JP2000302749A - (meth)acrylic polyoxyethylene-modified bisphenol s ester, its production and photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a component of image- forming photosensitive resin compositions, with an ultraviolet-curable or electron beam-curable resin as a curing component. SOLUTION: This new compound is a compound of formula I (R1 and R2 are each H or methyl; the average of (m+n) is 6-20, pref. 8-14), e.g. polyoxyethylene-modified bisphenol S dimethacrylate ((m+n)=10). The compound of formula I is obtained by reaction between a polyoxyethylene-modified bisphenol S of formula II and a (meth)acrylic ester of formula III (R2 is a 1-5C alkyl) [e.g. (meth)acrylic methyl, ethyl, propyl, butyl ester] in the presence of a catalyst (e.g. an alkali metal amide, 1-4C alkyl titanate) pref. in the molar ratio of the latter reactant to former reactant of 4-10 under normal or reduced pressures at 60-130 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel (meth) acrylic acid polyoxyethylenated bisphenol S ester which can be easily polymerized in the presence of heat, ultraviolet radiation, ionizing radiation or in the presence of a radical initiator. And a method for producing the same, and a photosensitive resin composition.

[0002]

2. Description of the Related Art Various (meth) acrylates are used as a curable component in an ultraviolet-curable or electron beam-curable resin. Among these, photosensitive resins for image formation that can be developed with an alkaline aqueous solution include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyoxyethyltrimethylolpropanetri (meth) acrylate. (Meth) acrylates such as acrylates have been used. However, when these resins are used as a photoresist for a printed wiring board, satisfactory characteristics such as resolution, flexibility, plating resistance and the like cannot be obtained.

For this reason, Japanese Patent Application Laid-Open No. 58-1142 discloses polyoxyethylenated bisphenol A di (meth) acrylate, and Japanese Patent Application Laid-Open No. 5-1146 discloses polyethylene glycol / polypropylene glycol. Although rublockdiol di (meth) acrylate has been proposed, it cannot be said that the compound satisfies all the required properties.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a novel poly (meth) acrylate containing an ultraviolet-curable or electron-beam-curable resin as a curable component, which can be used particularly as a photosensitive resin composition component for image formation. Oxyethylenated bispheno-
And a method for producing the same.

[0005]

The present invention provides a compound represented by the general formula (I):
(Meth) acrylic acid polyoxyethylenated bisphenol S ester (where m and n are m +
n is a positive integer selected so that the average value of n is from 6 to 20, and R ¹ and R ² each independently represent hydrogen or a methyl group) and a photosensitive resin composition containing the same. .

[0006]

Embedded image

In the present invention, the average value of m + n in the general formula (I) is preferably in the range of 8 to 14.

The present invention also relates to a polyoxyethylenated bisphenol S represented by the general formula (II) and a compound represented by the general formula (I)
The present invention relates to a process for producing a poly (meth) acrylic acid polyoxyethylenated bisphenol S ester, which comprises reacting the (meth) acrylic ester represented by II) in the presence of a catalyst.

[0009]

Embedded image

[0010]

Embedded image Here, m and n are positive integers selected so that the average value of m + n is 6 to 20, R ^{1 in} the formula is hydrogen or a methyl group, and R ² is an alkyl group having 1 to 5 carbon atoms. Represents

In the present invention, m + of the general formula (II)
It is preferable to use polyoxyethylenated bisphenol S having an average value of n in the range of 6 to 20.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the polyoxyethylenated bisphenol S (meth) acrylate and the method for producing the same of the present invention will be described in detail.

In the present invention, the polyoxyethylenated bisphenol S represented by the general formula (II) is m + n
Is preferably 6 to 20, and more preferably m + n is 8 to 14. When the average value of m + n is less than 6, (meth) acrylic acid polyoxyethylenated bisphenol S represented by the general formula (I)
If the ester tends to crystallize, and if the average value of m + n exceeds 20, the polyoxyethylenated (meth) acrylate represented by the general formula (I) is used as a photoresist when manufacturing a printed wiring board. When bisphenol S ester is used, its resolution, flexibility and plating resistance tend to decrease.

Here, the average value of m + n is determined by measuring a nuclear magnetic resonance spectrum (NMR), an infrared absorption (IR) spectrum and a hydroxyl value. Specifically, ¹ H N
Confirm the number of hydrogen atoms by MR, confirm the chemical structure by IR, JIS
The molecular weight is determined by measuring the hydroxyl value according to K0075.

