JPS6157385A - Photo-setting type biocapsule - Google Patents

Abstract

PURPOSE:To obtain photo-setting type biocapsules easily and inexpensively, by a method wherein a photo-setting resin and a photopolymerization initiator are ingested by true fungi such as yeast to form photo-setting type biocapsules. CONSTITUTION:A photo-setting resin and a photopolymerization initiator are ingested by true fungi such as yeast, followed by a treatment at 35-70 deg.C to form photo-setting type biocapsules. The photo-setting resin enclosed in the cap?sules may be, for example, a photo-dimerized type resin having a photosensitive group such as a cinnamic acid residue, a cinnamylidene residue and alpha,beta-unsaturated ketone residue. As the photopolymerization initiator, a known compound such as benzoin alkyl ether and benzophenone can be used. Yeast may be in any of various forms suchas oval, lemon-like and cylindrical form, and the diameter thereof is preferably 5-20mum.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a photocurable biocapsule whose destruction can be controlled.

(Bl Prior art and its problems) So-called microcapsules have traditionally encapsulated liquid, solid, or gas as fine particles with a size of 1 μm to several hundred μm.
The surrounding area is uniformly covered with a thin film of several micrometers to several micrometers, and U.S. Pat.
Since it was disclosed in Specification No. 2507 (4), it has come to be used for various purposes.The most common application is pressure-sensitive recording paper. A color developer, which is a colorless electron-accepting acidic substance, is coated on the surface of the upper paper and another support, which are coated with microcapsules containing a color former, which is a color former that is a color former that is a color dye precursor, dissolved in a nonvolatile solvent. When the coated paper sheets are stacked so that their respective coated surfaces face each other and pressure is applied, the microcapsules are destroyed and the inclusions are released, and the coloring agent and developer come into contact and the colored substance is released through a chemical reaction. It is formed on the surface of the base paper, and this is what is obtained as a copy image.In this way, microcapsules can be formed by forming a thin film on the outside of a substance that has certain properties, thereby simultaneously sealing off those properties. When necessary, the substance can be extracted by breaking the thin film.

On the other hand, when microcapsules are broken to release the contents, the degree of destruction can be freely controlled as necessary, and the
Photocurable microcapsules are microcapsules that can be partially or completely destroyed.

This is a photocurable microcapsule that mainly contains a photocurable resin and a photopolymerization initiator, and the destruction of the microcapsule is controlled by light.

The present inventors previously filed an application for photocurable microcapsules in Japanese Patent Application Laid-open No. 14943/1983, and the known phase separation method (US Patent No. 280045) was used as a microencapsulation method.
No. 7, No. 2800458), interfacial polymerization method (Special Publication No. 3
No. 8-19574, No. 42-446, Kaikai No. 42-7
No. 71), in aitu method by polymerization of mono and mer (
Japanese Patent Publication No. 36-9168, Japanese Patent Publication No. 51-9079),
Melting dispersion cooling method (British Patent Nos. 952807 and 96)
No. 5074), spray drying method (U.S. Pat. No. 31
11407, British Patent No. 930422).

The present inventors further investigated capsules produced by a microencapsulation method that is simpler and lower in cost than the above-mentioned known microencapsulation methods.

Growing microorganisms with a quality content of 10wt96 or more (e.g., oleaginous yeast, beer brewing bacteria, etc.) are supplemented with organic substances for increasing fat content (e.g., aliphatic alcohols, esters, aromatic hydrocarbons, etc.).
The microbial capsule consists of ingesting a liquid (liquid selected from hydrogenated aromatic hydrocarbons).

However, in the above-mentioned microorganism capsule, the growth microorganism must be a growing microorganism, that is, a growing microorganism that has the ability to reproduce when a medium is provided, and the lipid content must be 10wt96, so the growth microorganism must be managed. We had to focus on preservation and maintaining the fat content.

(C) Object of the Invention An object of the present invention is to provide a simple and low-cost photocurable biocapsule.

