JP2931693B2 - Light shielding agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a high absorptivity in the near ultraviolet to visible short wavelength range from 300 nm to 450 nm as a specific wavelength range for use in a photosensitive resin, a photosensitive resin base material, and a substrate for a laminated substrate. It relates to a light shielding agent.

[0002]

2. Description of the Related Art In recent years, ultraviolet absorbing materials used in photoresist-related fields used for manufacturing integrated circuits, semiconductor devices, printed wiring boards, etc., which require ultra-high integration, ultra-high density, and fineness, or The following structural formula as an ultraviolet shielding material

Embedded image 1,5-diphenyl-3-styrylpyrazoline represented by is known (JP-B-63-15571).

[0003]

However, this known substance has the disadvantage that it is very crystalline and therefore often results in unfavorable results when used.

That is, when this compound is used for a photoresist, particularly as an ultraviolet shielding agent, it is kneaded into a resin and diffused and dissolved, or dissolved in a solvent together with an adhesive resin to form a paint, or recently dispersed in fine particles. The product is used by dip coating on a substrate. And, not only this known compound but also a compound obtained by introducing a normal substituent such as a halogen, an alkoxy or a lower alkyl group into a phenyl group of this compound also has a strong crystallinity. A cohesion phenomenon occurs, so that the uniform distribution in the resin is impaired, and the ultraviolet shielding effect cannot be exerted uniformly. Aggregation during drying is inevitable even by a coating method using a solvent and a resin. The use of a fine particle dispersion product which is immersed and attached to, for example, a glass cloth of a printed wiring board has also recently been proposed, but when using the above-mentioned known compound in the form of the fine particle dispersion, the compound also has the chemical structure Aromaticity is strong and therefore lacks stability of particles, which is the most important property of this kind of dispersion composition,
That is, the finely divided primary particles undergo secondary aggregation with the passage of time, resulting in a disadvantage that the particles are enlarged and sedimented and separated, and it is difficult to obtain an excellent dispersion composition. Prevention of the aggregation of the fine particles can be prevented by increasing the amount of the dispersing agent or the dispersing agent if the purpose of use of the compound is not an ultraviolet shielding agent. Such measures cannot be adopted because the absorption effect is significantly reduced. Therefore, in any of the kneading method, the coating method, and the dispersion method, a conventional compound cannot provide a UV-shielding substrate having a high degree of homogeneity. It was a major obstacle to gaining.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the drawbacks of the known pyrazoline compounds,
1 to 6, preferably 2 to 3 phenyl groups in the molecule
By introducing higher alkyl groups (C ₄ -C ₁₂ ), it was found that the strong crystallinity or cohesiveness of the above-mentioned known compounds could be completely eliminated. It has been found that it is an ideal ultraviolet ray shielding agent which can be dispersed in fine particles by using a small amount of a dispersing agent or dispersing agent which can be applied or which can be stored for a long period of time.

That is, the present invention relates to the general formula

Embedded image (Wherein R represents a C _{4 to} C ₁₂ linear or branched alkyl group independent of each other, and each of a, b and c represents 0 to 2
Wherein the value of a + b + c is 1 or more).

The effect of reducing high crystallinity or cohesion is achieved only by the long-chain alkyl group linked to the phenyl group as described above, and is a unique phenomenon that cannot be achieved by other ordinary substituents. In addition, the higher alkyl group introduced into the 1-position phenyl group on the pyrazoline ring not only has an excellent effect on homogeneous dispersion in the resin, but also has the property of shifting the absorption wavelength to the longer wavelength range. This is also consistent with the tendency of this type of ultraviolet shielding compound to be oriented. According to the present invention, a highly uniform ultraviolet shielding film material or ultraviolet shielding substrate, which cannot be achieved by the conventional compounds, is obtained, and by using this, a highly accurate pattern can be produced, thereby sufficiently satisfying the needs of the art.

The following are typical examples of the pyrazoline compound of the present invention.

