JPH04218583A - Heat-sensitive sustained release material - Google Patents

Abstract

PURPOSE:To obtain a heat-sensitive sustained release material dissipating a volatile substance exclusively in use and durable to the use over a long period by compounding a resin component with a meltable component and a material obtained by including a volatile substance in a sustained release material. CONSTITUTION:The objective sustained release material is produced by compounding (A) a material produced by including a volatile substance selected from perfumery, insecticide, fungicide, repellent, rust-proofing agent, lubricant, algicide, etc., in a sustained release material composed of maltose, anhydrous silica, laminar crystal, porous material, etc., and (B) a meltable component selected from fatty acid, glycerol, higher alcohol, polyethylene glycol, wax, surfactant, etc., preferably having a freezing point or melting point of -15 to +88 deg.C to (C) a resin such as thermoplastic resin, thermosetting resin, synthetic resin and natural resin.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a controlled release material containing a volatile substance that lacks long-lasting efficacy and a melt component, which can be applied to a resin. By setting the volatilization start temperature of volatile substances and suppressing volatilization below the volatilization start temperature,
The present invention relates to a heat-sensitive sustained release material that is improved into a vaporizable substance with long-lasting efficacy.

(Prior art) Conventionally, sustained release structures include inclusion compounds in which volatile substances are confined within the molecular cavities of anhydrous crystalline maltose, hydrous crystalline maltose, or cyclodextrin in the presence of water. There is.

Since these clathrates are obtained as solidified products, they are often used in the form of powder products.

The emission of volatile substances by this clathrate powder occurs only in the part of the clathrate that comes into contact with the outside air, regardless of whether it is used alone or in combination with resin, and the emission also depends on the inner diameter of the molecular cavity. Since it is only regulated, the encapsulated volatile substances will be dissipated in a short period of time.

Furthermore, sustained release structures using porous carriers include those using organic porous carriers and inorganic porous carriers.

The former includes materials made of synthetic resins such as nylon, acrylic, polyester, polypropylene, and polyethylene;
Some are made of cellulose and coconut shell activated carbon.

These porous carriers are usually spherical.

The latter include porous carriers made of zeolite, talc, kaolin, synthetic aluminum silicate, diatomaceous earth, silica, and the like.

The amount of volatile substances included in both the former and latter carriers is about 20 to 100% of the carrier weight, and the emission of volatile substances is also possible regardless of the presence or absence of resin, and the narrow diameter of each carrier in contact with the outside air. Since it is only carried out under the regulations, volatile substances will be dissipated in a short period of time.

For sustained release structures other than those mentioned above, see Patent Application No. 2 of 1999.
Layered crystal body described in No. 1811 and Patent Application No. 161 of 1999
There is a product using anhydrous silica described in No. 829.

The sustained release power of these sustained release structures using layered crystals or anhydrous silica for volatile substances is several hundred times higher than that of the above sustained release structures.

However, since volatile substances are constantly emitted as long as the device is in contact with the outside air, a contradiction may arise in that the total number of hours of use is short compared to the duration of the emitted light.

(Problems to be Solved by the Invention) In view of the above circumstances, the present invention aims to provide a temperature-sensitive sustained release material that releases volatile substances only during use and is durable for long-term use. .

(Means for Solving the Problems) In order to achieve the above object, the temperature-sensitive sustained release material of the present invention contains a sustained release material containing a volatile substance and a melt component in a resin. The structure is as follows.

That is, this temperature-sensitive sustained release material is obtained by coating a sustained release material containing a volatile substance with a melt component, and further coating this melt component coating with a resin.

Therefore, in this temperature-sensitive sustained release material, when the melt component reaches the softening point or melting point during use, volatile substances are only released through the coating between the melt component and the resin.
This allows the total number of hours of use to be extended.

In the above-mentioned temperature-sensitive sustained release material, the constituent components of the sustained release material are one or more selected from the group of maltoses, anhydrous silica, layered crystals, and porous materials.

Typical examples of these sustained release materials include cyclodextrin, anhydrous crystalline maltose, and hydrous crystalline maltose.

