JPH07330837A - Curable resin composition and resin molding having sustained release of gas - Google Patents

Abstract

PURPOSE:To obtain a curable resin composition capable of maintaining action effect of gas generation for a long period and providing a molding excellent also in control and use efficiency of the generating gas amount, and useful as an oxygen generating material, etc., by embedding an inorganic material capable of generating gas by reaction with water in a specific resin composition. CONSTITUTION:This composition is obtained by combining (A) 1-90 pts.wt. of an inorganic material generating a gas by reaction with water with (B) 5-80 pts.wt. of a urethane poly(meth)acrylate having >=2 (meth)acryloyloxy groups in one molecule, (C) 1-60 pts.wt. of a compound of the formula (R1 and R2 are each H or methyl; R3 and R4 are each a 2-5C saturated hydrocarbon; (l) and (m) are each 1-5; (n) is 0-5), (D) 1-20 pts.wt. of an aliphatic polythiol compound having at least two thiol groups in the molecule and (E) 0.01-5 pts.wt. of an active energy beam polymerization initiator so that total amount of the components A to E becomes 100 pts.wt.

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 a specific resin composition is embedded with an inorganic substance that reacts with water to generate a gas, and a sustained release of a gas obtained by curing it into a predetermined shape. Resin molded article. 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 for 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 solidified solid state and used. Generally, as specific examples of inorganic substances that react with water to generate gas, an adduct of sodium carbonate and hydrogen peroxide, calcium peroxide, sodium hydrogen carbonate, and the like are widely known. For fragrances,
A method in which a volatile substance dissolved in a liquid volatile substance is directly sprayed on an object to be treated is mainly used.
As the insect repellent, a method of volatilizing the insect repellent by packaging a sublimable solid insect repellent in a film or the like having a partially 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, it is not possible to control the amount of gas generated, which is short. The amount of effective gas generated ends up being generated in 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 is dissolved in air because the amount of dissolved oxygen in water is several ppm at room temperature. Is released into the water 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 agents are uniformly dispersed in water and some substance capable of controlling oxygen gas permeability. It is necessary to disperse and embed.

In order to provide a volatile insecticide with sustained release, a method of mixing the insecticide with a thermoplastic resin and embedding it has been attempted, but molding the resin composition into a predetermined shape suitable for the intended use. In order to achieve this, high temperature shaping is required, so there was the problem that the insecticide decomposes during this molding process and 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 may decompose when treated at a high temperature to generate a gas and lose its effectiveness, or in the case of an oxygen gas generating agent, it may ignite a resin. However, the thermoplastic polymer cannot be applied as a resin for embedding an inorganic substance.

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 moreover, a gas sustained release 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 an inorganic substance that reacts with water to generate a gas is a specific urethane poly (meth) acrylate or a specific structure. Of the carbonate di (meth) arylate, the aliphatic polythiol compound having at least two thiol groups in the molecule, and the active energy ray polymerization initiator are uniformly dispersed in a composition and then cast. A plastic molded product obtained by pouring into a mold by a polymerization method and irradiating active energy rays from the outside of the mold to polymerize and cure is a gas while controlling the amount of gas generated per unit time in water to a constant amount. It has been found that it is possible to continuously generate the above, and the present invention has been completed.

That is, the present invention relates to (A) 1 to 90 parts by weight of an inorganic substance which reacts with water to generate a gas, and (B) a urethane poly (meth) having two or more (meth) acryloyloxy groups in one molecule. ) 5 to 80 parts by weight of acrylate, (C)
Compounds 1 to 60 represented by the following general formula (I),

[Chemical 2] (In the formula, R ₁ and R ₂ are hydrogen or a methyl group, R ₃ and R ₄ are linear or branched saturated hydrocarbon groups having 2 to 5 carbon atoms, 1,
m shows the integer of 1-5, n shows the integer of 0-5. ) (D) 1 to 20 parts by weight of an aliphatic polythiol compound having at least two thiol groups in the molecule, (E) 0.01 to 5 parts by weight of an active energy ray polymerization initiator,
A curable resin composition in which the total amount of (A), (B), (C), (D) and (E) is 100 parts by weight,
And a gas sustained-release resin molded product obtained by injecting the curable resin composition into a mold and then irradiating an active energy ray from the outside of the mold to polymerize and cure.