1- (4-tert-butyl-phenyl)
-3-Styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5-
(4-tert-butyl-phenyl) -pyrazoline,
1,5-bis- (4-tert-butyl-phenyl)-
3- (4-tert-butyl-styryl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3-
Styryl-5-phenyl-pyrazoline, 1-phenyl-
3- (4-tert-octyl-styryl) -5- (4
-Tert-octyl-phenyl) -pyrazoline, 1,
5-bis- (4-tert-octyl-phenyl) -3
-(4-tert-octyl-styryl) -pyrazolin, 1- (4-dodecyl-phenyl) -3-styryl-
5-phenyl-pyrazoline, 1-phenyl-3- (4-
Dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl)-
3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4 -Tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl)-
3- (4-tert-octyl-styryl) -5- (4
-Tert-octyl-phenyl) -pyrazoline, 1-
(4-dodecyl-phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4 -Dodecyl-styryl) -5- (4
-Dodecyl-phenyl) -pyrazolin, 1- (4-dodecyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl)
-Pyrazolin, 1- (4-tert-octyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazolin, 1- (2,4-dibutyl-phenyl) -3 -(4-dodecyl-styryl)-
5- (4-dodecyl-phenyl) -pyrazoline, 1-phenyl-3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-
tert-butyl-styryl) -5- (2,6-di-t
tert-butyl-phenyl) -pyrazolin, 1-phenyl-3- (2,5-di-tert-butyl-styryl)
-5- (2,5-di-tert-butyl-phenyl)-
Pyrazoline, 1-phenyl-3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazolin, 1- (3,4-di-tert) −
Butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (3,5-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1
-(4-tert-butyl-phenyl) -3- (3,5
-Di-tert-butyl-styryl) -5- (3,5-
Di-tert-butyl-phenyl) -pyrazoline, 1-
(3,5-di-tert-butyl-phenyl) -3-
(3,5-di-tert-butyl-styryl) -5-
(3,5-di-tert-butyl-phenyl) -pyrazoline.

The light-shielding agent of the present invention is used by being added to and blended with a photosensitive resin, a photosensitive resin base material, a laminated substrate substrate, and the like. Any known one can be used, and examples thereof include a photosensitive resin obtained by combining an orthoquinonediazide and a novolak resin, a rubber-azide obtained by combining an azide compound with a natural rubber, a synthetic rubber or a cyclized rubber thereof. -Type photosensitive resin, photosensitive resin with azide group incorporated in molecule, cinnamic acid-based photosensitive resin, photopolymerizable photosensitive resin with ethylenically unsaturated double bond Can raise the resin,
As the photosensitive resin base material, any base material that flattens a substrate having steps or irregularities can be used without being limited by its type.
Hydroxydiphenylamine and pentabutoxymethyl-
Condensates of hydroxymethyl-melamine, condensates of p-hydroxydiphenylamine and trimethoxymethyl-hydroxymethyl-melamine, condensates of p-hydroxydiphenylamine and dimethoxymethyl-hydroxymethyl-melamine, p-hydroxydiphenylamine and hexa A condensate of hydroxymethyl-melamine, a condensate of p-hydroxydiphenylamine and trihydroxymethyl-melamine, a condensate of m-hydroxydiphenylamine and trihydroxymethyl-melamine, and a laminated substrate substrate. Examples thereof include those made of paper, cloth, glass cloth, and a solution (varnish) of a phenol resin, an epoxy resin, or the like.

The light shielding agent of the present invention is added and blended in an amount of 1 to 40%, preferably 4 to 35% by weight with respect to the photosensitive resin, photosensitive resin base material or laminated substrate base material. When used in a varnish when used for a laminated substrate, it is used in an amount of 0.1 to 10%, preferably 0.5 to 6%. Furthermore, it is also possible to use dip coating directly on glass cloth in the form of aqueous fine particles.

Now, the present invention will be described in further detail with reference to Synthesis Examples and Examples, but it should not be construed that the invention is limited thereto.

In the examples, "parts" indicates parts by weight.

