JP2002020624A - Aqueous solution of casein - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous solution of casein which is excellent not only in antiseptic and antifungal properties but also in storage stability and workability, and is excellent in sensitivity and resolution when of using as a photosensitive resist by adding a photosensitive agent. SOLUTION: The aqueous solution of casein comprises an isothiazolone compound and a benzoisothiazolone compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a casein aqueous solution, and more particularly, to a casein aqueous solution which is excellent in antiseptic / antifungal properties, storage stability, sensitivity and resolution when used as a photosensitive resist material.

[0002]

2. Description of the Related Art A casein aqueous solution is used as a photosensitive resist material to impart photosensitivity to a casein aqueous solution by adding a dichromate as a sensitizing agent, thereby providing a shadow mask for a color cathode ray tube, an IC lead frame, It is used in the production of fluorescent display tubes, color filters and black matrices in phosphor screens. These aqueous casein solutions are obtained by dissolving acid casein such as casein sulfate, casein hydrochloride and casein lactate in water with ammonia, a base such as sodium hydroxide, or an alkaline salt such as borax or sodium phosphate. In order to suppress the growth of nonionic surfactants and microorganisms for the purpose of improving coatability and dispersibility,
Contains antiseptic and antifungal agents.

[0003] However, conventional preservatives and fungicides used in aqueous casein solutions include phenol, 4-chloro-3-methylphenol, 3-methyl-4-isopropylphenol, monochloro-2-phenylphenol, and parachlorophenol. Examples include phenol-based preservatives and fungicides such as phenol and orthophenylphenol. The aqueous solution of casein using these phenolic antiseptic / antifungal agents has a problem in that environmental pollution is caused by the above antiseptic / antifungal agents in waste liquid generated after use. Also,
The above-mentioned antiseptic / antifungal agent has a problem of deteriorating the working environment when handling the aqueous casein solution and has a danger as a carcinogenic substance.

In view of the above problems, triazine-based triazines such as hexahydrotriazine and N, N ', N "-trishydroxyethylhexahydro-s-triazine have been used as phenolic preservatives and fungicides. And non-phenolic preservatives and fungicides such as biguanides such as chlorhexidine gluconate, chlorhexidine hydrochloride, polyhexamethylene biguanidine, etc. However, these preservatives and fungicides are proposed. The fungicide does not have a sufficient effect on the aqueous casein solution, and furthermore, the storage stability and workability of the aqueous casein solution are poor, and the casein aqueous solution is added with a dichromate to impart photosensitivity. The sensitivity and resolution of the photosensitive resist material decrease due to the influence of the propagation of microorganisms.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive resist composition which is excellent in preservability and antifungal properties, and furthermore excellent in storage stability and workability. Another object of the present invention is to provide an aqueous casein solution having excellent sensitivity and resolution.

[0006]

The above object is achieved by the present invention described below. That is, the present invention provides an aqueous casein solution containing an isothiazolone-based compound (hereinafter, referred to as a component A) and a benzoisothiazolone-based compound (hereinafter, referred to as a component B).

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the aqueous casein solution containing the component A and the component B was replaced with a conventional phenol-based, triazine-based, biguanide-based antiseptic and fungicide. Compared to the casein aqueous solution contained, it has excellent antiseptic and antifungal properties, storage stability and workability,
By imparting photosensitivity to the aqueous casein solution, when used as a photosensitive resist material, bacteria, fungi, good sensitivity and resolution are not impaired by microorganisms such as yeast.
It was unexpectedly found that the casein aqueous solution had significantly improved sensitivity and resolution.

[0008]

Next, the present invention will be described in more detail with reference to preferred embodiments. As casein constituting the aqueous casein solution of the present invention, acid casein, sodium caseinate, calcium casenate and the like can be used. When producing casein, milk has a pH of 6.2 to 6.8, but when an acid is added to the milk to adjust the pH to 4.6, casein micelles lose charge and coagulate and precipitate. This is separated to obtain acid casein. There are lactic casein, casein hydrochloride, and casein sulfate depending on the type of acid. Aqueous casein solution is prepared by dissolving acid casein in water containing ammonia, amines such as triethylamine, and borax, sodium carbonate, sodium hydroxide, and other inorganic alkali agents, particularly from the viewpoint of storage stability. ), Preferably 10 to 15% by weight (solids concentration)
Is preferably used. Further, if necessary, a nonionic surfactant, a defoaming agent, a sensitizer, an adhesion promoter (such as γ-aminopropyltrimethoxysilane), a crosslinking agent, a plasticizer, and a coloring material that improve the wetting of the substrate are used. Can be added.