These maltoses can be used alone or in combination.

Anhydrous silica has an average primary particle diameter of 1 millimicron to 1000 millimicrons and a specific surface area of 3.
One or more types selected from the group ranging from 0 m2/g to 500 m2/g.

These anhydrous silicas are made hydrophobic by reacting the silanol groups with silane compounds such as trimethylchlorosilane and dimethylchlorosilane and/or organic cations in order to prevent moisture absorption and increase the inclusion rate of volatile substances. This is desirable.

However, if the stability of the volatile substance contained in the sustained release material over time is desired, it is necessary to make it hydrophobic using a silane compound.

This is because if a hydrophobized silanol group is used with an organic cation, the unreacted organic cation may cause discoloration of the volatile substance and change in physical properties.

These anhydrous silicas can be used alone or in combination.

The layered crystal is one or more selected from the group of kaolin mineral, serpentine mineral, smectite, vermiculite, mica clay mineral, and chlorite.

In order to prevent moisture absorption and increase the inclusion rate of volatile substances in these layered crystals, inorganic cations such as Na+, K+, Mg2+, and Ca2+ may be replaced with organic cations, or they may be made hydrophobic with a silane compound. desirable.

In particular, since hydrophobization of layered crystals may lead to the use of an excessive amount of hydrophobized material, it is necessary to use a silane compound that does not cause changes in the physical properties of volatile substances due to unreacted components.

Representative examples of these layered crystals other than vermiculite and chlorite include kaolinite, nacrite, detsuite, and halloysite.

Serpentine includes antigorite, chrysotile, amethyte, cronstedite, and chamosite.

Smectites include montmorillolite, beidellite, and nontrolite.

Mica clay minerals include sericite, illite, glauconite, and theodolite.

These layered crystals can be used alone or in combination.

Porous bodies include zeolite, porous silica, hollow silica,
One or more materials selected from the group of activated carbon, synthetic aluminum silicate, hydrotalcite, and diatomaceous earth.

As with anhydrous silica and layered crystals, it is effective for these porous materials to be hydrophobized with organic cations or silane compounds.

These porous bodies can be used alone or in combination.

The constituent components of the volatile substance included in the above-mentioned sustained release material are one or more selected from the group of fragrances, insecticides, bactericides, repellents, rust preventives, lubricants, and algaecides. It is.

Typical examples of these volatile substances include fragrances,
Ja incense, Reineko incense, Ryukyu incense, Beaver incense, Jasmine, Rose, Ylang Ylang, Neroli, Bloom, Abies oil, Cedar oil, Kyara, Rakuni, Manaban, Managa, Sunmontara,
Sasora, sandalwood, labdanum, patchouli oil,
Vetiver oil, citronella oil, orange oil, lemon oil, lime oil, apple, passion fruit, lavender oil, peppermint oil, rosemary oil, geranium oil, frankincense, myrrh, dibutol and dibour.

These fragrances can be used alone or in combination.

Insecticides include 3-methyl-1,5-bis(2,4-xylyl)-triazapenta-1,4-diene, dimethyl-(
2,4-dichlorophenyl)-thiophosphate, 0,
0-dimethyl-0-(3-methyl-4-nitrophenyl)thiophosphate, 2-isopropylphenyl N-
Methyl carbamate, 0,0-dimethyl-0-[3-methyl-(methylthio)phenyl]thiophosphate, 3
, 5-xylyl N-methylcarbamate, 1,3-bis(carbamoylthio)-2-(N.N-dimethylamino)propane hydrochloride, hexakis(β,β-dimethylphenethyl)distannoxane, 2-chloro-1- (2,4
-dichlorophenyl) vinyl diethyl phosphate, birethrin, allethrin and dimethyl 2,2-dichlorovinyl phosphate.

These insecticides can be used alone or in combination.

The fungicide is lauryldimethylbenzylammonium chloride, butyl paraoxybenzoate, 5-chloro-2-
Methyl-4-isothiazoline and 2-methyl-4isothiazolin-3-one.

These fungicides can be used alone or in combination.

