JPH0881521A - Polyfunctional vinyl ether compound - Google Patents

Abstract

PURPOSE: To obtain a polyfunctional vinyl ether compd. which is quick-curing, has good surface-curing characteristics avoiding polymn. inhibition due to oxygen, and can be made sol. in a dil. aq. alkali soln. by adopting a specific molecular structure. CONSTITUTION: The polyfunctional vinyl ether compd. is represented by formula I or II. In formula I, Q is -H or -CH2 CH(OH)CH2 OCH=CH2 provided the molar ratio of -H to -CH2 CH(OH)CH2 OCH=CH2 in the compd. is (0/100)-(90/10); R is -H, 10C or lower alkyl or cycloalkyl, 15C or lower aryl, or halogen provided R's in the same ring may be the same or different from each other; and n is 1-50. In formula II, Q and R are each the same as in formula I; A is a unit derived from a compd. having an unsatd. group capable of undergoing chain polymn.; m and n are each 1 or higher provided m+n is 2-50; and formula II represents a random copolymer too.

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]

Acrylic resins represented by epoxy acrylate, urethane acrylate, etc. 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 properties, has good surface-curing properties by avoiding polymerization inhibition by oxygen, and has a further Providing a polyfunctional vinyl ether compound that can impart solubility in dilute alkaline water by adjusting the balance between phenolic hydroxyl groups and vinyloxyalkyl groups (the latter is necessary especially when used in negative photoresists) It is to be.

[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 have completed the present invention. I arrived. That is, the present invention is as follows. (1) General formula (I)

[0005]

[Chemical 4] Wherein, Q is a hydrogen atom or the formula -CH ₂ CH (OH)
CH ₂ OCH═CH ₂ represents a group, R represents a hydrogen atom, an alkyl group or a cycloalkyl group having 10 or less carbon atoms, an aryl group having 15 or less carbon atoms, or a halogen atom, and R is the same. Within one part, they may be the same or different from each other. In Q, -H / -CH
The ratio of ₂ CH (OH) CH ₂ OCH = CH ₂ is a value in the range of 0/100 to 90/10 (molar ratio) as an average value. n is the average number of repeating units and represents a positive number from 1 to 50. ] The polyfunctional vinyl ether compound represented by these.

(2) General formula (II)

[Chemical 5] Wherein, Q is a hydrogen atom or the formula -CH ₂ CH (OH)
CH ₂ OCH═CH ₂ represents a group represented by R, R represents a hydrogen atom, an alkyl group or a cycloalkyl group having 10 or less carbon atoms, an aryl group having 15 or less carbon atoms, or a halogen atom; Within one part, they may be the same or different from each other. In Q, -H / -CH
The ratio of ₂ CH (OH) CH ₂ OCH = CH ₂ is a value in the range of 0/100 to 90/10 (molar ratio) as an average value. A is a unit derived from a compound having an unsaturated group capable of causing chain polymerization. m and n are the average number of repeating units, each is 1 or more, and m + n is 2
Indicates a positive number in the range from 1 to 50. This formula also represents a random type copolymer. ] The polyfunctional vinyl ether compound represented by these.

(3) General formula (III)

[Chemical 6] Wherein, Q is a hydrogen atom or the formula -CH ₂ CH (OH)
A group represented by CH ₂ OCH═CH ₂ is shown. In _{Q, -H / -CH 2 CH (} OH) CH 2 OCH = CH
The ratio of ₂ is a value in the range of 0/100 to 90/10 (molar ratio) as an average value. m and n are average number of repeating units, each is 1 or more, and m + n is 2 to 5
Indicates a positive number in the range of 0. This formula also represents a random type copolymer. ] 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 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; cycloalkyl having 10 or less carbon atoms such as cyclopentyl group and cyclohexyl group Examples include groups. Further, Rs may be the same or different from each other in the same ring. n
Represents an integer of 1 to 50.

Q is independently a hydrogen atom or a formula
-CH₂CH (OH) CH₂OCH = CH₂Represented by
A group, -H / -CH₂CH (OH) CH₂OCH =
CH ₂The ratio is 0/100 to 90/10 as an average value.
It can be arbitrarily set within the range of (molar ratio).