When the casein aqueous solution is used as a photosensitive resist material by adding a photosensitizer such as dichromate, the casein aqueous solution to which the photosensitizer is added exhibits a thickening phenomenon due to a dark reaction, and the pot life is increased. And storage stability is poor. For this reason, the aqueous casein solution is often stored without adding a dichromate. The main component of casein is protein and has high nutritional value, so that microorganisms such as bacteria represented by Pseudomonas aerobacter and fungi represented by blue mold, red mold and black mold easily propagate during storage.

[0010] For this reason, when an aqueous casein solution in which microorganisms such as the above-mentioned bacteria, yeasts and molds are propagated is used as a photosensitive resist material, high sensitivity and high sensitivity are caused by uneven coating due to a decrease in viscosity and the appearance of deposits. Decreases resolution, adhesion to metal substrates, developability, and etching resistance. Furthermore, there is also the appearance of putrefaction odor due to the propagation of microorganisms.Therefore, in order to suppress the growth of microorganisms such as these bacteria, yeasts, and molds, it is necessary to improve the storage stability of the casein aqueous solution with a preservative / antifungal agent. is necessary. As already described, the casein aqueous solution using the conventional antiseptic and antifungal agent,
These properties are insufficient, and particularly when used as a photosensitive resist material, the sensitivity cannot be sufficiently prevented from inhibiting the sensitivity due to propagation of microorganisms.

The present invention has solved the above-mentioned problems by using a specific compound in combination as an antiseptic / antifungal agent. A component and B which mainly characterize the present invention
The components are compounds represented by the following general formulas A and B.

Embedded image

As the component A, for example, 5-chloro-2
-Methyl-3-isothiazolone, 4-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, 2-ethyl-3-isothiazolone, 4,5-dichloro -2-cyclohexyl-3-isothiazolone, 5-chloro-2-
Ethyl-3-isothiazolone, 4,5-dichloro-2-
n-octyl-3-isothiazolone, 5-chloro-2-
t-octyl-3-isothiazolone, 4-bromo-5-
Chloro-2-methyl-3-isothiazolone, 4,5-dimethyl-2-octyl-3-isothiazolone, 4-bromo-2-n-octyl-3-isothiazolone, and the like, and mixtures thereof. These compounds are
"Bioside 800" from Taisho Technos Co., Ltd.
S "," Bioside 800K "," Bioside 814 "
0 ”or“ San Ibak IT-20 ”or“ San Ibak IT-10 ”from Sanai Sekiyu KK
It can be obtained under a trade name such as "0" and used in the present invention.

The B component includes 1,2-benzisothiazolone, N-methyl-1,2-benzisothiazolone,
2-octyl-4-chloro-1,2-benzisothiazolone, 2-octyl-4,7-dichloro-1,2-benzisothiazolone, 2-t-octyl-6-chloro-
1,2-benzisothiazolone, 2-butyl-5-bromo-1,2-benzisothiazolone, 2- (N-butylcarbamoyl) -5-chloro-1,2-benzisothiazolone, 2-butyl-5-bromo- 1,2-benzisothiazolone, 2-pentyl-4,6-dichloro-1,2
-Benzoisothiazolone, 2- (Nt-octylcarbamoyl) -4-methyl-6-chloro-1,2-benzisothiazolone, and the like, and mixtures thereof. These compounds are trade names such as "Sun-I-Back BST" from San-Ai Oil Co., Ltd., trade names such as "Fine Side C-3000" and "Fine Side C-3800" from Tokyo Fine Chemical Co., Ltd., or Clariant Polymer. It can be used in the present invention by obtaining it under a trade name such as [Melgar K-15] from Co., Ltd.

The preferred component A is 5-chloro-2
-Methyl-3-isothiazolone, 4-chloro-2-methyl-3-isothiazolone, 2-n-octyl-3-isothiazolone, 2-methyl-3-isothiazolone, and the like, and mixtures thereof. Preferred B components include 1,2-benzisothiazolone, N-methyl-1,2-benzisothiazolone, and mixtures thereof. More preferably, 5-chloro-2-methyl-3-isothiazolone and / or 4-chloro-2-methyl-3-isothiazolone are used in combination with the A component and 1,2-benzoisothiazolone as the B component.

