, R represents an alkylene group containing 1 to 12 carbon atoms), and R ₁ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, or a cycloalkyl group. Represents an aryl group having 15 or less carbon atoms or a halogen atom, and R ₁ is the same ring;
Further, they may be the same or different in different rings. R ₂ represents an alkyl group having 10 or less carbon atoms, and R ₂ may be the same as or different from each other.
n shows the integer of 0-3. In Q, the ratio of hydrogen atom / vinyloxyalkyl group is 0/1 as an average value.
It is a value in the range of 00 to 90/10 (molar ratio). ] The polyfunctional vinyl ether compound represented by these.

The present invention will be described in detail below. In the general formula (I), the substituent R ₁ is a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a heptyl group, a nonyl group. And a linear or branched alkyl group having 10 or less carbon atoms such as decyl group; an aryl group having 15 or less carbon atoms such as phenyl group, tolyl group and naphthyl group; cyclo having 10 or less carbon atoms such as cyclopentyl group and cyclohexyl group An alkyl group etc. are illustrated. Examples of the substituent R ₂ include a linear or branched alkyl group having 10 or less carbon atoms such as methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, nonyl group and decyl group. It is illustrated. R ₁ may be the same or different in the same ring or in different rings. R ₂
May be the same as or different from each other. n is
Indicates an integer of 0 to 3. The substitution position of R ₁ is not particularly limited.

Q is independently a hydrogen atom or a vinyloxyalkyl group represented by the above formula, and the alkylene group R in the formula is methylene, dimethylene,
Examples thereof include trimethylene, tetramethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, and isomers having a branch thereof. The ratio of hydrogen atom / vinyloxyalkyl group can be arbitrarily set within the range of 0/100 to 90/10 (molar ratio) as an average value. As a general method for synthesizing the compound represented by the general formula (I), the general formula (II)

[0009]

[Chemical 3] (In the formula, the definitions of R ₁ and R ₂ are the same as those of the general formula (I).) The polyhydric phenol compound (S)
And a haloalkyl vinyl ether (T) represented by the general formula XROCH = CH ₂ (wherein X represents a halogen atom and R represents an alkylene group containing 1 to 12 carbon atoms).
Can be obtained by contacting with.

The polyhydric phenol compound (S) represented by the general formula (II) can be obtained by an acid-catalyzed dehydration condensation reaction of resorcinols and aliphatic ketones. Examples of resorcinols include resorcinol,
Methyl resorcinol, ethyl resorcinol, n-propyl resorcinol, isopropyl resorcinol,
Examples thereof include n-butylresorcinol, isobutylresorcinol, t-butylresorcinol, amylresorcinol, hexylresorcinol, cyclohexylresorcinol, methyl-cyclohexylresorcinol, methylbutylresorcinol, phenylresorcinol and naphthylresorcinol. These resorcinols can be used alone or as a mixture of two or more kinds.

Examples of the aliphatic ketones as the other raw material include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, methyl isobutyl ketone, etc., and carbonyl carbon atom in the molecule. Aliphatic ketones in which each of the two straight-chain or branched-chain alkyl groups bonded to C have 10 or less carbon atoms can be mentioned. These aliphatic ketones can be used alone or as a mixture of two or more kinds.

In the condensation reaction between the polyhydric phenol compound (S) and the haloalkyl vinyl ether (T), a suitable condensation accelerator, for example, an alkali metal compound such as sodium hydroxide, potassium hydroxide or sodium hydride; sodium metal An alkali metal alcoholate such as sodium methylate; a quaternary ammonium salt such as triethylbenzylammonium chloride, tetraethylammonium chloride, tributylbenzylammonium chloride; a metal salt such as sodium carbonate or potassium carbonate may be added to accelerate the reaction. it can.

When using these condensation accelerators, the charging ratio of the base is in the range of 0.1 to 10.0 moles of the condensation accelerator with respect to 1.0 mole equivalent of the OH group of the compound (S),
A high reaction accelerating effect can be obtained by preferably setting it in the range of 0.3 to 2.0 mol.