The repellents are diethyl toluamide, di-normal propyl isocincomelonate, N-octylbicycloheptenedicarboximide, ethylene glycol monoallyl ether, lemongrass oil and dibutyl succinate.

These repellents can be used alone or in combination.

Rust inhibitors are dicyclohexylammonium nitrite and benzotriazole.

These rust preventives can be used alone or in combination.

The lubricants are cetostearyl alcohol ester of 2-ethylhexanoic acid, cetyl alcohol ester of 2-methylhexanoic acid, and octyl alcohol ester of 3-ethylhexanoic acid.

These lubricants can be used alone or in combination.

Algaecides are the above-mentioned bactericides, insecticides, repellents and lubricants.

These algaecides can be used alone or in combination.

However, these volatile substances are not limited to those mentioned above.

The constituent components of the melt component that coats the volatile substance included in the above-mentioned sustained release material have a freezing point or melting point of -15°C to 88°C (fats and oils, fatty acids, glycerin, higher alcohols, polyethylene glycol, One or more substances selected from the group of waxes and surfactants).

Typical examples of these melt components include fats and oils,
These are hydrogenated beef tallow oil, hydrogenated fish oil, and hydrogenated castor oil.

These fats and oils can be used alone or in combination.

Fatty acids are stearic acid, oleic acid, lauric acid, myristic acid, behenic acid and stearic acid.

These fatty acids can be used alone or in combination.

Glycerin is monoglycerin and polyglycerin.

These glycerins can be used alone or in combination.

Higher alcohols are lauryl alcohol, cetyl alcohol and stearyl alcohol.

These higher alcohols can be used alone or in combination.

Polyethylene glycol has an average molecular weight of 300 or more, preferably 2,000 to 30,000.

These polyethylene glycols can be used alone or in combination.

Waxes are carnauba wax, paraffin wax, wood wax and beeswax.

These waxes can be used alone or in combination.

Surfactants include polyoxyethylene, nonylphenyl,
ether, polyoxyethylene octylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene laurate, and polyoxyethylene sorbitan laurate.

These surfactants preferably have an added mole number of ethylene oxide of 12 moles or more, and can be used alone or in combination.

The above melt components are selected based on conditions such as solubility in water and non-water, freezing point, and melting point, depending on the atmosphere in which the temperature-sensitive sustained release material is used.

Constituent components of the resins containing the sustained-release volatile substance coated with the above-mentioned melt components are thermoplastic resins,
It is one or more selected from the group of thermosetting resins, synthetic resins, and natural resins.

Typical examples of these resins include: ionomer resins, acrylonitrile/acrylic styrene resins, acrylonitrile/butadiene/styrene copolymers, ethylene/vinyl acetate copolymers, vinylidene chloride resins, vinyl chloride resins, chlorine polyethylene,
Vinyl acetate resin, phenoxy resin, butadiene resin, vinylidene fluoride resin, polyacetal resin, nylon 6
6. Polyimide, polyarylate, polyetherimide, polyetheretherketone, polyethylene resin, polyester resin, polycarbonate resin, polystyrene resin, polysulfone resin, polyparamethylstyrene resin, polyphenylene oxide, polybutylene terephthalate resin, polypropylene resin, methacrylic resin and methylpentene polymer.

These thermoplastic resins can be used alone or in combination.

Thermosetting resins are guanamine resins, diallyl phthalate resins, vinyl ester resins, phenolic resins, unsaturated polyester resins, furan resins, polyimide resins, polyurethane resins, melamine resins, and urea resins.

These thermosetting resins can be used alone or in combination.

Synthetic resins include epoxy resin, vinylidene chloride latex, xylene resin, coumaron resin, ketone resin, vinyl propionate resin, polyethylene oxide resin, polyterbene resin, polyvinyl alcohol, polyvinyl ether, acetate plastic, silicone, cellulose acetate, carboxymethyl cellulose, These are ethyl cellulose, polyglutamic acid resin, chloroprene rubber, cyanoacrylate resin, and maleic acid resin.

These synthetic resins can be used alone or in combination.