In the present invention, as the (meth) acrylic ester represented by the general formula (III), methyl, ethyl, propyl and butyl esters of acrylic acid and methacrylic acid are used. In the case of a methacrylate, a methyl ester is preferred, and in the case of an acrylate, it is appropriately selected from methyl, ethyl and butyl esters.

In the present invention, first, a polyoxyethylenated bisphenol S represented by the general formula (II) is
The esterification reaction is performed with the (meth) acrylate represented by the general formula (III). At the time of the reaction, the (meth) acrylate represented by the general formula (III) is
It is preferable to use an excess of the polyoxyethylenated bisphenol S represented by the general formula (II) in order to complete the reaction in a short time and to improve the reaction conversion.

In the present invention, it is preferable to use the (meth) acrylic acid ester in an amount of 4 to 10 mol per 1 mol of the polyoxyethylenated bisphenol S. If the amount of the (meth) acrylate used is less than 4 moles per mole of the polyoxyethylenated bisphenol S, the reaction becomes slow, and unreacted polyoxyethylenated bisphenol S remains. Tends to be easy.
On the other hand, if the amount of the (meth) acrylate exceeds 10 moles, the productivity becomes poor, and the process of recovering the excess (meth) acrylate after the reaction is completed tends to take a long time.

The catalyst used for the transesterification in the present invention includes alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate. , Lithium methoxide, sodium methoxide, sodium ethoxide, alkali metal alkoxides such as potassium t-butoxide, lithium amide, sodium amide, alkali metal amides such as potassium amide,
And tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate,
And C1-C4 alkyl titanates such as tetrabutyl titanate. Among these, alkali metal amides or C1 to C4 alkyl titanates are preferable from the viewpoint of handling of the catalyst.

The amount of the catalyst used in the present invention is (meth)
The content is preferably in the range of 0.01 to 5.0% by weight based on the total amount of the acrylate and the polyoxyethylenated bisphenol S. The amount of the catalyst used is (meth) acrylate and polyoxyethylenated bispheno-
If the amount is less than 0.01% by weight based on the total amount of the sulfur S, the progress of the reaction tends to be slow, and if it exceeds 5.0% by weight, no particular effect tends to be obtained. When tetraalkyl orthotitanate is used as a catalyst, if the reaction system contains a large amount of water, the catalyst activity is likely to be lost. It is preferable to keep the water content low or to prevent water from entering during the reaction.

In the transesterification in the present invention, it is preferable to add a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, t-butylhydroquinone, 2,4-dimethyl-6-tbutylphenol, 2,6-tbutyl-p-cresol, parabenzoquinone, 2,5 -Diphenylparabenzoquinone, phenothiazine, diphenylamine and the like are used, but hydroquinone monomethyl ether is preferred as a polymerization inhibitor having less coloring during storage and use of the product.

The amount of the polymerization inhibitor used in the present invention is 5 to 5% based on the amount of the polyoxyethylenated bisphenol S.
2000 ppm is preferable, and 10 to 500 ppm is more preferable. If the amount of the polymerization inhibitor used is less than 5 ppm with respect to the polyoxyethylenated bisphenol S, the polymerization inhibitory effect tends to be insufficient, and 2,000
When the content exceeds ppm, when the product is polymerized, the polymerization tends to be inhibited.

In the present invention, it is preferable to blow a small amount of molecular oxygen during the reaction to prevent polymerization of the reaction solution. The molecular oxygen is preferably used in a diluted state, and air is particularly preferable. In addition, it is preferable that the blowing of the molecular oxygen evaporates into a vapor in order to prevent polymerization of the (meth) acrylic acid ester condensed on the upper kettle wall or the like. The amount of molecular oxygen used is also affected by the shape of the reactor and stirring power,
5 to 500 ml / min per mole of polyoxyethylenated bisphenol S (25 to 2.5
(00 ml / min).

In the transesterification reaction of the present invention, a solvent can be appropriately used as long as it is inert to the reaction. For example, hydrocarbons such as benzene, toluene, xylene, hexane, heptane, octane, isooctane, and cyclohexane, and ethers such as dioxane are exemplified.