In the general formula (II), the substituent R 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 linear or branched alkyl group having 10 or less carbon atoms such as a nonyl group and a decyl group;
Examples thereof include aryl groups having 15 or less carbon atoms such as phenyl group, tolyl group and naphthyl group; and cycloalkyl groups having 10 or less carbon atoms such as cyclopentyl group and cyclohexyl group. Further, Rs may be the same or different from each other in the same ring. m and n are the average number of repeating units, each is 1 or more, and m + n is 2 to 50.
Indicates a positive number in the range.

[0011] Q is independently a group represented by hydrogen or the formula _{(-CH 2 CH (OH) CH} 2 OCH = CH 2), -H / -CH 2 CH (OH) CH 2 OC
The ratio of H = CH ₂ is 0/100 to 90/1 as an average value.
It can be arbitrarily set within the range of 0 (molar ratio).

A is a unit derived from a compound having an unsaturated group capable of causing chain polymerization. Examples of the compound that gives A include the following compounds. Acrylic acid, methacrylic acid, acrylic (or methacrylic) acid esters, styrene, α-methylstyrene, vinyl acetate, isoprene, butadiene, isobutene, propylene, isobutyl vinyl ether, methyl vinyl sulfide, ethylene, vinyl chloride, vinylidene chloride, methyl vinyl Ketone, acrylonitrile, acrylamide, maleic anhydride, vinylidene cyanide, etc. The compound represented by the general formula (II) includes a random type or block type copolymer.

The compound represented by the general formula (III) is
It is one of the examples of the compound represented by the general formula (II). General
In formula (III), Q is independently hydrogen atom.
Child or formula-CH ₂CH (OH) CH₂OCH = CH₂
Is a group represented by₂CH (OH) CH
₂OCH = CH₂The ratio is 0/100 to 9 as an average value.
It can be arbitrarily set within the range of 0/10 (molar ratio). m, n
Is the average number of repeating units and each is 1 or more.
And m + n is a positive number in the range of 2 to 50.
Compounds represented by the general formula (I), (II) or (III)
As a general synthetic method of the compound, there are general formula (IV),
(V) or (VI)

[0014]

[Chemical 7]

[0015]

Embedded image

[0016]

[Chemical 9] (In the formulae, R, A, m and n are defined by the general formula (I),
It is the same as that of (II) or (III). It can be obtained by contacting the polyhydric phenol compound (S1), (S2) or (S3) represented by) with glycidyl vinyl ether (T).

Polyphenol compounds (S1), (S2)
Alternatively, in the addition reaction of (S3) with glycidyl vinyl ether (T), a suitable catalyst, for example, organic phosphines such as triphenylphosphine; imidazoles such as 4-methylimidazole and 2-methylimidazole;
1,8-diazabicyclo (5,4,0) undecene-
7. A tertiary amine such as triethylamine can be added to accelerate the reaction.

When these catalysts are used, the amount of the catalyst charged is in the range of 0.1 to 10.0 parts by weight based on 100 parts by weight of glycidyl vinyl ether (T),
A high reaction accelerating effect can be obtained by preferably setting it in the range of 0.2 to 3.0 parts by weight.

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 from room temperature to 120 ° C is preferred. As a method for isolating and purifying the desired product after the completion of the reaction, a known method can be adopted. For example, after cooling the reaction solution to room temperature, by extracting the organic layer with toluene or methyl isobutyl ketone and washing with water several times,
Examples include a method of removing the unreacted compound (S) and the inorganic salt, drying the organic layer with a drying agent such as anhydrous sodium sulfate, and then concentrating under reduced pressure to obtain the desired product. However, the method is not limited to this method. Not a thing. The polyfunctional vinyl ether compound obtained by the present invention has various uses as a photosensitive resin.

[0020]

INDUSTRIAL APPLICABILITY When the polyfunctional vinyl ether compound of the present invention is used as a photosensitive resin composition, it has the same or higher curing speed, cured physical properties, and oxygen content as those of conventional photosensitive resins using acrylate resins. Good surface curability with no polymerization inhibition by the compound, and by optimizing the balance of the phenolic hydroxyl group and vinyloxyalkyl group in the compound, it is a dilute alkalinity that is a necessary property when using it as a negative photoresist. It is possible to exhibit very excellent characteristics of the photosensitive resin, such as being able to impart water solubility (phenomenon characteristics).