Natural resins are starch, casein, pine tar, gum arabic, gelatin, sodium alginate, rubber latex, gluten, gum tragacanth, locust bean gum and agar.

These natural resins can be used alone or in combination.

The temperature-sensitive sustained release material of the present invention obtained in this way can be used in clothing, bedding, air filters, wall coverings, printing inks, paints, packaging materials, and decorative products by selecting volatile substances and melt components. It is used for things such as, to extend the total usage time.

(Effects of the Invention) Since the temperature-sensitive sustained release material of the present invention has the above-mentioned configuration,
Since the volatile substance and melt components can be selected in advance according to the application and the atmosphere in which it will be used, it is possible to safely and economically extend the total usage time of the volatile substance, that is, the practical time.

Example 1 There is a notebook in which a rayon nonwoven fabric with a fabric weight (g/m2) of 30 g and a polyethylene film with a fabric weight of 5 g are laminated. Cut this sheet into 5 pieces with dimensions of 10 x 20 cm, apply the entire amount of chemicals A to E below using a bar coater, and place them outdoors in a sunny area at an average temperature of 25 degrees Celsius. After hanging for 7 days, the average temperature is 20℃.
After being left in a room for 30 minutes, a test was conducted by five panelists to confirm that the lily of the valley fragrance remained on the surface of the nonwoven fabric.

However, the test method for confirming the residual fragrance is as follows: (a): Place the material on a wooden stand and after 1 minute has elapsed, perform the confirmation test without touching the material.

(B): Perform a confirmation test 10 seconds after the film surface contacts the skin.

Drug A: Lily of the Valley fragrance (Lily of the Valley K- manufactured by Soda Perfume Co., Ltd.)
1629) and 5 g of a 30% toluene solution of chlorinated polypropylene (hereinafter simply referred to as "resin").

B: 1 g of 50% alcohol solution of lily of the valley fragrance is included in 1 g of montmorillonite powder, and 5 g of "resin" is prepared.
The substance contained in

C: A product in which 1 g of a 50% alcoholic solution of lily of the valley fragrance was included in 1 g of montmorillonite powder, coated with 2 g of stearic acid, and then incorporated into 5 g of "resin".

D: 1 g of 50% alcoholic solution of lily of the valley fragrance contained in 1 g of montmorillonite powder having C12H25NH3+ as an organic cation was contained in 5 g of "resin".

E: 1 g of 50% alcoholic solution of lily of the valley fragrance contained in 1 g of montmorillonite powder having C12H25NH3+ as an organic cation, and 2 g of stearic acid.
This product was coated with 5g of resin and then added to 5g of resin.

Result A: For both (a) and (b), all panelists could not detect any scent.

B: For both (a) and (b), all panelists could not detect any scent.

C: (a) All panelists could not detect any scent.

(b) Two panelists detected a faint scent of lily of the valley.

The remaining three panelists had no feelings whatsoever. I couldn't know.

D: For both (a) and (b), all panelists sensed the faint scent of lily of the valley.

E: (a) Two panelists detected a faint scent of lily of the valley.

The remaining three panelists had no feelings whatsoever. I couldn't know.

(b) All panelists sensed the strong scent of lily of the valley.

Example 2 50 g of nylon 12 powder was placed in each of nine 100 cc glass beakers and placed on a pot plate at 190° C. to form a molten resin.

After adding and stirring the following chemicals F to N to this molten resin, a shallow stainless steel vat (dimensions 1.5×
12.7 x 2.5 cm) and allowed to cool naturally, then taken out from the vat and used as a drug-containing plate (hereinafter simply abbreviated as "plate"). This "plate" was submerged in the sea at a depth of 5 m for 3 months with a plow attached so that it was fixed vertically at a position 50 cm below the sea surface, and was subjected to an algae and barnacle adhesion test.

Drug F: 1.5 g of cetostearyl alcohol ester of 2-ethylhexanoic acid.

G: 1.8 g of smectite having (C6H5)3NH+ (hereinafter simply referred to as "carrier") containing 1.5 g of cetostearyl alcohol of 2-ethylhexanoic acid.