The transesterification of the present invention is preferably carried out at 60 to 130 ° C. under normal pressure or reduced pressure. As a form of the transesterification reaction, a general method for producing a (meth) acrylate ester from a (meth) acrylate ester and an alcohol by a transesterification reaction is used. In this method, in order to increase the conversion rate of the raw material alcohol, the lower alcohol by-produced and the raw material (meth) acrylate or solvent are azeotropically distilled to remove the lower alcohol by-produced from the system. It is preferred to synthesize. For this reason, it is preferable to use a batch type reaction vessel equipped with a rectification column as the reaction apparatus.

The (meth) acrylic acid polyoxyethylenated bisphenol S ester represented by the general formula (I) is
It is useful as a curable component of a curable resin composition by radiation or thermal means. Radiation curing is performed by particulate radiation such as ionization or electron beam, or actinic radiation such as ultraviolet radiation. In the case of curing by actinic radiation, it is carried out by incorporating various photosensitizers or photopolymerization initiators.
The thermosetting technique is performed by a general method.

The novel (meth) acrylate in the present invention may be used alone or with another monomer such as an aliphatic or aromatic alcohol (meth) acrylate or an unsaturated group-containing resin. It can be used in combination with resins such as unsaturated polyester, polyester acrylate, epoxy acrylate and urethane acrylate. Further, the novel (meth) acrylic acid polyoxyethylenated bisphenol S ester according to the present invention can be polymerized by adding an organic peroxide, and the photosensitive resin is used for producing a printed wiring board. When used as a photoresist, it has excellent properties such as resolution, flexibility, and plating resistance.

[0027]

The present invention will be described below with reference to examples, but the present invention is not limited by these examples. Here, the value of m + n indicates an approximate number of the average value.

Example 1 Polyoxyethylenated bisphenol S dimethacrylate
Synthesis of (m + n = 10) Polyoxyethylenated bisphenol S (m + n = 10) was placed in a 1-liter flask equipped with a stirrer, thermometer, air inlet tube and rectification tower (15 stages). 248 g (0.728 mol), (Nika Chemical Co., GK1039), methyl methacrylate
7 g (5.097 mol) and 0.06 g of hydroquinone monomethyl ether were charged under a normal pressure at 100 ml / dry air.
The mixture was heated and refluxed while blowing at a rate of min to remove water in the system. Next, 2.5 g of isopropyl orthotitanate (titanium tetraisopropoxide) was added, and a transesterification reaction was performed. Initially, heat the reaction mixture to reflux,
The top temperature of the rectification column is 10 which is the boiling point of methyl methacrylate.
Although the temperature was around 0 ° C, the boiling point of the azeotropic mixture of methanol and methyl methacrylate was approached with the progress of the reaction, so the reflux ratio was adjusted so that the tower top temperature was 65 ° C, and methanol was added to methyl methacrylate. The reaction was carried out while distilling off as an azeotrope with.

About 3 hours after the catalyst was added, the temperature at the top of the column increased, and the reflux ratio was gradually increased at 90 ° C.
Finally, the reaction was continued at a reflux ratio of 15. Four hours after the start of the reaction, the reaction solution was subjected to high performance liquid chromatography (H
As a result of PLC) analysis, no starting alcohol, polyoxyethylenated bisphenol S (m + n = 10), was detected, and an intermediate product, polyoxyethylenated bisphenol S (m + n = 10), was not detected. 4% monomethacrylate (HPLC
(Area ratio), and the reaction was completed when the dimethacrylic acid ester of the alcohol, which was the target compound, was 96% (HPLC area ratio).

The reaction solution was cooled to 80 ° C., and 100 g of 17% by weight saline was added to hydrolyze the catalyst to make it insoluble. 3
After standing for 0 minutes, the oil layer was placed in a 1-liter eggplant-shaped flask by decantation, excess methyl methacrylate was distilled off under reduced pressure using a rotary evaporator, and the solution in the eggplant flask was filtered by vacuum suction filtration. Polyoxyethylenated bisphenol S dimethacrylate (m + n = 10)
I got The yield was 280.6 g (94% overall yield). No crystallization occurred even after one month of standing. FIG. 1 shows an infrared absorption spectrum and FIG. 2 shows a nuclear magnetic resonance spectrum of data of the obtained polyoxyethylenated bisphenol S dimethacrylate (m + n = 10).