The above components A and B alone do not have excellent effects on both the preservative and antifungal properties of the aqueous casein solution. For example, an A component such as 2-methyl-4-chloroisothiazolone and / or 2-methyl-5-chloroisothiazolone has fungicidal properties against an aqueous casein solution, but does not have preservative properties. The B component has antiseptic properties, but does not have fungicide resistance. In particular, the B component is used as a photosensitive resist material provided with photosensitivity by adding dichromate as a sensitizer to an aqueous casein solution. When used, they have been found to have excellent sensitization (2 to 3 times normal). The present invention
By using these components A and B in combination, the casein aqueous solution exhibits excellent effects on both the preservative and antifungal properties. In particular, the component B is used for the casein aqueous solution of the present invention. When used as, it exhibits excellent sensitization. 1,2-Benzoisothiazolone is mentioned as the component B exhibiting preferable sensitization.

The components A and B are directly added to the aqueous casein solution, or are added to the aqueous casein solution in a state where the components A and B are dissolved in an organic solvent compatible with water in advance. Examples of organic solvents compatible with water include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; ethers such as diethyl ether and dioxane; ketones such as acetone; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and the like. And organic solvents such as glycols, and mixtures thereof. Preferred organic solvents include glycol solvents such as ethylene glycol, propylene glycol and diethylene glycol, and mixtures thereof. These solvents may be added to the aqueous casein solution beforehand for use. If necessary, additives such as all stabilizers and dispersants for preventing the decomposition and precipitation of the component A and the component B may be added as long as the object of the present invention is not hindered.

The above antiseptic / antifungal agent contains 100 parts by weight of casein and the component A as a solid content exceeds 0 to 0.20.
Parts by weight, B component 0.10 to 10.0 parts by weight, preferably A component 0.04 to 0.08 parts by weight, and B component 0.1 to 1.0 parts by weight.
It is used in a proportion of 25 to 8.5 parts by weight. If the use amount of the component A and the component B exceeds the above upper limit by weight, the casein aqueous solution thickens and the coating property of the resist film and the adhesive strength to the substrate are reduced, the sensitivity is reduced, the resolution is reduced, and the storage is reduced. If the amount used is less than the above-mentioned lower limit weight, the effects of antiseptic and fungicide are undesirably reduced.

When a dichromate is added as a sensitizer to the aqueous casein solution to be used as a photosensitive resist material, the component B has excellent sensitizing properties. 1.25 to 100 parts by weight of casein
It is significantly improved when 8.5 parts by weight of the B component is added.
If the above upper limit is exceeded, the drying property of the photosensitive resist material is reduced, the phenomenon of reducing the thickness of the resist film is exhibited, and the sensitizing effect is not further exhibited, which is not preferable. Further, when the amount is less than the above lower limit, there is a problem that the sensitizing effect is reduced.

The combination ratio of the component A and the component B is 15 to 100 parts by weight of the component B with respect to 1 part by weight of the component A. If the proportion of the B component exceeds the above upper limit, there is no sensitizing effect due to the B component, and there is a problem that the sensitivity is lowered. Even if it is less than the above lower limit, there is no sensitivity improvement due to the sensitizing effect of the B component. .

The aqueous casein solution of the present invention has a pH of 7 to 10 in view of the solubility of casein and stability of viscosity, and preferably has a pH of 7.3 to 8.3. When the pH exceeds the above upper limit, there is a problem of thickening of the casein aqueous solution, and when the pH is less than the above lower limit, there is a problem that casein is hardly dissolved.

The aqueous casein solution of the present invention is added with a photochromic agent such as ammonium bichromate or potassium dichromate, or a photo-crosslinking agent to impart photosensitivity. It can be a resist material. The above dichromate is preferably used in a ratio of 0.5 to 2.0 parts by weight based on 100 parts by weight of the casein aqueous solution.

Other additives such as a nonionic surfactant and an antifoaming agent may be added to the aqueous solution of casein of the present invention as long as the object of the present invention is not hindered. These components are kneaded and provided as a homogenized aqueous solution.