The curable resin composition of the present invention and the gas sustained-release resin molded product using the curable resin composition will be described in more detail below.

[Regarding Component (A)] The component (A) is an inorganic substance that reacts with water to generate a gas, and any known substance generated by reacting a target gas with 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 (Ca), which does not easily raise the pH of water, is used for supplying oxygen to fish.
O ₂ ) is particularly preferred.

The proportion of component (A) used is from (A) to (E).
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 gas sustained-release resin molded product made from a resin composition having an amount of less than 1 part by weight cannot obtain a sufficient amount of gas,
In the case of a molded product made of a resin composition in which the amount of the component (A) exceeds 90 parts by weight, the mechanical strength of the gas sustained release resin molded product decreases.

[Regarding Component (B)] The component (B), a urethane poly (meth) acrylate compound having two or more (meth) acryloyloxy groups in one molecule is
It is a binder resin for embedding the inorganic substance of component (A), and is a component for adjusting the viscosity of the resin composition by selecting the type of resin according to the content of component (A). It is also a component that imparts mechanical strength, impact resistance, and heat resistance to the manufactured plastic molded product.

That is, specifically, a urethanization reaction product of a hydroxyl group-containing (meth) acrylate and an isocyanate compound having two or more isocyanate groups in the molecule, or two or more isocyanates in the molecule A urethane-forming reaction product obtained by reacting a polyisocyanate having a group with a polyol, polyester, or polyamide diol to synthesize an adduct, and then adding a (meth) acrylate containing a hydroxyl group to the remaining isocyanate group. Is mentioned.

The former urethanization reaction product is preferable because it can improve the surface height and heat resistance of the molded product, and a compound having a molecular weight of 400 to 2000 is particularly preferable. Further, the polyol used for the synthesis of the adduct required to obtain the latter urethanization reaction product is not particularly limited. Specific examples of the polyol include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, alkyl polyols such as glycerin, and polyether polyols thereof and polyhydric alcohols. There are polyester polyols synthesized from polybasic acids.

Specific examples of the polyisocyanate compound used when synthesizing these urethanization reaction products include 1,6-hexamethylene diisocyanate, tris (isocyanatohexyl) isocyanurate, and 1,4.
-Tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, bis (4,4'-isocyanatocyclohexyl) methane, bis (4,4'-isocyanatocyclohexyl)
Propane, 1,3-bis (isocyanatomethyl) cyclohexane, metaxylylene diisocyanate, paraxylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (4,
4'-isocyanatophenyl) methane, naphthalene diisocyanate and the like can be mentioned. Among the above, tris (isocyanatohexyl) isocyanurate, isophorone diisocyanate, bis (4,4′-isocyanatocyclohexyl) methane, 1,3-bis (isocyanatomethyl) cyclohexane, metaxylylene diisocyanate, 2,4- Tolylene diisocyanate, 2,
6-Tolylene diisocyanate is particularly preferred.

Specific examples of the hydroxyl group-containing (meth) acrylate used for obtaining these urethanization reaction products include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.
Addition reaction of (meth) acrylic acid with monoepoxy compounds such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and glycidyl methacrylate in addition to acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. Examples thereof include mono (meth) acrylic acid esters of polyethylene glycol and polypropylene glycol, mono (meth) acrylic acid esters of polycaprolactone diol, and the like.

The reaction of polyisocyanate for obtaining these urethanization reaction products with various diols and (meth) acrylates containing a hydroxyl group is carried out in the presence of a tin catalyst such as n-butyltin dilaurate in the presence of isocyanate. When the group and the hydroxyl group are used so as to be almost equal,
It may be heated at 70 ° C. for several hours. The reaction product is
In general, the viscosity is high in many cases, so it is preferable to dilute with another diluting monomer during or after the reaction.

