JPH04153290A - Light ray screening agent - Google Patents

Abstract

PURPOSE:To obtain a light ray screening agent which is excellent in the resistance to high-temperature treatment and whose solubility in organic solvents can be varied by selecting the skeleton and the substituent, by using a specified benz- or naphth-azole compound as the constituent. CONSTITUTION:A light ray screening agent comprising a benz- or naphtho-azole compound of the formula, wherein R<1> and R<2> are each H, or substituted or unsubstituted alkyl; R<3> is H, hydroxyl, halogen, alkyl or alkoxy; R<4> and R<5> are each H, halogen, alkyl or alkoxy; X is O, S, NH or NR (R is alkyl); n is 0 or 1; and A is a benzene or naphthalene ring. This azole compound can be produced by the condensation of, for example, a corresponding 2-methyl benz- or naphtho-azole and a corresponding benzaldehyde in the presence of a dehydration catalyst comprising piperidine or zinc chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention focuses on a specific wavelength range of 300 nm to 450 nm for use in photosensitive resins, photosensitive resin base materials, and laminated substrate base materials.
The present invention relates to a light shielding agent that has high absorption ability in the near ultraviolet to visible short wavelength range of nm.

[Prior art]

In recent years, in fields related to 7-photoresists, which are increasingly demanding ultra-high integration, ultra-heavy weight, and fine definition, research into photosensitive resins and base materials for photosensitive resins, as well as research into laminated substrates for printed wiring, has been actively conducted. It is being said. However, there are problems in that the precision of the desired pattern decreases and it is difficult to obtain a high-resolution pattern due to standing waves caused by reflection from the substrate during actinic light exposure and diffused reflection due to irregularities on the substrate surface, and it is difficult to process both sides of the printed circuit board simultaneously. In some cases, the actinic rays may pass through to the opposite surface, preventing simultaneous exposure. A way to solve this problem is to mix and use a substance that has absorption ability in a specific wavelength range with a synthetic resin or base material for the purpose of preventing halation.Thus, it is possible to provide even stronger antireflection effects. is already known, and in order to prevent active rays from passing through to the opposite side of the laminated wiring board I for double-sided simultaneous processing, the layer members (prepreg) are coated with general ultraviolet ν absorbers and general It is already known to contain optical brighteners for textiles.

Examples of additive substances that have such absorption ability include marine compounds such as Ri 1 Rin 1, Coumarin 7, Coumarin 314, Kumari 338, etc., Quinoline Yellow, Others Magneson ■, Magneson ■, Paris First Yellow (manufactured by Orient Chemical Co., Ltd.), Sumitomo Chemical Co., Ltd. Plast Yellow (manufactured by Sumitomo Chemical),
Macro lettuce yellow (manufactured by Bayer), Kayaset yellow (manufactured by Nippon Kayaku), oil yellow (manufactured by Shirad Chemical)
, p-hydroxy-p-dimethylaminoazobenzene, yellow azo and azo metal-containing dye compounds, and other compounds such as optical brighteners for general fibers are known.

[Problems to be Solved by the Invention] However, since coumarin compounds have a relatively low thermal decomposition temperature, there is a problem in their resistance to treatment at high temperatures.

In addition, regarding the solubility in organic solvents, the above-mentioned coumarin l
Because it is easily soluble in almost all organic solvents, it has the disadvantage that it easily leaches into layers other than the resist layer, and other coumarin-based compounds, yellow azo-based azo alloy thread dye compounds, and fluorescence enhancers for fibers are not recommended. Since the solubility of whitening agents in organic solvents is very low, they have the disadvantage that they precipitate on the resist layer or underlayer when used in an amount sufficient to achieve the desired antireflection effect or shielding effect. Furthermore, it is desirable for the additive substance to be colorless due to its intended use, but in order to provide the photosensitive resin with absorption ability in the photosensitive wavelength range, it is necessary to use a group of yellow dyes alone or in combination. There is a need for a light shielding agent that overcomes these drawbacks.

[Means to solve the problem]

In view of the above-mentioned drawbacks of the prior art, the present inventor has conducted repeated research on substances that have absorption ability in a specific wavelength range. It has much better resistance to processing at high temperatures compared to other compounds, and depending on the selection of the core and substituents of this compound, its solubility in organic solvents can be changed. It is necessary to make it insoluble in specific solvents such as methylene chloride, to increase absorption ability in specific short and long wavelength ranges, and to use yellow dyes together. It has been found to be useful as an ideal ultraviolet shielding agent for photosensitive resins, photosensitive resin base materials, and laminated substrate base materials. The invention has been completed.

