JPH0776544A - Polyfunctional vinyl ether compound - Google Patents

Abstract

PURPOSE:To provide the novel compound photocurable by addition of a photocationic polymerization initiator such as a Lewis acid or protonic acid, useful as a raw material for photosensitive resins for negative-type photoresists, coatings or inks. CONSTITUTION:The polyfunctional vinyl ether compound of formula I [ R<1> is halogen, alkyl, aryl, aralkyl, alkoxyl, aryloxyl or cycloalkyl; Q is OH or OROCH=CH2 (R is l-12C alkylene), the molar. ratio of (OH)/(OROCH=CH2) being (0:100) to (90:10), is 0-4], e.g. a compound of formula II (where, Q is OCH2). The compound of the formula I can be obtained, for example, by contact between a polyhydric phenolic compound of formula III and a haloalkyl vinyl ether of formula XROCH=CH2 (X is halogen).

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]

Acrylate resins represented by epoxy acrylates and urethane acrylates are known as compounds that have been put into practical use as photocurable resins.

[0003]

However, in these conventional acrylate resins, polymerization inhibition by oxygen is inevitable during curing, the curability of the cured film surface is extremely poor, and polymerization inhibition by oxygen is not observed. Photosensitive resins that use photo-cationic polymerization of epoxy groups for the curing reaction have another problem that the curing speed is very slow, and all of them are sufficiently satisfied with the required properties as photosensitive resins. Absent. The object of the present invention is to improve the above-mentioned drawbacks found in conventional acrylate resins, that is, it has fast-curing property, avoids polymerization inhibition by oxygen, and has good surface-curing properties. An object of the present invention is to provide a polyfunctional vinyl ether compound capable of imparting solubility in dilute alkaline water by adjusting the balance between the phenolic hydroxyl group and the vinyloxyalkyloxy group. Solubility in dilute alkaline water is necessary, especially when used in negative photoresists.

[0004]

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)

[0005]

[Chemical 2] [R ¹ represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, or a cycloalkyl group, and when R ¹ is present in the same ring or a plurality of different rings, they are the same as each other. Or may be different. Q is independently, -OH or the general formula (II) -OROCH = CH ₂ (wherein, R
Represents an alkylene group containing 1 to 12 carbon atoms. ) Represents a group represented by (), and represents (-OH) / (-OROC
H = CH ₂₎ = 0/100 to 90/10 (molar ratio). n shows the integer of 0-4. ] 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 halogen atom such as fluorine, chlorine and bromine; methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group,
A linear or branched alkyl group having 10 or less carbon atoms such as nonyl group and decyl group; an aryl group having 15 or less carbon atoms such as phenyl group, tolyl group and naphthyl group; aralkyl such as benzyl group, phenethyl group and benzhydryl group Examples thereof include alkoxy groups such as methoxy group, ethoxy group and propoxy group; aryloxy groups such as phenoxy group, naphthoe group and anthroxy group; cycloalkyl groups having 10 or less carbon atoms such as cyclopentyl group and cyclohexyl group.

Q is independently a hydroxyl group or a vinyloxyalkyloxy group represented by the general formula (II), and the alkylene group R in the formula is methylene, dimethylene, trimethylene, tetramethylene or hexamethylene. , Heptamethylene, octamethylene, nonamethylene, decamethylene, dodecamethylene, or branched isomers thereof. The ratio of hydroxyl group / vinyloxyalkyloxy group is 0 / as the average value of the entire molecule.
It can be arbitrarily set within the range of 100 to 90/10 (molar ratio). As a general synthetic method of the compound represented by the general formula (I), the compound represented by the general formula (III)

[0008]

[Chemical 3] (In the formula, the definitions of R ¹ and n 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). it can.

The polyhydric phenol compound (S) represented by the general formula (III) can be obtained by an acid-catalyzed dehydration condensation reaction of phenols and glyoxal.
Examples of phenols include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, isobutylphenol, t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, diphenol. Various o-, m-, p-isomers of alkylphenol typified by -t-amylphenol or various o-, m-, p of alkoxyphenol typified by methoxyphenol, ethoxyphenol, propoxyphenol and the like. −
Isomer, or cycloalkylphenol typified by cyclopentylphenol, cyclohexylphenol, cyclohexylcresol, or halogen-substituted phenol typified by chlorophenol, dichlorophenol, bromophenol, dibromophenol,
Alternatively, examples include substituted phenols such as arylphenol and aralkylphenol. These phenols may be used alone or in combination of two or more.

