JPH07331027A - Curable resin composition and gas sustained-release resin molded product - Google Patents

Abstract

(57) [Abstract] [Structure] (A) Inorganic substances that react with water to generate gas 1-
90 parts by weight, (B) at least one (meta) in the molecule
At least one compound having an acryloyl group 5 to 9
0 parts by weight, 1 to 60 parts by weight of at least one (C) non-radical polymerizable compound, (D) radical polymerization initiator 0.0
A curable resin composition comprising 01 to 5 parts by weight (however, the total amount of (A), (B), (C), and (D) is 100 parts by weight). [Effect] Since the amount of gas generated can be controlled for a long period of time, the gas can be efficiently provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition in which an inorganic substance that reacts with water to generate a gas is embedded, and a gas sustained-release resin molded product obtained by curing the curable resin composition into a predetermined shape. More specifically, an inorganic substance in a molded product reacts with water to generate a gas, which can be maintained for a long period of time while controlling the gas generation amount to a constant amount, and a curable resin that can make it. It relates to a resin composition.

[0002]

2. Description of the Related Art Conventionally, a sustained-release material has been disclosed in JP-A-2-28.
As disclosed in Japanese Patent Publication No. 221 and Japanese Patent Publication No. 42561/1992, it is widely used in various fields such as an oxygen generating material, a bleaching agent, a bath agent, a fragrance, and an insecticide. In particular, as the oxygen generating material, mainly used for the purpose of supplying oxygen to animals and plants such as fish and plants. Specifically, the oxygen generating material is put into a water tank for transporting live fish, and oxygen gas is put into water. It is used by a method of supplying the oxygen-generating material to a tank filled with water outside the water tank and supplying only the generated oxygen to the water tank.

As the shape of these sustained-release materials, a method is known in which an inorganic substance which reacts with water to generate a gas is molded into a granular or compacted solid state and used. In general, as specific examples of inorganic substances that react with water to generate gas, an adduct of sodium carbonate and hydrogen peroxide, calcium oxygen peroxide, sodium hydrogen carbonate, and the like are widely known. For fragrances,
A method of directly spraying a substance in which a fragrance or the like is dissolved in a liquid volatile substance is directly applied to an object to be treated, and as the insect repellent, a solid insect repellent containing a repellent substance in a sublimable substance is partially used. A method of volatilizing the insect repellent by wrapping it in a film or the like having an open portion is used.

However, since the volatile substances in these sustained-release materials necessarily have high volatility, their action tends to disappear in a short period of time. In particular, the inorganic substance in the oxygen generating material reacts with water to generate oxygen gas as soon as it is put into water, but since the reaction occurs rapidly, the amount of the gas generated cannot be controlled, The effective gas generation amount ends in a short time.

Specifically, when oxygen gas is generated in water, most of the oxygen gas generated from the oxygen generating material does not dissolve in water and does not dissolve in water because the amount of dissolved oxygen in water is several ppm at room temperature. It is released inside and the oxygen supply efficiency into water is extremely poor.

[0006]

In order to control the amount of gas generated by reacting with water over time, these gas generating materials are uniformly mixed with water and some substance whose oxygen gas permeability can be controlled. It is necessary to disperse and embed.

In order to provide the volatile insecticide with sustained release, a method of mixing the insecticide with a thermoplastic resin and embedding it has been attempted, but the resin composition is molded into a predetermined shape suitable for the intended use. In order to do so, high temperature shaping is required, and there is a problem that the pesticide is decomposed in this molding step or is scattered during the molding.

[0008] Generally, in order to obtain a plastic molded product with high productivity, a method of injection molding a thermoplastic polymer such as polyethylene, PMMA, polycarbonate or ABS is known. However, the inorganic substance that reacts with water to generate a gas used in the present invention decomposes when treated at a high temperature,
The thermoplastic polymer cannot be applied as a resin for embedding an inorganic substance, because it may generate gas and lose its efficacy, or in the case of an oxygen gas generating agent, it may ignite the resin.

The present invention has been made under the background as described above, and an object thereof is a curable resin composition containing an inorganic substance which reacts with water to generate a gas. By using, the effect of gas generation can be maintained for a long period of time, and the gas sustained release resin molded product excellent in control of the gas generation amount and use efficiency can be provided with high productivity.

[0010]

Means for Solving the Problems As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that at least one (meta) inorganic substance which reacts with water to generate a gas is ) A plastic molded product obtained by shaping and uniformly radically polymerizing an acryloyl group-containing compound maintains the gas while controlling the amount of gas generated per unit time in water to a constant amount. It has been found that the gas generation rate can be increased by adding a non-radical polymerizable compound to the radical curable composition, and the present invention has been completed.