[0021]

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 12.0 g of Maruka Linker M (a polyvalent phenol compound of the general formula (IV) type, manufactured by Maruzen Petrochemical Co., Ltd.) under the trade name, 3.2 g of dimethyl sulfoxide, 1 of methyl isobutyl ketone
7.5 g, 4-methylimidazole 0.08 g, and glycidyl vinyl ether 3.0 g were charged into a reactor equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introducing device, and the temperature inside the reactor was raised to 100 ° C. After dissolution, the reaction was allowed to proceed by further maintaining the temperature at 100 ° C. for 20 hours.

Methyl isobutyl ketone 30.0 g, 20
% NaCl aqueous solution (50.0 g) was added to extract the target substance into the organic layer. After that, 30.0 g of a 20% aqueous sodium chloride solution was repeatedly washed with salt water three times, the organic layer was dried over anhydrous sodium sulfate, filtered, and methyl isobutyl ketone was distilled off under reduced pressure to give 11.
3 g were obtained.

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 . The vinyl ether equivalent was determined by the iodine-methanol method and the vinyl ether introduction rate was calculated. As a result, the introduction rate was 28%. The obtained compound is a polyfunctional vinyl ether compound represented by the following formula [hereinafter referred to as compound (1)].

[0025]

[Chemical 10] (Wherein, Q is -H or _{-CH 2 CH (OH) CH 2} O
CH = CH ₂ and the ratio of both is 72/28. The value of n is 13 on average. )

Example 2 26.0 g of Maruka Linker CST50 (trade name) (general formula (V) type polyvalent phenol compound, manufactured by Maruzen Petrochemical Co., Ltd.),
3.2 g of dimethyl sulfoxide, 35.0 g of methyl isobutyl ketone, 0.08 g of 4-methylimidazole, and 4.0 g of glycidyl vinyl ether were charged into a reactor equipped with a reflux condenser, a thermometer, a stirrer, and a nitrogen introducing device to carry out a reaction. After the temperature inside the vessel was raised to 100 ° C. to dissolve it, the temperature was further kept at 100 ° C. for 20 hours to allow the reaction to proceed.

Methyl isobutyl ketone 30.0 g, 20
% NaCl aqueous solution (50.0 g) was added to extract the target substance into the organic layer. After that, washing with 30.0 g of 20% aqueous sodium chloride solution was repeated 3 times, the organic layer was dried with anhydrous sodium sulfate, filtered, and methyl isobutyl ketone was distilled off under reduced pressure to give 21.
7 g were obtained.

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 . The vinyl ether equivalent was determined by the iodine-methanol method and the vinyl ether introduction rate was calculated. As a result, the introduction rate was 30%. The obtained compound is a polyfunctional vinyl ether compound represented by the following formula [hereinafter referred to as compound (2)].

[0029]

[Chemical 11] (Wherein, Q is -H or _{-CH 2 CH (OH) CH 2} O
CH = CH ₂ and the ratio of both is 70/30. The average values of m and n are 10. This compound is a random type copolymer. )

Example 3 22.0 g of Maruka Linker CMM (general formula (VI) type polyvalent phenol compound, manufactured by Maruzen Petrochemical Co., Ltd.), 3.2 g of dimethyl sulfoxide, 32.0 g of methyl isobutyl ketone, 4 -Methylimidazole (0.08 g) and glycidyl vinyl ether (5.0 g) were charged into a reactor equipped with a reflux condenser, thermometer, stirrer, and nitrogen introducing device, and the temperature inside the reactor was raised to 100 ° C to dissolve it. Further, the reaction was allowed to proceed by keeping the temperature at 100 ° C. for 24 hours.

Methyl isobutyl ketone 30.0 g, 20
% NaCl aqueous solution (50.0 g) was added to extract the target substance into the organic layer. Thereafter, washing with 30.0 g of a 20% aqueous sodium chloride solution was repeated three times, the organic layer was dried over anhydrous sodium sulfate, filtered, and methyl isobutyl ketone was distilled off under reduced pressure to give 20.
3 g were obtained.

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 . The vinyl ether equivalent was determined by the iodine-methanol method and the vinyl ether introduction rate was calculated. As a result, the introduction rate was 45%. The obtained compound is a polyfunctional vinyl ether compound represented by the following formula [hereinafter referred to as compound (3)].