The photosensitive resist material can be prepared by adding the above-mentioned water-soluble photosensitizer or photocrosslinking agent to the aqueous casein solution, mixing and stirring uniformly. This photosensitive resist material can be applied to a metal substrate such as a shadow mask or a lead frame by using an immersion method, a spin coating method, or the like. Drying of the resist film can be performed using hot air drying or infrared drying. Ultraviolet rays are used for the exposure of the resist film, and any light source may be used as long as it can emit ultraviolet rays, such as a high-pressure mercury lamp or an ultra-high-pressure mercury lamp. Use hot water to develop the resist film.
Pure water, hard water, soft water and the like can be used. The resist film formed by the development is cured using an acid such as chromic acid and heat-treated, whereby a resist film resistant to etching can be formed.

[0024]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the text, "part" means
Based on weight. <Example 1> The following components were thoroughly stirred to prepare an aqueous casein solution of the present invention. -Casein sulfate 12.000 parts-Borax 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.400 parts-Ethylene glycol 0.360 parts-5-Chloro-2- Methyl-3-isothiazolone 0.005 parts ・ 4-chloro-2-methyl-3-isothiazolone 0.005 parts ・ 1,2-benzoisothiazolone 0.030 parts

Example 2 The following components were thoroughly stirred to prepare an aqueous casein solution of the present invention. -Casein hydrochloride 12.000 parts-Sodium carbonate 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.600 parts-Ethylene glycol 0.160 parts-5-Chloro-2 -Methyl-3-isothiazolone 0.005 parts ・ 2-n-octyl-3-isothiazolone 0.005 parts ・ 1,2-Benzoisothiazolone 0.030 parts

Example 3 The following components were thoroughly stirred to prepare an aqueous casein solution of the present invention. -Casein hydrochloride 12.000 parts-Sodium carbonate 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.760 parts-4-Chloro-2-methyl-3-isothiazolone 0 0.010 parts ・ 1,2-Benzoisothiazolone 0.030 parts

Example 4 The following components were thoroughly stirred to prepare an aqueous casein solution of the present invention. -Casein sulfate 12.000 parts-Borax 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.760 parts-4-Chloro-2-methyl-3-isothiazolone 0. 010 parts ・ 1,2-Benzoisothiazolone 0.030 parts

Example 5 The following components were thoroughly stirred to prepare an aqueous casein solution of the present invention. -Casein sulfate 12.000 parts-Borax 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.760 parts-5-Chloro-2-methyl-3-isothiazolone 0. 010 parts ・ 1,2-Benzoisothiazolone 0.030 parts

Example 6 The following components were stirred well to prepare an aqueous casein solution of the present invention. -Casein sulfate 12.000 parts-Borax 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.490 parts-4-Chloro-2-methyl-3-isothiazolone 0. 010 parts ・ 1,2-Benzoisothiazolone 0.300 parts

Example 7 The following components were well stirred to prepare an aqueous casein solution of the present invention. -Casein sulfate 12.000 parts-Borax 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 85.790 parts-4-Chloro-2-methyl-3-isothiazolone 0. 010 parts ・ 1,2-benzisothiazolone 1.000 parts

Example 8 The following components were thoroughly stirred to prepare an aqueous casein solution of the present invention.・ Casein hydrochloride 12.000 parts ・ Sodium carbonate 1.000 parts ・ Nonionic surfactant (polyoxyethylene type) 0.200 parts ・ Ion exchange water 86.480 parts ・ Ethylene glycol 0.160 parts ・ 5-chloro-2 -Methyl-3-isothiazolone 0.005 parts ・ 2-n-octyl-3-isothiazolone 0.005 parts ・ 1,2-Benzoisothiazolone 0.150 parts

Comparative Example 1 The following components were thoroughly stirred to prepare a casein aqueous solution of a comparative example. -Casein sulfate 12.000 parts-Borax 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.500 parts-Phenol 0.300 parts

Comparative Example 2 The following components were thoroughly stirred to prepare a casein aqueous solution of a comparative example. -Casein sulfate 12.000 parts-Borax 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.770 parts-1,2-Benzoisothiazolone 0.030 parts

Comparative Example 3 The following components were thoroughly stirred to prepare a casein aqueous solution of a comparative example. -Casein sulfate 12.000 parts-Borax 1.000 parts-Nonionic surfactant (polyoxyethylene type) 0.200 parts-Deionized water 86.790 parts-4-Chloro-2-methyl-3-isothiazolone 0. 010 copies

Propagation state, storage stability and sensitivity of bacteria, fungi and yeast in each casein aqueous solution obtained above
The resolution was evaluated by the following measurement method. <Propagation state of bacteria, mold and yeast> Mixed bacteria, mixed mold and yeast were added to each of the above casein aqueous solutions, and the viable cell count (viable) of each test bacterium after 7, 14, 21 and 28 days The number of bacteria / sample g) was measured and evaluated by the Japan Food Research Laboratories. Table 1 shows the evaluation results.