The proportion of the component (B) used is (A) to (E).
The total amount of the components is 5 to 80 parts by weight, more preferably 15 to 70 parts by weight, based on 100 parts by weight. A molded article made of a curable resin composition in which the amount of the component (B) used is less than 5 parts by weight cannot give a gas sustained-release resin molded article having sufficient mechanical strength and heat resistance. ) In the gas sustained-release resin molded product made from the composition having the component amount exceeding 80 parts by weight,
Not only does the monomer composition become highly viscous, the workability of injecting it into a silicon mold deteriorates, but also a sufficient amount of gas generated cannot be obtained.

[About component (C)] The compound represented by the general formula (I), which is the component (C), is a polyethylene glycol, polypropylene glycol or polybutylene glycol having a degree of polymerization of 1 to 5 represented by l and m. Or an aliphatic diallyl carbonate obtained by the reaction of poly (methylbutylene) glycol with phosgene or dimethyl carbonate, and (meth) allyl alcohol. The most preferable compound as the component (C) is diethylene glycol diallyl carbonate.

The proportion of component (C) used is from (A) to (E).
The total amount of each component is 100 parts by weight, and preferably 1 to 60 parts by weight, more preferably 5 to 40 parts by weight. When the amount of the component (C) is less than 1 part by weight, the curable resin composition becomes highly viscous, and not only the workability of injecting into the mold is lowered, but also the gas generation rate is lowered. Further, when a molded product is made from a resin composition in which the amount of the component (C) exceeds 60 parts by weight, the mechanical strength of the gas sustained release molded product decreases.

[About Component (D)] The aliphatic polythiol compound having at least two thiol groups in the molecule, which is the component (D), is a component that improves moldability during curing by irradiation with active energy rays. is there.

Specific examples of the component (D) include 1,2-ethylenedithioglycol, 1,2-propylenedithioglycol, 1,4-butylenediglycol, and di (2-
Mercaptoethyl) thiol thiol, di (2-mercaptopropyl) thiol, ethylene glycol dithioglycolate, 1,2-propylene glycol dithioglycolate, 1,4-butanediol dithioglycolate, trimethylolpropane tris (thioglycolate) , Pentaerythritol tetrakis (thioglycolate), ethylene glycol dithiopropionate,
1,2-propylene glycol dithiopropionate,
1,4-butanediol dithiopropionate, trimethylolpropane tris (β-thiopropionate),
Pentaerythritol tetrakis (β-thiopropionate) and the like can be mentioned. Among these, trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis (β-thiopropionate)
Is particularly preferable because it has less odor peculiar to polythiol.

The proportion of component (D) used is from (A) to (E).
The total amount of each component is 1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight. A molded article made of a resin composition having an amount of component (D) less than 1 part by weight has poor moldability upon curing, and a molding made from a resin composition having an amount of component (D) exceeding 20 parts by weight. The product has reduced mechanical strength and heat resistance.

[Regarding Component (E)] The active energy ray polymerization initiator, which is the component (E), has a high radical generation rate and can be molded at a low temperature, and therefore loses the effect of the gas generated from the component (A). It is possible to obtain a sustained-release resin composition which is excellent in productivity without being produced.

Specific examples of the component (E) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, Carbonyl compounds such as 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, ethylphenyl glyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, tetramethylthiuram monosulfide, tetramethylthiuram Sulfur compounds such as disulfide, 2,
An acylphosphine oxide such as 4,6-trimethylbenzoyldiphenylphosphine oxide can be used. These are used in one kind or a mixture of two or more kinds.

Among these, benzophenone, benzoin isopropyl ether, methylphenyl glyoxylate, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferable.

The proportion of the component (E) used is from (A) to (E).
The total amount of each component is 0.01 to 5 parts by weight, more preferably 0.02 to 2 parts by weight, based on 100 parts by weight. A curable resin composition having an amount of component (E) of less than 0.01 part by weight has insufficient curability, and a molded product made of the resin composition having an amount of component (E) of more than 5 parts by weight has a deep curability. Not only will it run short, but it will also cause coloration of the resin molded product.