+Di Structure and Function of the Invention The present invention is a photocurable biocapsule characterized in that it mainly ingests a microorganism, a fungus, a photocurable resin, and a photopolymerization initiator.

More preferably, the photocurable biocapsule is characterized in that the fungus is yeast.

The photocurable biocapsules used in the present invention are mainly used for microorganisms such as fungi, especially yeast, and photocurable resins and photopolymerization (i.e.
It consists of ingesting or encapsulating the ff initiator.

In the classification of fungi, there are two types of yeast: spore-bearing yeast, which belong to the Ascomycetes, and non-spore-forming yeast, which do not form spores, which belong to Deuteromycota.

Spore-bearing yeast (Saccharomycetaaeae)
) is Saccharomycodiae (Saccharom).
ycatoideae) subfamily (this subfamily includes Saaccharomycodes)
As a family, Saccharomyces [Saccharomyces]
ces], Schwaniomyces (Schmaniomyces)
myces) genus, Debaryomyces
myces) genus, Saccharomycobsis (Saccharomycobsis)
aromycopsis), and Nadsoniae (
Nndoaonaae) family, Saccbaromycodes genus, etc.), Lipomycetodiae (Lipomycetodiae), etc.
as ) subfamily (this subfamily includes Lipomyces
yces) genus).

Non-spore yeast (Cryptococceae) include Cryptococcoid
eae ) subfamily (this subfamily includes Cryptococcus (
Cryptococcus) genus, Bretsutatsumyce 7,
(Brettanomyces,) genus, Candida genus, Kroecker
a) ff4, etc.) Trichosporodiae (Tric
hoaporoideaa) (this subfamily includes the genus Trichogporon).

More specifically, S. cervisiae (S, cervisiae), S. cervisiae (S.
bergen+s1g) Endomyces
ces )i of Endomyces vernalis (E, ver.
nalia), Ribomyces lipophor (L, 1ipofor), Ribomyces starkei
(L, atarkeyl), Trichosporonus notorichosporon pullulana (T, pullulana), Trichosporoncthaneum (T, cutaneum), Candida genus Candida curvata (C, curvat).
a), Candidautilus (C, utilg)
, Candida tropicalis (C. tropicalis)
s), Candeida flaveri (C0flaveri)
, Rhodotorula glutinis (R. glutinis) of the genus Rhodotorula.

The yeasts exemplified above include so-called oleaginous yeasts with a high lipid content and yeasts with a low lipid content, and both can be used in the present invention.

The present invention uses these yeasts to infiltrate a mixture mainly consisting of a photocurable resin and a photopolymerization initiator into the yeast by diffusion from the yeast cell wall without destroying the cell wall. It has been found that the yeast used can be ingested (encapsulated) even if it has a low lipid content of 10wt96 or less.

In addition, yeast that has a proliferation function (activity) can be used, but especially in inactive yeast that does not have a proliferation function, it is possible to ingest the photocurable resin and photopolymerization initiator in a shorter time (
Connotation) I discovered what I could do. This has the advantage that, while yeast with a proliferation function requires sealed low-temperature storage in order to maintain its function, it does not require such tight storage.

The yeast used in the present invention has various shapes such as oval, circular, lemon-shaped, columnar, and oval, but preferably circular, oval, and oval. Further, the diameter of the yeast varies depending on the type, but is preferably 5 to 20 μm.

For the encapsulation of the present invention, the temperature is 35-70°C.
1 Preferably, the temperature is 40 to 60°C. The time is 30 minutes or more, but can be changed as appropriate depending on the amount to be ingested (internalized).

Amount ratio (weight) of substances to be ingested (internalized) to yeast
is 2 or less, preferably 1 or less per yeast. Next, the photocurable biocapsule using the above-mentioned yeast will be described in more detail.