[0033]

[Chemical 12] (Wherein, Q is -H or _{-CH 2 CH (OH) CH 2} O
CH = CH ₂ and the ratio of both is 55/45. The values of m and n are 27 on average. ) This compound is a random type copolymer.

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

[0035]

[Table 1] Irgacure 261: trade name, manufactured by Ciba-Geigy, cationic photopolymerization initiator This 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 KA.
As a result of performing patterning exposure in the atmosphere using a SPER 2001C exposure machine (manufactured by KASPER), a light amount of 30
mJ / cm ² , post exposure bake 120 ° C ×
A cured film without tack (stickiness) was obtained in 2 minutes.
This indicates that there is no polymerization inhibition by oxygen. Further, when a phenomenon was caused with a 2.3% aqueous sodium hydroxide solution, a good pattern with a resolution of 10 μm was obtained. "Resolution" is measured using a figure (line & space) in which several lines are arranged at intervals equal to the line width. The set of line & space in which the line width is changed little by little is used as a mask and the resolution limit is shown.

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

[0037]

[Table 2] Irgacure 261: trade name, manufactured by Ciba-Geigy, cationic photopolymerization initiator This 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 KA.
As a result of performing patterning exposure in the atmosphere using a SPER 2001C exposure machine (manufactured by KASPER), a light amount of 20
mJ / cm ² , post exposure bake 120 ° C ×
A cured film without tack (stickiness) was obtained in 5 minutes.
This indicates that there is no polymerization inhibition by oxygen. Furthermore, when the phenomenon was caused with a 50% acetone aqueous solution, a good pattern with a resolution of 10 μm was obtained.

Reference Example 3 The compound (3) obtained in Example 3 was blended as follows to prepare a photosensitive resin composition.

[0039]

[Table 3] This photosensitive resin composition was spin-coated on a glass substrate to a thickness of 1.2 μm, prebaked at 60 ° C. for 5 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 15 m
J / cm ² , post exposure bake 120 ° C x 2
A cured film having no tack was obtained in a minute. Furthermore, when a phenomenon was caused with acetone, a good pattern with a resolution of 10 μm was obtained.

Claims (3)

[Claims] 1. A compound represented by the general formula (I): Wherein, Q is a hydrogen atom or the formula -CH ₂ CH (OH)
CH ₂ OCH═CH ₂ represents a group, R represents a hydrogen atom, an alkyl group or a cycloalkyl group having 10 or less carbon atoms, an aryl group having 15 or less carbon atoms, or a halogen atom, and R is the same. Within one part, they may be the same or different from each other. In Q, -H / -CH
The ratio of ₂ CH (OH) CH ₂ OCH = CH ₂ is a value in the range of 0/100 to 90/10 (molar ratio) as an average value. n is the average number of repeating units and represents a positive number from 1 to 50. ] The polyfunctional vinyl ether compound represented by these. 2. A compound represented by the general formula (II): Wherein, Q is a hydrogen atom or the formula -CH ₂ CH (OH)
CH ₂ OCH═CH ₂ represents a group represented by R, R represents a hydrogen atom, an alkyl group or a cycloalkyl group having 10 or less carbon atoms, an aryl group having 15 or less carbon atoms, or a halogen atom; Within one part, they may be the same or different from each other. In Q, -H / -CH
The ratio of ₂ CH (OH) CH ₂ OCH = CH ₂ is a value in the range of 0/100 to 90/10 (molar ratio) as an average value. A is a unit derived from a compound having an unsaturated group capable of causing chain polymerization. m and n are average number of repeating units, each is 1 or more, and m + n is a positive number in the range of 2 to 50. This formula also represents a random type copolymer. ] The polyfunctional vinyl ether compound represented by these. 3. A compound represented by the general formula (III): Wherein, Q is a hydrogen atom or the formula -CH ₂ CH (OH)
A group represented by CH ₂ OCH═CH ₂ is shown. In _{Q, -H / -CH 2 CH (} OH) CH 2 OCH = CH
The ratio of ₂ is a value in the range of 0/100 to 90/10 (molar ratio) as an average value. m and n are average number of repeating units, each is 1 or more, and m + n is 2 to 5
Indicates a positive number in the range of 0. This formula also represents a random type copolymer. ] The polyfunctional vinyl ether compound represented by these.