The reaction can be carried out in an inert solvent such as ethyl cellosolve, dimethyl sulfoxide, ethylene glycol monomethyl ether, dimethyl acetamide. In addition, the reaction temperature is not limited,
The range of room temperature to 100 ° C. is preferable.

The method for isolating and purifying the desired product after completion of the reaction is as follows:
A known method can be adopted. For example, after cooling the reaction solution to room temperature, the organic layer is extracted with toluene or methyl isobutyl ketone and washed several times with water to remove the unreacted compound (S) and inorganic salts, and the organic layer is dried with a drying agent such as anhydrous sodium sulfate. Examples of the method include a method of obtaining the target substance by drying under reduced pressure and then concentrating under reduced pressure. However, the method is not limited to this method. The polyfunctional vinyl ether compound obtained by the present invention has various uses as a photosensitive resin.

[0016]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 30.0 g of trifunctional phenol (OH equivalent: 100) obtained by the condensation reaction of resorcinol and acetone, 120.0 g of dimethyl sulfoxide, and 4.5 g of tetrabutylammonium bromide were mixed with a reflux condenser, a thermometer, After charging and dissolving in a reactor equipped with a stirrer and a nitrogen introducing device, 13.3 g of powdered sodium hydroxide is added and stirred at 60 ° C. for 30 minutes. Then 2-chloroethyl vinyl ether 38.4
g was added dropwise over 15 minutes while maintaining the temperature inside the reactor at 60 ° C., and the temperature was kept at 70 ° C. for 9 hours to complete the reaction.

After neutralizing excess sodium hydroxide with 2.9 g of an 85% phosphoric acid aqueous solution, methyl isobutyl ketone 1 was added.
00.0 g and 200.0 g of water were added, and the target substance was extracted into the organic layer and the inorganic salt was dissolved in the aqueous layer. After this,
Brine washing with 200.0 g of 20% aqueous sodium chloride solution was repeated 5 times, the organic layer was dried with anhydrous sodium sulfate, filtered, and methyl isobutyl ketone was distilled off under reduced pressure to obtain 48.7 g of the desired product.

From its infrared absorption spectrum, 1610c
Absorption by vinyl group at m ^-1 and 975 cm ^-1 1200c
Absorption based on an ether bond was observed at m ^-1 . Also,
It was confirmed that the absorption by the hydroxyl group near 3400 cm ^-1 was completely disappeared and the hydrogen atom of the phenolic hydroxyl group was completely replaced by the vinyloxyethyl group. The obtained compound is a polyfunctional vinyl ether compound represented by the following formula [hereinafter referred to as compound (1)].

[0020]

[Chemical 4] (In the formula, Q is a all _{-CH 2 CH 2 OCH = CH 2} .Me represents a methyl group.)

Example 2 30.0 g of trifunctional phenol (OH equivalent: 100) obtained by the condensation reaction of resorcinol and acetone, 120.0 g of dimethyl sulfoxide, and 4.5 g of tetrabutylammonium bromide were refluxed with a condenser, a thermometer, and A reactor equipped with a stirrer and a nitrogen introducing device is charged and dissolved, 4.0 g of powdery sodium hydroxide is added, and the mixture is stirred at 60 ° C. for 30 minutes. Then 2-chloroethyl vinyl ether 12.8
g was added dropwise over 10 minutes while maintaining the temperature inside the reactor at 60 ° C., and the temperature was kept at 70 ° C. for 5 hours to complete the reaction.

After neutralizing excess sodium hydroxide with 2.9 g of an 85% phosphoric acid aqueous solution, methyl isobutyl ketone 1 was added.
00.0 g and 200.0 g of water were added, and the target substance was extracted into the organic layer and the inorganic salt was dissolved in the aqueous layer. After this,
Brine washing with 200.0 g of 20% aqueous sodium chloride solution was repeated 5 times, the organic layer was dried with anhydrous sodium sulfate, filtered, and methyl isobutyl ketone was distilled off under reduced pressure to obtain 36.4 g of the desired product.