[0036]

[Table 1]

<Sensitivity and Resolution> After leaving the aqueous solution of casein of each of the above Examples and Comparative Examples for one month, 100 parts of each aqueous solution of casein was added with ammonium dichromate 1 part.
The photosensitive resist material prepared by adding a part was coated to a thickness of 5 μm (after drying) on a 42-alloy metal substrate by a general method, and then 500 mJ through an ultra-high pressure mercury lamp through Kodak Photographic Step Tablet NO2. /
Irradiation with ultraviolet light of cm ² (365 nm) was performed, and after exposure, spray development and etching were performed with water at 30 ° C., and the sensitivity / resolution (1) to the naked eye and the sensitivity according to the number of steps of the remaining gray scale step number. (Sensitization)
(2) was determined based on the following criteria. Tables 2 and 3 show the determination results.

Sensitivity / Resolution (1) Evaluation point A: There is no pinhole or unevenness, and the sensitivity / resolution is good. C: Pinholes and unevenness occurred, and the sensitivity and resolution were poor.

[0039]

[Table 2]

Sensitivity (sensitivity) (2) The step number of the remaining gray scale of Kodak Photographic Step Tablet NO2 after development was measured. The unit represents the number of steps of the step number.

[0041]

[Table 3]

<Storage Stability> The aqueous casein solutions of the above Examples and Comparative Examples were stored for three months, and the viscosity change and the presence or absence of putrefaction odor were determined according to the following criteria. Table 4 shows the evaluation results. Evaluation points ：: No decrease in viscosity or generation of putrefaction odor, and good storage stability. ×: There is a decrease in viscosity and generation of putrefaction odor, and storage stability is not good.

[0043]

[Table 4]

[0044]

According to the present invention, a casein aqueous solution having excellent antibacterial properties, antifungal properties, yeast-proofing properties and storage stability is provided by adding an A component and a B component to an aqueous casein solution. . In addition, when the aqueous casein solution of the present invention is used as a photosensitive resist material, the sensitivity and the resolution are remarkably excellent. Further, the antiseptic / antifungal agent used in the present invention is a phenolic antiseptic / antifungal agent having a bactericidal property comparable to or higher than that of the phenolic antiseptic / fungicidal agent, and having fungicidal and yeast-proof performance and workability. Low environmental impact.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuyoshi Satake 450 Aotomachi, Midori-ku, Yokohama, Kanagawa Prefecture Inside The Inktech Co., Ltd. (72) Inventor Takehiko Nitta 450 Aotomachi, Midori-ku, Yokohama-shi, Kanagawa The・ Inktec Co., Ltd. F term (reference) 2H025 AA01 AA02 AA11 AB13 AB14 AC01 AD01 BB01 CB03 CC01 CC03 CC04 CC20 4J002 AD021 CH022 EV306 EV307 FD186 FD187 FD312 GP03 HA04

Claims (9)

[Claims] 1. An aqueous casein solution comprising an isothiazolone compound (component A) and a benzoisothiazolone compound (component B). 2. As 100% by weight of casein, the amount of component A exceeds 0.2 and the amount of component B is 0.10.
The casein aqueous solution according to claim 1, which contains 0 to 10.0 parts by weight. 3. The method according to claim 1, wherein the component A is 5-chloro-2-methyl-3.
-Isothiazolone and / or 4-chloro-2-methyl-3-isothiazolone, and the B component is 1,2.
The aqueous casein solution according to claim 1, which is -benzoisothiazolone. 4. The aqueous casein solution according to claim 1, wherein the ratio of the component A to the component B is 15 to 100 parts by weight of the component B based on 1 part by weight of the component A. 5. The aqueous casein solution according to claim 1, further comprising one or more water-soluble organic solvents. 6. The aqueous casein solution according to claim 1, wherein the water-soluble organic solvent is a glycol such as ethylene glycol or propylene glycol. 7. The aqueous casein solution according to claim 1, further comprising one or more nonionic surfactants. 8. The casein aqueous solution having a pH of 7.0 to 10.
The casein aqueous solution according to claim 1, which is 0. 9. The casein aqueous solution according to claim 1, which is provided with photosensitivity.