The destruction of the biocapsule can be freely controlled by light by ingesting (encapsulating) a photocurable resin and a photopolymerization initiator into yeast. When you want to take out the contents, apply pressure from the outside like normal microcapsules.
By applying heat, etc., the cell walls can be destroyed and the inclusions can be released. In addition, when it is desired to keep the inclusions in the capsule as they are, when the biocapsule is exposed to light, the light that passes through the cell wall hardens the photocurable resin that is the inclusion and sharpens it into a hard resin.

As a result, the photocurable biocapsule becomes a capsule that is more rigid than the inside, and will no longer be destroyed even by external impact, and the contained substances will not be released. Furthermore, the release of inclusions can also be controlled by the amount of light.

The photocurable biocapsule of the present invention must necessarily contain a photocurable resin and a photopolymerization initiator, but it can also contain any other substance. Examples include, but are not limited to, agricultural chemicals, foods, cosmetics, catalysts, young additives, curing agents, oxidizing agents, reducing agents, dyes, pigments, plasticizers, polymer flocculants, rust preventives, antioxidants, and soil conditioners. Organic substances, inorganic substances, and the like used for such purposes can be contained in the inclusions in a solid or liquid state.

The photocurable biocapsule of the present invention can be used for floor boxes in various fields. For example, a photo-curable biotechnology produces capsules with different degrees of curing and different amounts of released contents. After that, by stacking it on a support coated with a co-reactive substance that reacts with the reactive substance to form a colored substance and applying pressure at a constant pressure, it can be used as an optical sensor that can display the amount of light exposure in terms of color shading. When a support coated with photocurable biocapsules containing a similar substance is exposed overlappingly with an original, the imaged areas of the original do not pass through or reflect light, so the capsules remain as they are; The capsule hardens from the inside because the area is exposed to light. After that, when an image-receiving sheet coated with a co-reactive substance is placed and pressed, a copy of the original is obtained on the image-receiving sheet, and it is also used as a copying material that can make multiple copies, but is not limited to this. Yes, you can freely use anything that can utilize the functions of a photocurable biocapsule.

The photocurable resins included in the photocurable biocapsules used in the present invention include cinnamic acid residues, cinnamylidene residues, α,β-unsaturated ketone residues, and phosphoric acid residues. Photodimerizable resins having photosensitive groups such as IJ residues, anthracene residues, α-phenylmaleimide residues, benzophenone residues, and stilbene residues, diazonium salt residues, quinonediazide residues,
Photodegradable resins with photosensitive groups such as azide residues, dithiocarbamate residues, and benzoin residues, and photopolymerizable resins with acryloyl groups, allyl groups, vinyl groups, epoxy groups, etc., can be used as desired; Known compounds that are commonly used as polymerizable resins may be used, such as pentwin alkyl ether, benzophenone, Michler's ketones, thioxantho7, acetophenones, etc., and the sensitizing wavelength range of the photopolymerization initiator can be expanded. Examples of effective photosensitizing aids include anthraquinone, 5-nitrofluorene, etc., and to improve storage stability, electrostatic agents such as radical polymerization inhibitors, modifiers, relatively low molecular weight oligomers or monomers, etc. In some cases, a diluent, etc. may be included at the same time. At the same time, in order to improve the solubility of the substance to be encapsulated, oil-based solvents with high boiling points, such as alkylnaphthalenes, alkylbiphenyls, alkylidene biphenyls, and esters, are sometimes used as solubilizing agents, but this has an adverse effect on the degree of hardening. It is inappropriate to use large amounts for feeding purposes.

Ultraviolet light is generally used as light for curing the photocurable biocapsules used in the present invention.

As the light source, sunlight, xenon lamps, low pressure and high pressure mercury lamps, etc. are used. There is little degradation in the properties of the photocurable biocapsules during manufacturing and normal handling time, such as exposure to light such as occurs with room lights or indirect sunlight.

(El Example The present invention will be explained in more detail by way of examples.