That is, the present invention relates to the general formula (wherein R1 and R2 may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, and R3 is a hydrogen atom, a bitroxyl group, a halogen atom, an alkyl group) or represents an alkoxy group, R4 and R6 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and X is 0, S, NH or NR (R is a substituted or unsubstituted alkyl The present invention relates to a light shielding agent comprising a benzo-(or naphtho-)azole compound represented by the following formula, where n is O or l, and the ring represents a benzene ring or a 7-talene ring.

In the above formula, when the groups R1 and R2 are alkyl groups, the alkyl groups of 01 to 4 are preferable, and specific examples thereof include methyl, ethyl, n-propyl, i-propyl, n-butyl, ]-butyl, Tert-butyl is mentioned. Further, when R1 and R2 are substituted alkyl, substituents on the alkyl group include hydroxyl group, CI
~, an alkoxy group, and a cyano group. Specific examples of the alkyl moiety in this alkoxy group include methyl,
Ethyl, n-propyl, i-propyl, n-butyl, l
-butyl and tert-butyl. That is,
Specific examples when R1 and R2 are substituted alkyl include hydroxymethylhydroxyethyl, hydroxypropyl, hydroxybutyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, Examples include cyanomethyl and cyanoethyl.

Specific examples when the group R3 is a halogen atom include fluorine,
Mention may be made of chlorine, bromine and iodine.

Specific examples when the group R3 is an alkyl group include methyl, ethyl, n-propyl, 1-propyl,
Specific examples of alkoxy groups include methoxy, nidoxy, n''-propoxy, and l-propoxy.

Specific examples when the groups R4 and R8 are halogen atoms include fluorine, chlorine, bromine and iodine.

When the groups R4 and R5 are alkyl groups, preferred are C3~ alkyl groups, specific examples of which are methyl, ethyl, D-propyl, i-propyl n-butyl, 1-butyl, tert-butyl, n- pentyl, j-pentyl, 5ec-pentyl/, tart-bentyl, n-
Examples include hexyl, 1-hexyl, n-heptyl, 1-heptyl, n-octyl, -octyl, and ethyl-hexyl.

In addition, when the groups R6 and R'' are alkoxy groups, 01-
4 is preferable, and specific examples include methoxy, ethoxy, n-propoxy, i-propoxy,
Examples include n-butoxy, i-butoxy, and tert-butoxy.

In the above-mentioned formula, when X is NR, R is an alkyl group or a substituted alkyl group, and this alkyl group is c
Preferably, 1 to 2 alkinomerides, ie, methyl and ethyl. Specific examples of substituents on this alkyl group include a cyan group and a phenyl group. That is, specific examples when R is substituted alkyl include cyanoethyl, benzyl, and phenethyl.

Furthermore, in the above formula, X is O, S, NH or NR.
Therefore, benzo-(or naphtho-)azole in the ring system fused to ring A means benzoxazole, benzothiazole, benzimidazole, naphthoxazole, naphthothiazole and naphthimidazole.

The compound represented by the above-mentioned formula is a compound that is stable at high temperatures, so it can be used in places exposed to high temperatures. In addition to changing the solubility in the solvent, it is also possible to adjust the light absorption ability in any specific wavelength range, so it has high absorption ability in the near-ultraviolet to visible short wavelength range of 300 nm to 450 nm. As a light shielding agent, it is suitably used for photosensitive resins, photosensitive resin base materials, laminated substrate base materials, and the like.

Representative examples of the benzo-(or naphtho-)azole compounds of the present invention include the following.