H: 1.8 g of 0.3 g of "carrier" containing 1.5 g of cetostearyl alcohol of 2-ethylhexanoic acid and 1.8 g of stearic acid.

I: 3.6 g of a mixture of 1.5 g of cetostearyl alcohol of 2-ethylhexanoic acid incorporated into 0.3 g of "carrier" and kneaded into a melt of 1.8 g of stearic acid.

J: 3.6 g of 0.3 g of "carrier" mixed with 1.5 g of cetostearyl alcohol of 2-ethylhexanoic acid and kneaded with a melt of 1.8 g of polyethylene glycol having an average molecular weight of 10,000.

K: 3.6 g of 0.3 g of "carrier" mixed with 1.5 g of cetostearyl alcohol of 2-ethylhexanoic acid and kneaded with a melt of 1.8 g of polyethylene glycol having an average molecular weight of 2000.

L: 0.3 g of "carrier" containing 1.5 g of dipropylene glycol monopropyl alcohol ester,
3.6 g of a product kneaded with a melt of 1.8 g of stearic acid.

M: 0.3 g of "carrier" containing 1.5 g of dipropylene glycol monopropyl alcohol ester,
3.6 g of a melt of 1.8 g of polyethylene glycol with an average molecular weight of 10,000 was kneaded.

N: 0.3 g of "carrier" containing 1.5 g of dipropylene glycol monopropyl alcohol ester,
1.8g of polyethylene glycol with an average molecular weight of 2000
3.6g of kneaded into the melt.

Result F: Algae and barnacles were attached to both surfaces of the "plate".

G: On both sides of the "plate", algae were attached to slightly more than 1/4 of the area, and barnacles were also observed attached to one part.

H: Algae were attached to just over 1/6 of the area on both sides of the plate, and some barnacles were also observed.

I: Compared to "H", the adhesion of algae was slightly less, but the adhesion of barnacles was at the same level.

J: Algae adhered to more than 10% of the area on both sides of the "plate", and barnacles were also found attached to one part.

K: No algae was observed on both sides of the plate, but only one barnacle was found on one side.

L: Algae were attached to about 10% of the area on both sides of the "plate", but no barnacles were observed.

M: Approximately 5% of the area of algae was attached to both sides of the lower part of the "plate", but no barnacles were observed.

N: No deposits were observed on both sides of the "plate".

However, the above test period is from March 1, 1990 to March 5, 1990.
The period is 3 months, ending on the 31st of the month, and the distance between each "plate" is 2 meters.

Example 3 The following chemicals were added in an amount of 3% based on the weight of polyethylene terephthalate chips (hereinafter simply referred to as "chips"), and each was heated at 280°C using an extruder equipped with a polystrope heating screw. It was melt-spun, and after stretching and pressing, it was made into short fibers with a fineness of 14 denier and a fiber length of 70 mm. Needle punch this short fiber to a thickness of 1 mm.
Made of non-woven fabric with a basis weight of 100g/m2, 40cm x 10c
The specimens were cut into pieces of 1.5 m in size and exposed outdoors for 24 hours, and used as insect repellent specimens in a cockroach repellent test.

The comparative specimen was a nonwoven fabric made only of polyethylene terephthalate and had dimensions of 40 cm x 65 cm.

Drug O: Diethyltoluamide (hereinafter simply abbreviated as "DET") P: "DET" was added to anhydrous silica hydrophobized with dimethyldichlorosilane (hereinafter simply abbreviated as "carrier") at a weight ratio of 7: A substance containing a ratio of 1:1.

Q: A product obtained by melt-kneading "DET" incorporated into a "carrier" at a weight ratio of 7 and polyethylene glycol having an average molecular weight of 2000 at a weight ratio of 21.

R: A product obtained by melt-kneading "DET" incorporated into a "carrier" at a weight ratio of 7:1 and polyethylene glycol having an average molecular weight of 20,000 at a weight ratio of 2:1.