Synthesis Example 1 Synthesis of 4,4'-di-tert-butyl-dibenzalacetone A mixed solution of 40 parts of caustic soda, 320 parts by volume of water and 400 parts by volume of ethanol was stirred at room temperature for 11 hours. .
A mixture of 6 parts of acetone and 64.8 parts of 4-tert-butylbenzaldehyde is added. Soon a pale yellow crystal will precipitate. Thereafter, the mixture was vigorously stirred for about 3 hours, filtered, sufficiently washed with water, pressed well, and dried. Yield 65.6 parts (yield 94.8%)

Synthesis Example 2 Synthesis of 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline 10.8 parts of phenylhydrazine and Synthesis Example 1 were obtained. 4,4 '
-Di-tert-butyl-dibenzalacetone 34.6
The mixture was reacted with 300 parts by volume of glacial acetic acid under heating and reflux for about 3 hours, filtered at 85 ° C., washed with acetic acid, washed with water, and purified once with ethanol. Yield: 35.1 parts (Yield: 80.5%). Its maximum absorption wavelength is 386.5 nm (DMF).
showed that.

Synthesis Example 3 1,5-bis- (4-tert-butyl-phenyl)-
Synthesis of 3- (4-tert-butyl-styryl) -pyrazoline 16.4 parts of 4-tert-butyl-phenylhydrazine and 4,4'-di-tert-butyl-dibenzalacetone 34 obtained in Synthesis Example 1. .6 parts were reacted with 320 parts by volume of glacial acetic acid under reflux for about 3.5 hours, filtered at room temperature,
It was washed with acetic acid and purified once from acetic acid. Yield: 37.9 parts (yield: 77.0%). Its maximum absorption wavelength is 392.6 nm (DMF).
showed that.

Synthesis Example 4 1- (4-Dodecyl-phenyl) -3-styryl-5
Synthesis of phenyl-pyrazoline 47.6 parts of 4-dodecyl-phenylhydrazine and 23.4 parts of dibenzalacetone were reacted with 270 parts by volume of 95% acetic acid under heating and reflux for about 3.5 hours, and filtered at room temperature.
It was washed with acetic acid and purified once from acetic acid. Yield 36.6 parts (yield 74.4%), whose absorption maximum wavelength is 394.1 nm (DMF)
showed that.

The maximum absorption wavelength of the pyrazoline compound synthesized by the same or similar method is shown below.

1- (4-tert-butyl-phenyl)
-3-styryl-5-phenyl-pyrazoline 392.
2 nm 1- (4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline 393.9 nm 1-phenyl-3- (4-tert-octyl-styryl) -5- (4-tert-octyl- Phenyl) -pyrazoline 387.1 nm 1,5-bis- (4-tert-octyl-phenyl)
-3- (4-tert-Octyl-styryl) -pyrazoline 394.2 nm 1-phenyl-3- (4-dodecyl-styryl) -5-
(4-Dodecyl-phenyl) pyrazoline 387.4n
m 1- (4-Dodecyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline 395.0 nm 1- (4-tert-octyl-phenyl) -3- ( 4
-Tert-butyl-styryl) -5- (4-tert
-Butyl-phenyl) -pyrazoline 394.0 nm 1- (4-tert-butyl-phenyl) -3- (4-
tert-octyl-styryl) -5- (4-tert
-Octyl-phenyl) -pyrazoline 392.9 nm 1- (4-dodecyl-phenyl) -3- (4-tert
-Butyl-styryl) -5- (4-tert-butyl-
Phenyl) -pyrazoline 394.3 nm 1- (4-tert-butyl-phenyl) -3- (4-
Dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline 393.1 nm 1- (4-dodecyl-phenyl) -3- (4-tert
-Octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline 394.5 nm 1- (4-tert-octyl-phenyl) -3- (4
-Dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline 394.3 nm 1-phenyl-3- (3,5-di-tert-butyl-
Styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazolin 388.8 nm 1- (3,5-di-tert-butyl-phenyl) -3
-(3,5-di-tert-butyl-styryl) -5-
(3,5-di-tert-butyl-phenyl) -pyrazoline 390.2 nm