2-(p-diethylamino-phenyl)-5-methyl-
Benzoxazole, 2-(+)-dimethylamino-styryl)-benzoxazole, 2-(p-(N-cyanoethyl-N-ethyl-amino)-styryl)-5-methoxy-benzoxazole, 2-(p- dimethylamino-styryl)-5,7-dimethyl-benzoxazole, 2-(p-diethylamino-phenyl)-〇-methyl-benzothiazole, 2-(p-(N-cyanoethyl-N-ethyl-amino)styryl) -6-Nitoxypenzothiazole, 2-(p-diethylamino-phenyl)-benzimidazole, 2- (p-(N-ethoxyethyl-N-ethylulamino)-styryl)-5-methyl-benzimidazole, 2- (p-(N-ethoxyethyl-N-ditylamino)-styryl)-N-methyl-benzimidazole, 2-(p-dimethylamino-
phenyl)-naphthoxazole, 2 (p-diethylamino-styryl)-naphthoxazole, 2-(p
-(N-cyanoethyl-N-ethyl-amino)styryl)-naphthoxazole, 2-(p-dimethylamino-
phenyl)-naphthothiazole, 2-(p-diethylamino-styryl)naphthothiazole, 2-(p-(N
-cyanoethyl-N-ethyl-amino)-styryl)-
naphthothiazole, 2-(p-(N-ethoxyethyl-
N-ethylamino)-styryl)-su7tothiazole,
2-(p-dimethylamino-phenyl)-naphthoimidazole, 2-(p-diethylamino-styryl)-su7
toimidazole, 2-(p-(N-cyanoethyl-N
-ethyl-amino)-styryl)-naphthoimidazole and the like.

These present compounds may be used in the form of powder or emulsified dispersion, and may be used by kneading them into the required area, dissolving them in combination with a solvent, or applying them, and each may be used alone, Two or more types may be used in combination.

Further, the benzo-(or naphtho-)azole compound of the present invention can be produced by a known method.

For example, a method in which a corresponding 2-methyl-benzo-(or cinnamic acids obtained by condensation reaction (so-called Perkin reaction) of benzaldehydes with malonic acid, malonic acid esters, acetic acid, active methylene groups or active methyl groups such as sodium acetate, and amino-phenols adjacent at the 〇-position. (naphthols), diaminobenzenes (naphthalenes), or amino-thiophenols (thionaphthales) using boric acid or zinc chloride as a dehydration catalyst.

The benzo-(or 7-)azole compound of the present invention is added to a photosensitive resin, a base material for a photosensitive resin, and a laminated substrate base material, and the amount added is preferably 0.1 to 35% by weight. is preferably 0.5 to 30% by weight.

In addition, as the photosensitive resin to which the benzo (or naphtho) azole compound of the present invention is added, all known photosensitive resins can be used, regardless of whether they are positive type or negative type, and examples include orthoquinone diazides and novolac resins. Rubber-azide photosensitive resins that combine an azide compound with natural rubber, synthetic rubber or their cyclized rubbers, photosensitive resins that incorporate azide groups into the molecule, cinnamic acid photosensitive resins Examples include various photosensitive resins used as the photoresist, such as polyester resins and photopolymerizable photosensitive resins having ethylenically unsaturated double bonds. These photosensitive resins may contain generally known thermal polymerization inhibitors, polymerization initiators, and sensitizers, if necessary.

As the base material for the photosensitive resin, any type of base material can be used as long as it is capable of flattening a substrate with steps or unevenness, but examples include p-
Hydroxydiphenylamine and pentabutoxymethyl-
Condensates of hydroxymethyl-melamine, condensates of p-hydroxydiphenylamine and trimethoxymethyl-hydroxymethyl-melamine, condensates of p-hydroxydiphenylamine and dimethoxymethyl-hydroxymethyl-melamine, and p-hydroxydiphenylamine Examples include a condensate of xahydroxymethyl-melamine, a condensate of p-hydroxydiphenylamine and trihydroxymethyl-melamine, and a condensate of m-hydroxydiphenylamine and trihydroxymethyl-melamine.

In addition, when using it as a base material for a laminated board, etc., it is preferable to dissolve it in advance in an epoxy resin for dipping a glass cloth, for example.

Hereinafter, the present invention will be explained in more detail with reference to synthesis examples and examples of compounds used as light shielding agents of the present invention.
The present invention is not limited to these examples.

Synthesis Example 1 13.3 g of 2-methyl-benzoxazole and 14.
99 p-dimethylamino-benzaldehyde in 13.
19.8 g of 2-(p-dimethylamino-styryl)-benzoxazole was obtained by heating with 0 g of zinc chloride at 170-180°C in a nitrogen stream for 3 hours and purifying with dimethylformamide and hydrochloric acid. . The maximum absorption wavelength of this substance is 393.2 nm (in dimethylformamide).