That is, the present invention comprises (A) 1 to 90 parts by weight of an inorganic substance which reacts with water to generate a gas, and (B) at least one compound having at least one (meth) acryloyl group in the molecule. 5 to 90 parts by weight, (C) at least one kind of non-radical polymerizable compound 1 to 60 parts by weight, (D)
Radical polymerization initiator 0.001 to 5 parts by weight, (however,
(A), (B), (C) and (D) in a total amount of 100 parts by weight), a curable resin composition, and a radical polymerization of the curable resin composition. It is a molded product of sustained-release gas. Hereinafter, the curable resin composition of the present invention and the gas sustained-release resin molded product obtained by curing the curable resin composition into a predetermined shape will be described in more detail.

[Regarding Component (A)] The component (A) is an inorganic substance which reacts with water to generate a gas, and a known substance which reacts with a desired gas to generate water may be used. Specifically, as an inorganic substance that generates oxygen gas, an adduct of sodium carbonate and hydrogen peroxide (Na ₂ CO ₃ · 3 / 2H ₂
O ₂ ), an adduct of sodium metaborate and hydrogen peroxide (N
_{aBO 2 · H 2 O 2 /} 3H 2 O), and calcium peroxide (CaO ₂₎ and the like, also sodium hydrogen carbonate (NaHCO _3), and the like as inorganic materials for generating carbon dioxide. Among them, calcium peroxide (C
aO ₂ ) is particularly preferred.

The proportion of the component (A) used is from (A) to (D).
1 to 90 when the total weight of each component is 100 weight
Parts by weight, more preferably 5 to 70 parts by weight. (A)
A molded product made of a curable resin composition having a component content of less than 1 part by weight cannot provide a sufficient amount of gas generation, and a molded product exceeding 90 parts by weight has reduced mechanical strength.

[Regarding Component (B)] The component (B) having at least one (meth) acryloyl group in the molecule is a binder resin for embedding the inorganic substance of the component (A). Further, it is a component that selects the type of curable resin according to the content of the component (A) and adjusts the viscosity of the resin composition.

Specifically, when the component (A) is used in a large proportion, the component (A) can be obtained by using a highly viscous urethane (meth) acrylate or epoxy (meth) acrylate as the component (B). It is better to prevent the sedimentation of Further, for the purpose of improving the casting workability, it is preferable to adjust the viscosity of the curable resin composition with an ester monomer.

Examples of the component (B) include mono- or poly (meth) acrylates of aliphatic, alicyclic or aromatic mono- or polyalcohols, and aliphatic, alicyclic or aromatic urethane poly (meth) acrylates. , Epoxy poly (meth)
Acrylate and polyester poly (meth) acrylate may be mentioned.

Specific examples of these include methyl (meth)
Acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth)
Acrylate, orthobiphenyl (meth) acrylate, 3- (2,4-dibromophenyl) -2-hydroxypropyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, 1,6-
Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (n = 2 to 15) di (meth) acrylate, polypropylene glycol (n = 2 to 15) di (Meth) acrylate, polybutylene glycol (n = 2 to 15) di (meth) acrylate, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxy-3, 5-dibromophenyl) propane, bis (4-methacryloxyethoxyphenyl) sulfide, bis (4-methacrylthiophenyl) sulfide, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate,
Dipentaerythritol hexa (meth) acrylate,
Epoxy di (meth) acrylate obtained by reacting bisphenol A type diepoxy with (meth) acrylic acid, epoxy di (meth) acrylate obtained by reacting tetrabromobisphenol A type diepoxy with (meth) acrylic acid,
Urethane di (meth) acrylate obtained by reacting tolylene diisocyanate with 2-hydroxypropyl (meth) acrylate, urethane di (meth) acrylate obtained by reacting hydrogenated xylylene diisocyanate with 2-hydroxypropyl (meth) acrylate, xylylene di Examples thereof include urethane di (meth) acrylate obtained by reacting isocyanate with 2-hydroxypropyl (meth) acrylate.

These monomers may be used alone or in combination of two or more.

The proportion of the component (B) used is from (A) to (D).
5 to 90 parts by weight in 100 parts by weight of the component, more preferably 1
It is 0 to 80 parts by weight. In the case of a molded product made from a resin composition in which the amount of the component (B) used is less than 5 parts by weight, the mechanical strength of the gas sustained release resin molded product is lowered, and the amount of the component (B) is 9%.
Molded articles made from the resin composition exceeding 0 parts by weight,
Sufficient gas generation cannot be obtained.

[Regarding Component (C)] The non-radical polymerizable compound which is the component (C) improves the moisture permeability of the gas sustained-release resin molded product and increases the amount of gas generated. Examples of component (C) include organic compounds containing no radically polymerizable vinyl group, allyl group, etc. in the molecule. Among organic solvents, those having a boiling point of 100 ° C. or less are volatilized from the molded product after molding. It is not preferable because it will happen.