FIG. 1 shows an infrared absorption spectrum of the data of the obtained polyoxyethylenated bisphenol S dimethacrylate (m + n = 10), and FIG. 2 shows a nuclear magnetic resonance spectrum. In Figure 1, ether 820 cm ^-1 para-substituted benzene ring, 940 cm ^-1, around 1350 cm ^-1, 1
320 cm ^-1, a sulfone group to 1,120 cm ^-1, 1620
benzene ring, each absorption methylene group to a carbonyl group and 1820 cm ^-1 to 1720 cm ^-1 was confirmed on cm ^-1.
In FIG. 2, the hydrogen of methyl is 1.90 ppm,
Ether at 4.5 ppm, methylene at 5.5 to 6.5 ppm and benzene ring peaks at 6.8 to 8.0 ppm were detected, and oxyethylenated bisphenol S dimethacrylate (m + n = 10).

[0032]

[Table 1]

In Table 1, the appearance was visually observed. Hue, acid value and viscosity (25 ° C) were evaluated according to JIS K6901-4.2,
The test was performed according to JIS K2501-4 and JIS K6901-4.4.1. The refractive index was measured using an Abbe refractometer. Purity was calculated using area% obtained by high performance liquid chromatography analysis.

Comparative Example 1 Polyoxyethylenated bisphenol S dimethacrylate
(M + n = 4) Polyoxyethylenated bisphenol S (m + n = 10) (Nika Chemical Co., GK1039) was converted to polyoxyethylenated bisphenol S (m + n = 4) ( The synthesis was carried out in the same manner as in Example 1 except that Nika was changed. The obtained polyoxyethylenated bisphenol S dimethacrylate (m + n = 4) crystallized and could not be operated or evaluated thereafter.

[0035]

According to the present invention, (meth) acrylic acid polyoxyethylenated bisphenol S ester, which is useful as a component of a photosensitive resin composition for image formation, is converted into polyoxyethylenated bisphenol-form in the presence of a catalyst. Methacrylate and (meth) acrylic acid esters.

[Brief description of the drawings]

FIG. 1 shows an infrared absorption spectrum of the polyoxyethylenated bisphenol S dimethacrylate (m + n = 10) obtained in Example 1. FIG. 2 shows the polyoxyethylenated bisphenol S dimethacrylate (m + n = 1) obtained in Example 1.
1 shows a nuclear magnetic resonance spectrum of (0).

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Katsuyasu Niijima 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Goi Plant F-term (reference) 2H025 AA00 AA02 AB15 AC01 AC06 AD01 BC14 BC43 BJ10 4H006 AA01 AA02 AB46 AB76 AC48 BA02 BA10 BA29 BA32 BA34 BA44 BA50 BA51 BA94 BC10 BC11 BE30 BN10 BP30 GP03 TA02 TB13 4J011 QA03 QA12 QA13 QA40 QB12 QB16 QB19 QB23 SA90 UA01 UA03 VA01 WA01

Claims (5)

[Claims] 1. A polyoxyethylenated bisphenol S ester of (meth) acrylic acid represented by the general formula (I) (where m and n are selected so that the average value of m + n is 6 to 20). And R ¹ and R ² each independently represent hydrogen or a methyl group). Embedded image 2. The polyoxyethylenated bisphenol S (meth) acrylate according to claim 1, wherein in formula (I), the average value of m + n is in the range of 8 to 14. 3. A method comprising reacting a polyoxyethylenated bisphenol S represented by the general formula (II) with a (meth) acrylate ester represented by the general formula (III) in the presence of a catalyst. The polyoxyethylenated bisphenol S (meth) acrylate according to claim 1 or 2,
Method for producing esters. Embedded image Embedded image Here, m and n are positive integers selected so that the average value of m + n is 6 to 20, R ^{1 in} the formula is hydrogen or a methyl group, and R ² is an alkyl group having 1 to 5 carbon atoms. Represents 4. The polyoxyethylene (meth) acrylate according to claim 3, wherein polyoxyethylenated bisphenol S having an average value of m + n in the range of 6 to 20 in the general formula (II) is used. For producing bisphenol S-esters. 5. A photosensitive resin composition comprising the polyoxyethylenated bisphenol S (meth) acrylate according to claim 1.