Synthesis Example 2 10.8g of 0-phenylenediamine and 19.3g of 4
- dimethylaminobenzoic acid with 8 g of boric acid and 8 g of ethylene glycol in a nitrogen stream at 165-175°C for 2 hours.
2-(p-diethylamino-phenyl)- by heating for hours and purification using dimethylformamide and hydrochloric acid.
21.2 g of benzimidazole was obtained. The maximum absorption wavelength of this product was 344.7 nm (in dimethylformamide).

Synthesis Example 3 26.3g of 4-(N-ethyl-N-ethoxyethyl-
Amino)-cinnamic acid and 17.5 g of 1-amino-2-thionaphthol were kept at 200-205°C for 3 hours in a nitrogen stream with 15 g of boric acid and 15 g of ethylene glycol, and purified by recrystallization from dimethylformamide. 28.
1 g of 2-(p'-(N-ethyl-N-ethoxy7-ytylamine)-styryl)-naphthothiazole was obtained. The absorption wavelength of this substance is 410.2 nm (in dimethylformamide).

Compounds synthesized by the same or similar methods as in Synthesis Examples 1 to 3 and their maximum absorption wavelengths (in DMF) are illustrated below.

2-(p-diethylamino-phenyl)-5-methyl-
Benzoxazole 348.6r+m2-(p-(N-
Cyanoethyl-N-ethyl-amino)-styryl)-5
-methoxy-benzoxazole 400.1r+m 2-(p-dimethylamino-styryl)-5,7=dimethyl-benzoxazole 395.0nm2- (p-
diethylamino-phenyl)-[-methyl-benzothiazole 354.4 nm 2- (p-(N,N-dicyanoethyl-amino)-styryl-6-nitoxybenzothiazole 405.3 nm 2- (p-(N-ethoxy Ethyl-N-ethel-amino)-styryl)-5-methyl-benzimidazole 4
00.8nm 2- (p-(N-ethoxyethyl-N-ethyl-amino)-styryl)-N-methyl-benzimidazole 3
89.4 nm 2-(p-dimethylamino-phenyl)-naphthoxazole 358.6 nm 2-(p-diethylamino-styryl)-naphthoxazole 407. Onm 2-(p-dimethylamino-phenyl)-naphthothiazole 360.6 nm 2-(p-diethylamino-styryl)-naphthothiazole 410.8 nm 2-(p-(N-cyanoethyl-N-ethyl-amine)
-styryl)-naphthothiazole 411.02-(p-
Dimethylamino-phenyl)-naphthoimidazole 35
8.6nm 2-gp-(N-cyanoethyl-N-ethyl-amino)-naphthoimidazole 406.7r+m
-Styryl)-naphthoimidazole 407.1 nm Example 1 As a base material, 3 g of a condensate of p-hydroxydiphenylamine and pentabutoxymethyl-hydroxymethyl-melamine and 0.3 g of the oxazole compound obtained in Synthesis Example 1
A photosensitive solution of the present invention was prepared by dissolving 0 g in 17 g of dimethylacetamide and filtering the solution under pressure using a membrane filter.

On the other hand, for comparison, a comparative photosensitive solution was prepared in the same manner except that 0.6 g of Coumarin 1 was used instead of the above-mentioned oxazole compound. Next, using an aluminum vapor-deposited silicon wafer as a substrate, the photosensitive liquid of the present invention and the comparative photosensitive liquid were each coated with a spinner, dried, and then a positive upper layer resist was applied to the photosensitive liquid using a novolak resin/σ-su7toquinonediazide based 5electilux. P (manufactured by Merck & Co.)
A photosensitive element was prepared by coating and drying. Next, this element was exposed to light for 4.8 seconds using a contact method using a mask aligner PLA 500 (manufactured by Canon Inc.), and exposed to light in a 2.2% tetramethylammonium hydroxide aqueous solution for 60 seconds at 25°C. After development, washing with water, and drying, a resist pattern faithful to the mask pattern was formed. As a result of microscopic observation, it was confirmed that a resist pattern with much higher precision was formed when the oxazole compound of the present invention was used than when Coumarin 1 was used.