The curable resin composition of the present invention may contain a compound having at least one radical-polymerizable double bond in the molecule, if necessary. The compound is
It is a component that imparts heat resistance, abrasion resistance, mechanical strength, etc. to the manufactured sustained-release resin molded product.

Specific examples of these include methyl (meth)
Acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, Mono (meth) acrylate monomers such as cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, 1,4-
Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2'-bis ((meth ) Di (meth) acrylate monomers such as acryloxyethoxyphenyl) propane, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, Examples include poly (meth) acrylate monomers such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The ratio of the compound used can be added to the curable resin composition in the range of 1 to 20 parts by weight based on 100 parts by weight of the total amount of the components (A) to (E). Further, in the curable resin composition of the present invention and molded articles using the same, if necessary, organic peroxides, antioxidants, yellowing inhibitors, ultraviolet absorbers, organic dyes, pigments, inorganic fillers. Various additives such as an anti-settling agent and an antifoaming agent may be contained.

In order to cure the resin composition using the above-mentioned mold, components (A) to (E) are mixed according to the desired performance, and then a master having a desired shape is embedded and cured. It may be injected into a transparent mold made of silicone from which the master has been removed, and radical-polymerized and cured by irradiation with active energy rays, heating, or a combination thereof.

As the active energy ray used in the present invention, an active energy ray of the sun, a chemical lamp, a high pressure mercury lamp, a metal halide lamp or the like can be used. The active energy ray having a wavelength of 200 to 500 nm is particularly preferable because it has excellent curability and good transmittance. The active energy ray irradiation atmosphere may be in air or in an inert gas such as nitrogen or argon.

The mold used for producing the sustained-release resin molded product of the present invention has a transparent surface irradiated with active energy rays or a wavelength of the active energy rays of 200 to
The material having a high transmittance of 500 nm is not particularly limited, and silicone rubber, glass, plastic, metal, or a combination thereof may be used. The silicone rubber mold is preferably a two-component curing type silicone rubber for forming various three-dimensional molded articles. When using two dies,
As the gasket used for fixing these, a thermoplastic resin such as vinyl chloride or an adhesive tape made of polyester may be used.

[0037]

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₎

[Example 1] [Preparation of silicone mold] Width 10 mm, length 100 m
m, 5 mm thick acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd .;
Product name: Acrylite L) made of acrylic plate with a thickness of 2 mm, opening 30 mm x 10 mm, depth 150 mm
Into a box-shaped outer frame, inject silicone rubber resin liquid (Toshiba Silicone Co., Ltd .; trade name: TSE3032) into it, leave it for 15 hours at room temperature to cure it, and then use a cutter knife to remove the transparent silicone rubber. After cutting and taking out the acrylic plate, a silicone mold was prepared.

[Preparation of Gas Slow Release Resin Molded Article] 2,6-
60 g of urethane dimethacrylate synthesized from 1 mol of tolylene diisocyanate and 2.1 mol of 2-hydroxypropyl methacrylate, diethylene glycol diallyl carbonate (manufactured by Tokuyama Soda Co., Ltd .; trade name: TS-1)
6) 12 g, trimethylolpropane tris (β-thiopropionate) (Yodo Chemical Co., Ltd .; trade name: TMTP) 8
g and benzophenone 1 g were mixed and stirred well at room temperature,
20 g of SC was added and stirred to obtain a resin composition. The resin composition thus obtained is poured into a silicone mold at room temperature and atmospheric pressure, and the resin composition is mixed with a 40-w chemical lamp from both sides of the mold.
After irradiating with ultraviolet light having an integrated ultraviolet light energy of 340 to 380 nm of 4 J / cm ² for 0 minutes, the cured molded product was released from the mold to obtain a gas sustained release resin molded plate.