Example 1 As a base material, 3 parts of a condensate of p-hydroxydiphenylamine and pentabutoxymethyl-hydroxymethyl-melamine and 1-phenyl-3- (4-tert-) of the present invention were used.
0.4 parts of (butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline was dissolved in 17 parts of dimethylacetamide, and the solution was filtered through a membrane filter to prepare a photosensitive solution of the present invention. On the other hand, for comparison, a comparative photosensitive solution was prepared in the same manner except that 0.6 parts of coumarin 1 was used instead of the pyrazoline compound. Next, a silicon wafer on which aluminum is deposited is used as a substrate, and the photosensitive solution of the present invention and a comparative photosensitive solution are respectively applied by spinner and dried, and then a novolak resin / α-naphthoquinonediazide-based Selectilux P is used as a positive upper resist.
(Manufactured by Merck) was applied and dried to produce a photosensitive element. Next, a mask eyeliner PL is added to this element.
A500 (manufactured by Canon Inc.) was used for contact exposure for 4.8 seconds, immersed in a 2.2% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 60 seconds, washed with water, dried, and then dried. A resist pattern faithful to the pattern was formed. As a result of microscopic observation, it was confirmed that a highly accurate resist pattern was formed using the pyrazoline compound of the present invention rather than using coumarin 1.

Example 2 3 parts of novolak phenol, 0.6 part of α-naphthoquinonediazide and 1- (4-tert-butyl- of the present invention)
0.42 parts of (phenyl) -3-styryl-5-phenyl-pyrazoline are dissolved in a mixed solvent consisting of 4.5 parts of butyl acetate, 4.5 parts of toluene and 9 parts of ethyl cellosolve acetate to prepare a photosensitive solution of the present invention. did. On the other hand, for comparison, a comparative photosensitive solution was prepared in the same manner except that 0.6 parts of coumarin 314 was used instead of the pyrazoline compound. Next, using the same substrate as in Example 1, the photosensitive solution of the present invention and the comparative photosensitive solution were respectively applied with a spinner and dried to produce a photosensitive element. Next, this element was exposed to the contact system for 3.2 seconds in the same manner as in Example 1, developed by an ordinary dipping method, washed with water, dried, and a resist pattern faithful to the mask pattern was formed. As a result of microscopic observation, it was confirmed that a highly accurate resist pattern was formed using the pyrazoline compound of the present invention rather than using coumarin 314.

Example 3 An epoxy varnish prepared by adding 1% of 1,5-bis- (4-tert-butyl-phenyl) -3- (4-tert-butyl-styryl) -pyrazoline of the present invention to an epoxy resin was used. Using two prepregs obtained by impregnating a glass cloth (manufactured by Nitto Boseki) with a thickness of 0.2 mm, sandwiching four prepregs obtained from an epoxy varnish without adding a shielding agent from both sides, and further 18 μm thick copper foil from both sides Were heated and pressed to obtain a copper-clad laminate having a predetermined thickness. The copper foil was peeled off with ammonium persulfate to obtain a laminate. The transmittance was determined from the irradiation light E ₀ and the transmitted light E ₁ using an ultraviolet irradiation device (manufactured by Oak Manufacturing Co., Ltd.) and an ultraviolet measuring device with sensors U-35 and U-42 (manufactured by Oak Manufacturing Co., Ltd.).

Sensor UV-35 0.16% Sensor UV-42 0.37%

For comparison, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl), which is a commercially available representative ultraviolet absorber for a wide wavelength range, is used in place of the compound of Synthesis Example 3. A laminate obtained by using only six prepregs obtained using the same amount of -6-chloro-benzotriazole was similarly irradiated with ultraviolet rays, and the transmittance thereof was obtained.

Sensor UV-35 1.08% Sensor UV-42 27.97%. As a result, the shielding effect in the ultraviolet long wavelength region was particularly higher than that of the ultraviolet absorber for the wide wavelength region.

Example 4 In place of the pyrazoline compound of Example 3, 1-
(4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline and 1,3-diphenyl-5
The procedure was as in Example 3, except that a 1: 1 mixture of-(4-tert-butyl-phenyl) -pyrazoline was used.

Sensor UV-35 0.12% Sensor UV-42 0.69%

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09K 3/00 104 G03F 7/004 H05K 1/03 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (Wherein R represents a C _{4 to} C ₁₂ linear or branched alkyl group independent of each other, and each of a, b and c represents 0 to 2
Wherein the value of a + b + c is 1 or more).