Example 2 3 g of novolac phenol, 0.69 g of σ-7toquinone diazide, and 0.49 g of the imidazole compound obtained in Synthesis Example 2 were added to a mixed solvent consisting of 4.5 g of butyl acetate, 4.5 g of toluene, and 9 g of ethyl cellosolve acetate. A photosensitive solution of the present invention was prepared by dissolving. On the other hand, for comparison, a comparative photosensitive solution was prepared in the same manner except that 0.6 g of Coumarin 314 was used instead of the imidazole compound.

Next, using the same substrate as in Example 1, a photosensitive liquid of the present invention and a comparative photosensitive liquid were respectively coated with a spinner and dried to prepare a photosensitive element. Next, this element was exposed to light for 3.2 seconds using a contact method as in Example 1, developed using a normal dipping method, washed with water, and then dried to form a resist pattern faithful to the mask pattern. As a result of microscopic observation, it was confirmed that a resist pattern with extremely higher accuracy was formed using the oxazole compound of the present invention than when using Coumarin 314.

Example 3 In place of the oxazole compound of the present invention in Example 1, 2-(p-(N-cyanoethyl-N-ethyl-
0.16 g of 2-(p-diethylamino-amino)-styryl)-5-methoxy-benzoxazole and 2-(p-diethylamino-
The treatment was carried out in the same manner as in Example 1 except that 0.14 g of 2-(p-styryl)-naphthoxazole and 0.6 g of quinoline yellow were used in place of coumarin l as a comparative compound. (N-cyanoethyl-
N-ethyl-amino)-styryl) 5-methoxy-benzoxazole and the 2-(p-diethylamino-
It was confirmed that a resist pattern with extremely high accuracy was formed when a mixture of (styryl) and naphthoxazole was used.

Example 4 0.3 g of the thiazole compound of Synthesis Example 3 was used in place of the imidazole compound of the present invention in Example 2, and 0.3 g of Coumarin 338 was used in place of Coumarin 314 as a comparative compound.
．． The process was carried out in the same manner as in Example 2 except that 6g was used, but it was confirmed that a resist pattern with extremely high accuracy was formed when the thiazole compound of Synthesis Example 3 of the present invention was used.

Example 5 In place of the thiazole compound of the invention in Example 4, 2-
The same procedure as in Example 4 was carried out except that (p-N-ethoxyethyl-N-dithylamino)-styryl)-5-methyl-benzimidazole was used, but the 2-(p-
N-ethoxyethyl-N-dithylamino)-styryl)
It was confirmed that a resist pattern with extremely high accuracy was formed when 5-methyl-benzimidazole was used.

Similarly, other benzo (or naphtho-
) The effect was confirmed using an azole compound, and a resist pattern faithful to the mask pattern was formed, similar to that obtained in Examples 1 to 5.

Example 6 Using two sheets of prepreg obtained by impregnating 0.2 nmH glass cloth (Nitto Boseki Group) with epoxy varnish containing 1% of the compound of Synthesis Example 1 of the present invention added to the epoxy resin, a shielding agent was added. Four sheets of prepreg obtained from non-containing epoxy varnish were sandwiched from both sides, and copper foil with a thickness of 18 μm was layered on both sides and heated and pressed to obtain a copper-clad laminate of a predetermined thickness. This copper foil portion was peeled off using ammonium pericate to obtain a laminate. UV irradiation machine (Oak Manufacturing Department) and UV illuminometer sensor UV
The transmittance was determined from the irradiated light E0 and the transmitted light E1 using UV-42 mounting (manufactured by FIF).

Sensor U-350, 15% Sensor U-420, 32% For comparison, in place of the compound of Synthesis Example 1, 2-(2-hydroxy- A laminate obtained using only six sheets of prepreg obtained using the same amount of 3-tert-butyl-5-methylphenyl)-6-chloro-benzotriazole was similarly irradiated with ultraviolet light, and its transmittance was determined. Ta.

Sensor U-351, 10% Sensor U-4228, 25%. The results showed that the shielding effect was particularly high in the long wavelength region of ultraviolet light, even compared to ultraviolet absorbers for a wide wavelength range.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 and R^2 may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl group where R^3 represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group,
R^4 and R^5 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and X is O, S, NH or NR (
R represents a substituted or unsubstituted alkyl group), n is 0 or 1, and ring A represents a benzene ring or a naphthalene ring. Shielding agent.