Then, the obtained resin molded plate was placed under a 200 cc graduated cylinder installed upside down in a water tank filled with water, and the amount of oxygen generated was measured.
The results of this evaluation are as shown in Table 1 and FIG. 1, and the amount of gas generated from the molded product increased linearly, and after one month it was 40% of the effective oxygen amount 107 cc of SC 43c.
After two months, 90% and 95 cc of oxygen gas generation was observed.

[Example 2] Width 10 mm, length 500 m
A gas-releasing resin molded product was prepared using the same resin composition as in Example 1 except that an acrylic square block having a thickness of 10 mm and a thickness of 10 mm was used as a master to prepare a silicone mold.
The evaluation results of the obtained molded product are shown in Table 1.

[Embodiment 3] Diameter 10 mm, length 65 mm
A gas sustained-release resin molded product was prepared using the same resin composition as in Example 1 except that the silicone mold was prepared using the thick columnar master. The evaluation results of the obtained molded product are shown in Table 1.

[Example 4] Diameter 5 mm, length 250 mm
A gas-releasing resin molded product was prepared using the same resin composition as in Example 1 except that the silicone mold was prepared using the thin columnar master. The evaluation results of the obtained molded product are shown in Table 1.

Example 5 Urethane dimethacrylate 33 synthesized from 1 mol of 2,6-tolylene diisocyanate and 2.1 mol of 2-hydroxypropyl methacrylate.
g, diethylene glycol diallyl carbonate (manufactured by Tokuyama Soda Co., Ltd .; trade name: TS-16) 12 g, trimethylolpropane tris (β-thiopropionate) (manufactured by Yodo Chemical Co., Ltd .; trade name: TMTP) 6 g, benzophenone 1
After thoroughly mixing and stirring g at room temperature, 40 g of CP was added and stirred to obtain a resin composition. Using the obtained resin composition, a gas sustained-release resin molded plate was obtained in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1 and FIG. 1, and the amount of gas generated from the molded product increased linearly, 43 cc which is 15% of the available oxygen amount of 286 cc of CP after 1 month, and 2 months after. 30% 87cc, 3 months later 50% 14
An oxygen gas generation amount of 0 cc was observed.

[Examples 6 to 8] Gas sustained-release resin molding was performed in the same manner as in Example 1 except that the same silicone molds as in Examples 2 to 4 and the same resin composition as in Example 5 were used. I got the goods. The evaluation results of the obtained resin molded product are shown in Table 1.

[Comparative Example 1] The amount of gas produced 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 40 g 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 CP.

[0048]

[Table 1]

EFFECTS OF THE INVENTION As described above, a gas sustained-release resin molded article containing an inorganic substance that reacts with the same volume and the same amount of water to generate a gas using the curable resin composition of the present invention has a surface area In proportion to this, the gas generation amount can be controlled over a long period of time to efficiently provide the gas.

[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.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08F 299/06 MRX C08J 5/00 CFF 7/00 302 C09D 4/02 PDZ C09K 3/00 110 B // B01J 7/00 A

Claims (2)

[Claims] 1. (A) 1 to 90 parts by weight of an inorganic substance which reacts with water to generate a gas, and (B) a urethane poly (meth) acrylate having 5 or more (meth) acryloyloxy groups in one molecule. 80 parts by weight, (C) 1 to 60 polymerized parts of a compound represented by the following general formula (I), (In the formula, R ₁ and R ₂ are hydrogen or a methyl group, R ₃ and R ₄ are linear or branched saturated hydrocarbon groups having 2 to 5 carbon atoms, 1,
m shows the integer of 1-5, n shows the integer of 0-5. ) (D) 1 to 20 parts by weight of an aliphatic polythiol compound having at least two thiol groups in the molecule, (E) 0.01 to 5 parts by weight of an active energy ray polymerization initiator,
A curable resin composition that is combined such that the total amount of (A), (B), (C), (D) and (E) is 100 parts by weight. 2. A gas-releasing resin molded article obtained by injecting the curable resin composition according to claim 1 into a mold and then irradiating active energy rays from the outside of the mold to polymerize and cure the resin.