In the condensation reaction of 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 these condensation accelerators are used, the charging ratio of the base is in the range of 0.1 to 10.0 mol of the condensation accelerator with respect to 1.0 mol 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 obtain the unreacted compound (S),
(T), inorganic salts, etc. are removed, and the organic layer is dried with a desiccant such as anhydrous sodium sulfate and then concentrated under reduced pressure to obtain the desired product, but the method is not limited to this method. Absent. The polyfunctional vinyl ether compound obtained by the present invention has various uses as a photosensitive resin.

[0014]

When the polyfunctional vinyl ether compound of the present invention is used in a photosensitive resin composition, the polyfunctional vinyl ether compound maintains the same rapid curing property and cured physical properties as those of a conventional photosensitive resin using an acrylate resin. It is possible to impart good surface curability without any inhibition of polymerization by oxygen. Furthermore,
By optimizing the balance of the phenolic hydroxyl group and vinyloxyalkyloxy group in the compound, it is possible to impart the solubility (development property) to diluted alkaline water, which is the property required when using it as a negative photoresist. It is possible to exhibit very excellent photosensitive resin characteristics.

[0015]

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 49.8 g of tetrafunctional phenol (OH equivalent: 100) obtained by the condensation reaction of phenol and glyoxal and 128 g of dimethylsulfoxide were equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introducing device. After being placed in a vessel and dissolved, 25.0 g of powdered sodium hydroxide was added,
Stir for 30 minutes at 0 ° C. Next, 64.0 g of 2-chloroethyl vinyl ether was added dropwise over 30 minutes while maintaining the temperature inside the reactor at 60 ° C, and the temperature was kept at 70 ° C for 6 hours to complete the reaction.

After neutralizing excess sodium hydroxide with 10.9 g of an 85% phosphoric acid aqueous solution, 250 g of methyl isobutyl ketone and 400 g of water are added, and the desired product is extracted into the organic layer and the inorganic salt is dissolved in the aqueous layer. Was done. After this, water 40
Washing with 0 g of water was repeated 5 times, the organic layer was dried over anhydrous sodium sulfate, filtered, and methyl isobutyl ketone was distilled off under reduced pressure to obtain 69.9 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)].

[0019]

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

Example 2 Reaction in which 49.8 g of tetrafunctional phenol (OH equivalent: 100) obtained by condensation reaction of phenol and glyoxal and 128 g of dimethyl sulfoxide were equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introducing device. After being placed in a vessel and dissolved, 10.4 g of powdered sodium hydroxide was added, and 6
Stir for 30 minutes at 0 ° C. Next, 32.0 g of 2-chloroethyl vinyl ether was added dropwise over 30 minutes while maintaining the temperature inside the reactor at 60 ° C, and the temperature was kept at 70 ° C for 6 hours to complete the reaction.

After neutralizing excess sodium hydroxide with 3.5 g of 85% aqueous phosphoric acid solution, methyl isobutyl ketone 2 was added.
50 g and 450 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, water 450
Water washing with g 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 56.7 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,
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.

[0023]

[Chemical 5] (Wherein, Q is -OH or -OCH ₂ CH ₂ OCH = C
H ₂ and the molar ratio of both is 50/50. )

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

[0025]

[Table 1] The photosensitive resin composition is spin-coated on a glass substrate to a thickness of 1.2 μm, prebaked at 60 ° C. for 30 minutes, and then KAS.
As a result of performing patterning exposure in the atmosphere using a PER 2001C exposure machine (manufactured by KASPER), a light amount of 50 m
A cured film free of tack (stickiness) was obtained at J / cm ² . This indicates that there is no polymerization inhibition by oxygen. Further development by butyl cellosolve gave a good pattern with a resolution of 10 μm. "Resolution" is a figure in which several lines are lined up at intervals equal to the line width.
& Space). The line and space pairs whose line widths are changed little by little are used as a mask and the pattern is printed on the substrate to show its resolution limit.

Reference Example 2 Compound (2) obtained in Example 2 was blended as follows to form a photosensitive resin composition.

[0027]

[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 performing patterning exposure in the atmosphere using an ER 2001C exposure machine (manufactured by KASPER), a light amount of 100 m
A tack-free cured film was obtained at J / cm ² . Furthermore,
When developed with a 3% aqueous sodium hydroxide solution, a good pattern with a resolution of 10 μm was obtained.

Claims (1)

[Claims] 1. A compound represented by the general formula (I): [R ¹ represents a halogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, or a cycloalkyl group, and when R ¹ is present in the same ring or a plurality of different rings, they are the same as each other. Or may be different. Q is independently, -OH or the general formula (II) -OROCH = CH ₂ (wherein, R
Represents an alkylene group containing 1 to 12 carbon atoms. ) Represents a group represented by (), and represents (-OH) / (-OROC
H = CH ₂₎ = 0/100 to 90/10 (molar ratio). n shows the integer of 0-4. ] The polyfunctional vinyl ether compound represented by these.