Cockroach repellent test Insect repellent specimens and comparative specimens were placed at the bottom of a transparent acrylic tank measuring 40 cm long, 75 cm wide, and 30 cm high.
A "U-shaped" roof with a width of 40 cm and a height of 10 cm is placed over each specimen at both ends with black cardboard on both sides to divide the specimen area.

The bait was a 5 cm square piece of fried tofu, placed on a non-woven fabric in the center of the bottom of the tank, then 10 Yamato cockroaches and 10 black cockroaches were placed in the dark and observed 5 times every 2 hours to calculate the total number in each specimen area. After determining, the average value was calculated.

However, on the wall of the acrylic aquarium, there are 1mm diameter holes at 2cm intervals.
In addition to suppressing the retention of chemicals in the aquarium by drilling holes in the tank,
A net with a mesh size of 1 mm was placed above the tank to prevent cockroaches from escaping.

Results When the test atmosphere temperature is 20°C O: Total number within the comparison sample area: 51.0 animals Average value: 10.2 animals Total number within the insect control sample area: 49.0 animals Average value: 9.8 P: Total number within the comparison sample area: 78.0 Average value: 15.6 animals Total number within the insect control sample area: 22.0 animals Average value: 4.4 animals Q: Total number released within the comparison sample area: 90.0 animals Average value: 18.0 animals Total number within the insect control sample area: 10.0 animals Average Value: 2.0 animals R: Total number within the comparison sample area: 53.0 animals Average value: 10.6 animals Total number within the insect control sample area: 47.0 animals Average value: 9.4 animals When the test atmosphere temperature is 35°C O: Within the comparison sample area Total number: 52.0 animals Average value: 10.4 animals Total number within the insect control sample area: 48.0 animals Average value: 9.6 animals P: Total number within the comparison sample area: 83.0 animals Average value: 16.6 animals Total number within the insect control sample area: 17. 0 animals Average value 3.4 animals Q: Total number within comparison sample area 91.0 animals Average value 18.2 animals Total number within insect control sample area 9.0 animals Average value 1.8 animals R: Total number within comparison sample area 100.0 Animal average value 10.0
Total number of insect repellent specimens within the sample area: 0.0 Average value: 0.0 Applicant: Shoko Chemical Research Institute Co., Ltd.

Claims (9)

[Claims] 1. A temperature-sensitive sustained release material, characterized in that the sustained release material contains a volatile substance and a melt component in a resin. 2. The temperature-sensitive sustained release according to claim 1, wherein the sustained release material is one or more selected from the group of maltoses, anhydrous silica, layered crystals, and porous materials. Material. Claim 3: The maltose is cyclodextrin,
The temperature-sensitive sustained release material according to claim 2, which is one or more selected from the group of anhydrous crystalline maltose and hydrated crystalline maltose. 4. Anhydrous silica is one or two types selected from the group having an average primary particle diameter of 1 millimicron to 1000 millimicrons and a specific surface area of 30 m2/g to 500 m2/g. 3. The temperature-sensitive sustained release material according to claim 2, wherein the temperature-sensitive sustained release material is more than 100%. 5. The layered crystalline material according to claim 2, wherein the layered crystal is one or more selected from the group of kaolin mineral, serpentine mineral, smectite, vermiculite, mica clay mineral, and chlorite. Temperature-sensitive sustained release material. 6. The porous body is zeolite, porous silica,
The temperature-sensitive sustained release material according to claim 2, which is one or more selected from the group of hollow silica, activated carbon, synthetic aluminum silicate, hydrotalcite, and diatomaceous earth. Claim 7: Claim 1, wherein the volatile substance is one or more selected from the group of fragrances, insecticides, bactericides, repellents, rust preventives, lubricants, and algaecides. Temperature-sensitive sustained release material described in Section 1. 8. The melt component is selected from the group of (oils and fats, fatty acids, glycerin, higher alcohols, polyethylene glycols, waxes, and surfactants) having a freezing point or melting point of -15°C to 88°C. The temperature-sensitive sustained release material according to claim 1, which is one or more kinds. 9. The resins are thermoplastic resins, thermosetting resins,
The temperature-sensitive sustained release material according to claim 1, which is one or more selected from the group of synthetic resins and natural resins.