From its infrared absorption spectrum, 1610c
Absorption by vinyl group at m ^-1 and 975 cm ^-1 1200c
Absorption based on an ether bond was observed at m ^-1 . Also,
The residual phenolic hydroxyl group was quantified by the neutralization titration method, and the vinyloxyethyl group substitution rate was calculated.
It was 0%. The obtained compound is a polyfunctional vinyl ether compound represented by the following formula [hereinafter referred to as compound (2)].
Is.

[0024]

[Chemical 5] (Wherein, Q is -H or -CH ₂ CH ₂ OCH = CH ₂
And the ratio of the two is 70/30. Me represents a methyl group. )

Reference Example 1 The compound (1) obtained in Example 1 was blended as follows to prepare a photosensitive resin composition.

[0026]

[Table 1] Irugacure 261: trade name, manufactured by Ciba-Geigy, cationic photopolymerization initiator

The photosensitive resin composition was spin-coated on a glass substrate to a thickness of 1.2 μm, prebaked at 60 ° C. for 30 minutes, and then exposed to a KASPER 2001C exposure machine (KASPE).
As a result of performing patterning exposure in the atmosphere using a product of R Co., Ltd., a cured film free of tack (stickiness) was obtained with a light amount of 15 mJ / cm ² and a post exposure bake of 120 ° C. for 5 minutes. This indicates that there is no polymerization inhibition by oxygen. Furthermore, when a phenomenon was caused with methyl ethyl ketone, a good pattern with a resolution of 5 μm was obtained. "resolution"
Is a figure in which several lines are arranged at intervals equal to the line width (li
ne & space). The line and space pairs whose line widths are changed little by little are used as masks to show the resolution limit.

Reference Example 2 The compound (2) obtained in Example 2 was blended as follows to prepare a photosensitive resin composition.

[0029]

[Table 2] The photosensitive resin composition is spin-coated on a glass substrate to a thickness of 1.2 μm, prebaked at 60 ° C. for 5 minutes, and then KASP.
As a result of patterning exposure in the atmosphere using an ER 2001C exposure machine (manufactured by KASPER), a light amount of 500 m
J / cm ² , post exposure bake 120 ° C x 5
A cured film free of tack was obtained in minutes. Furthermore, when the phenomenon was observed with a 6% sodium hydroxide aqueous solution, the resolution was 10μ.
A good pattern of m was obtained.

[0030]

INDUSTRIAL APPLICABILITY The polyfunctional vinyl ether compound of the present invention, when used as a photosensitive resin, has a curing rate, physical properties of a cured product which are equal to or higher than those of a photosensitive resin using a conventional acrylate resin, and further polymerization by oxygen. Good surface curability without any inhibition, and by optimizing the balance of the phenolic hydroxyl group and vinyloxyalkyl group in the compound, it becomes a dilute alkaline water which is the property required when using it as a negative photoresist. It is possible to develop a very excellent photosensitive resin property that the solubility (phenomenon property) can be imparted.

Claims (1)

[Claims] 1. A compound represented by the general formula (I):[In formula, Q is a hydrogen atom or general formula -ROCH = CH
₂(In the formula, R is an alkyl containing 1 to 12 carbon atoms.
A len group is shown. ) A vinyloxyalkyl group represented by
Show, R₁Is a hydrogen atom or an alkyl group having 10 or less carbon atoms
Or cycloalkyl group, aryl having 15 or less carbon atoms
A group or a halogen atom, and R₁Is in the same ring
And different from each other even if they are the same in different rings.
May be. R ₂Represents an alkyl group having 10 or less carbon atoms
And R₂May be the same or different from each other
Good. n shows the integer of 0-3. Also in Q, water
The ratio of elementary atom / vinyloxyalkyl group is the average value
It is a value in the range of 0/100 to 90/10 (molar ratio).
It ] The polyfunctional vinyl ether compound represented by these.