Specific examples of the component (C) include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, polycaprolactone diol, and hexanediol.
, Butanediol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, methoxypropanol, methoxybutanol, nonylphenol, nonylphenol
Alcohol compounds such as ethylene oxide adducts, hexanediol-diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, glycerin diglycidyl ether, pentaerythritol tetraglycidyl Epoxy compounds such as ether, pentaerythritol triglycidyl ether, bisphenyl A type diglycidyl ether, bisphenol F type diglycidyl ether, etc., and other relatively low molecular weight polyacrylpolyols, Examples thereof include polymethacrylic resin and vinyl chloride resin.

These compounds may be used alone or in combination of two or more.

The proportion of component (C) used is from (A) to (D).
1 to 60 parts by weight in 100 parts by weight of the component, more preferably 2
It is 0 to 50 parts by weight. Molded articles made from a resin composition in which the amount of component (C) used is less than 1 part by weight cannot produce a sufficient amount of gas, and the amount of component (C) exceeds 60 parts by weight. In the case of a molded product made from the above, the mechanical strength of the gas-releasing resin molded product is lowered.

[Regarding Component (D)] The radical polymerization initiator, which is the component (D), is a radical polymerization initiator that generates radicals by thermal energy, and radicals that are sensitive to active energy rays such as ultraviolet rays and visible rays. However, a known material may be used and is not particularly limited.

Specific examples of the former polymerization initiator which generates radicals by heat energy include organic peroxides such as benzoyl peroxide and t-butyl peroxyisobutyrate, and azo such as azobisisobutyronitrile. Examples thereof include compounds, but those having a relatively low reaction temperature represented by a 10-hour half-life temperature are more preferable. The latter active energy ray-sensitive polymerization initiator has a fast radical generation rate and can be molded at a low temperature, so that it does not lose the effect of generating the gas of the component (A) and is a sustained release resin excellent in productivity. A composition can be obtained.

Specific examples thereof include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone and 1-hydroxycyclohexyl. Phenyl ketone, methyl phenyl glyoxylate, ethyl phenyl glyoxylate, 2-hydroxy-2-methyl-1-
Carbonyl compounds such as phenylpropan-1-one,
Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and visible light-sensitive radical polymerization initiators such as camphorquinone You can

These are used in one kind or a mixture of two or more kinds. Among these, benzoin, benzoin isopropyl ether, methylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, benzyldimethylketal, 2,4,6- More preferred is trimethylbenzoyldiphenylphosphine oxide.

The proportion of the component (D) used is from (A) to (D).
0.001 to 5 parts by weight in 100 parts by weight of each component,
More preferably, it is 0.02 to 2 parts by weight. If the amount of component (D) used is less than 0.001 part by weight, the curability will be insufficient, and if the amount of component (D) exceeds 5 parts by weight, component (D) will be a thermal polymerization initiator. In the case where the component (A) is deactivated, and when the component (D) is an active energy ray sensitive initiator, the deep-curing property of the molded product of the resin composition is insufficient, resulting in a molded product containing an unpolymerized product. It is not preferable because it is easy.

The curable resin composition of the present invention and a molded product obtained by polymerizing and curing the curable resin composition into a predetermined shape may contain an antioxidant, an anti-yellowing agent, an ultraviolet absorber and a blue, if necessary. Various additives such as an ing agent, a pigment, an anti-settling agent, an antifoaming agent, an antistatic agent, and an antifogging agent may be contained.

As a method for obtaining the gas sustained-release resin molded product of the present invention, specifically, (A) to
The curable resin composition in which the component (D) is mixed in a predetermined amount is injected into a mold composed of two glass plates and a vinyl chloride gasket, and the mold is heated or irradiated with active energy rays, Alternatively, radical polymerization curing may be performed by a combination thereof.

The mold used for producing the sustained-release resin molded product of the present invention may be made of silicone rubber, glass, plastic, metal, or a combination thereof.

As a method for curing the curable resin composition of the present invention by casting polymerization, a method of placing it in a hot air oven or a hot water bath in the case of thermal polymerization, and a method of molding in a mold in the case of active energy ray polymerization. Examples include a method of irradiating an active energy ray such as a chemical reaction chemical lamp, a high pressure mercury lamp, a metal halide lamp and sunlight from one side or both sides. Among the active energy rays, an irradiation amount at a wavelength of 200 to 400 nm at which an integrated value of ultraviolet rays is 0.1 to 30 J / cm ² is particularly preferable because of excellent curability and good transmittance. Further, in the atmosphere of irradiation with active energy rays, it may be in air or in an inert gas such as nitrogen or argon.

As the gasket used to fix the two molds, a thermoplastic resin such as vinyl chloride or an adhesive tape made of polyester may be used.

[0034]

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples.