Example 1 0.2596 surfactant (trade name Adecatol LO-
15. 450 parts of water (manufactured by Asahi Denka Tia), 80 parts of epoxy acrylate photocurable C4 part Mt resin (trade name: Lipoxy, manufactured by Showa Kobunshi @ J) and 0 parts of benzoin ethyl ether.
．． The 2 parts of the mixture were emulsified using a homogenizer until the particle size was around 1 part. This emulsion was kept in a constant temperature bath at 50°C, and stirring was continued using a stirrer until the temperature of the emulsion reached 50°C.

Separately, we weighed 100 parts of 011 mother Satsuromyces cerevisiae (baker's yeast), which is an inactive dry yeast with no growth function, and made an emulsion kept at 50°C. The lipid content of the yeast used was approximately 9.
It was vit 96.

Thirty minutes after the addition, a sample was taken and observed under an optical microscope, and a bright sphere could be seen in the center of the yeast. However, emulsified particles were still observed at this point. The mixture was further stirred for 3 hours and then allowed to cool. When the yeast was observed again using an optical microscope, 30 minutes later, a large glittering sphere was found in the center of the yeast, and no emulsified particles were observed. The basis weight of the resulting aqueous dispersion of photocurable biocapsules is 50! /rd base paper.

A piece of black paper was applied to a part of the photocurable biocapsule-coated surface, and the exposed and unexposed areas of the litho-xenophat were observed using an electron microscope from the coated side. The capsules in the exposed area were not destroyed and remained spherical. However, it was confirmed that all the capsules in the unexposed areas were destroyed.

Example 2 Encapsulation was carried out in the same manner as in Example 1 except that Romyces cerevisiae (baker's yeast) was used as an active yeast with the ability to multiply dry yeast, but emulsified particles were not seen and the center of the yeast It took 5 hours before I was able to confirm the glittering spheres in the area.

Furthermore, in the same manner as in Example 1, non-destruction of the capsule in the exposed area was confirmed.

Example 3 In Examples 1 and 2, the effects of the prepared photocurable biocapsules were confirmed using an electron microscope, but in this example, 1. ”:1.', 'tL's 1'
This is an example of rl'fi recognition.

A mixed solution of 80 parts of the epoxy acrylate-based photo-41ij resin of Example 1 and 0.2 parts of benzoin ethyl ether (manufactured by Kyogyosui Koji), 3 parts of crystal violet lactone, and 0.2 g of benzoin ethyl ether. A photocurable biocapsule dispersion was prepared in the same manner except that the following was used. To 60 parts of the dispersion, 20 parts of 1096 polyvinyl alcohol aqueous solution and 20 parts of water were added and thoroughly stirred, and then coated uniformly on paper with a μt weight of 509/rn'' using a Meyer bar.The coated surface of this photocurable biocapsule sheet 7 lashes of xenon light were exposed from 1 to 5 times using a Litho-Xenofax FX-150.3.5-GTC
When an image-receiving sheet coated with a mixed dispersion of rt-butylsalicylic zinc oxide was stacked so that the coated surfaces faced each other and pressure was applied to the entire surface with a pressure roll, the density on the image-receiving sheet varied depending on the number of flash exposures. A red colored image was obtained.

Table 1 shows the relationship between the number of flash exposures and the red color density obtained on the image receiving sheet.

Table 1 shows that when the photocurable biocapsules containing reactants are not exposed to light, they are completely destroyed and a high-density colored image is obtained on the image receiving sheet, but as the number of exposures is increased, the biocapsules are hardened and destroyed. The number of biocapsules that are exposed to light decreases (as the number of exposures increases, the color density decreases, and eventually the biocapsules completely harden and become rigid capsules, which will no longer be destroyed. It can be seen that no color develops.

(Fl Effects of the Invention As described above, the photocurable biocapsule of the present invention is a capsule produced by a simple and low-cost method using microorganisms such as fungi, particularly yeast, and has great industrial significance.

Claims (1)

[Claims] A photocurable biocapsule characterized in that a photocurable resin and a photopolymerization initiator are mainly ingested by microorganisms such as fungi.