The abbreviations of the monomers described in the examples are as follows. SC: Addition product of sodium carbonate and hydrogen peroxide (Na ₂ C
_{O 3 · 3 / 2H 2 O} 2) CP: calcium peroxide (CaO ₂₎ UM1: xylylene diisocyanate and 2-hydroxypropyl methacrylate and urethane dimethacrylate obtained by reacting EM1: bisphenol A diglycidyl ether and methacrylic Epoxy dimethacrylate obtained by reacting with acid HDM: Hexanediol dimethacrylate 9GA: Nonaethylene glycol diacrylate PEG: Polyethylene glycol having a molecular weight of 600 TTG: Trimethylolpropane triglycidyl ether TPO: 2,4 , 6-Trimethylbenzoyldiphenylphosphine oxide MPG: methylphenylglyoxylate

Example 1 UM1 40 g, HDM 2
After mixing 0 g, 20 g of PEG and 0.05 g of TPO and stirring well at room temperature, 20 g of SC was added and stirred. This mixture is 125mm x 125mm, thickness 5m
Between two glass plates of m, made of vinyl chloride, outer diameter 8 mm
It was enclosed in a tube of No. 1 and was injected into a mold whose injection portion had a thickness of 5 mm. Then 40w from one side of the mold
30 minutes with a chemical lamp of about 3.6 J / cm ²
After irradiating with the ultraviolet ray, the cured molded product was demolded from the mold to obtain a gas sustained release resin molded plate. The obtained resin molded plate is cut into a width of 10 mm and a length of 100 mm,
The resin plate was placed under a 200 cc measuring cylinder installed upside down in a water tank filled with water, and the amount of oxygen generated was measured. The evaluation results are shown in Table 1 and FIG. 1, and the amount of gas generated from the molded product increased linearly,
After one month, 42 cc, which is 40% of 107 cc of available oxygen in SC, was observed, and after two months, 90%, and 97 cc of oxygen gas generation was observed.

Example 2 EM1 30 g, 9GA 2
0 g, TTG 10 g, and MPG 0.2 g were mixed and well stirred at room temperature, and then CP 40 g was added and stirred.
A gas sustained-release resin molded plate was prepared in the same manner as in Example 1 except that this mixture was used, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 1 and FIG.
The amount of gas generated from the shaped plate linearly increased, and after 1 month, 34 cc, which was 12% of the available oxygen amount 286 cc of CP, 30% after 2 months, 50% after 87 cc, and 3 months. An oxygen gas generation amount of 145 cc was observed.

[Comparative Example 1] The amount of gas generated from 20 g of SC powder was measured by the same evaluation method as in Example 1, and the results are shown in Table 1 and FIG. As a result, it was found that, after about 2 days, almost 100% of oxygen gas was generated with respect to the effective oxygen amount of SC.

[Comparative Example 2] The amount of generated gas of the powder of CP 40g was measured by the same evaluation method as in Example 1, and the results are shown in Table 1 and FIG. As a result, it was found that, after about 10 days, almost 100% of oxygen gas was generated with respect to the effective oxygen amount of CP.

[Comparative Example 3] EM1 30 g, 9GA 30
g and MPG 0.2 g were mixed and well stirred at room temperature, and then CP 40 g was added and stirred. A gas sustained-release resin molded plate was prepared in the same manner as in Example 1 except that this mixture was used, and the same evaluation as in Example 1 was performed. The results of this evaluation are shown in Table 1 and FIG. 1, and the amount of gas generated from the molded plate increased linearly, and one month later, it was 6% of the available oxygen amount 286 cc of CP, 17 cc, and 2 16 months after 46%, 46 cc, 3 months after 28%, 80 cc
The amount of oxygen gas generated was observed.

[0041]

[Table 1]

[0042]

The curable resin composition of the present invention contains an inorganic substance which reacts with water to generate a gas,
It is possible to provide, with good productivity, a gas sustained-release resin molded product which can maintain the action and effect of gas generation for a long period of time and is excellent in gas control and usage efficiency and safety.

[Brief description of drawings]

FIG. 1 is a diagram showing changes in the amount of generated oxygen with respect to the amount of available oxygen in terms of the number of days elapsed from the start of use.

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Claims (2)

[Claims] 1. 1 to 90 parts by weight of an inorganic substance (A) which reacts with water to generate a gas, and (B) at least one kind of a compound having at least one (meth) acryloyl group in the molecule 5.
To 90 parts by weight, (C) at least one kind of non-radical polymerizable compound 1 to 60 parts by weight, (D) radical polymerization initiator 0.001 to 5 parts by weight (however, (A), (B),
A total amount of (C) and (D) is 100 parts by weight). 2. A gas sustained-release resin molded product obtained by shaping the curable resin composition according to claim 1 into a predetermined shape and radical-polymerizing and curing it.