JP2017008192A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition capable of being molded to an article having high heat resistance at 300°C or more, flexibility and antibacterial property, transparency and self-support property, having activity on MRSA and capable of being used for a medical device, a touch panel film, a film for flexible printed circuit board or the like.MEANS FOR SOLVING THE PROBLEM: There is provided a curable resin composition consisting of (A) at least one kind of diallyl phthalate, (B) at least one kind of compound selected from triallyl isocyanurate, triallyl cyanurate or polycarbonic acid ester represented by the general formula:R-O-CO-[-O-R-O-CO-]n-O-R, where R represents a monovalent unsaturated group, Rrepresents a bivalent aliphatic or aromatic group and n represents the number of 1 to 9, (C) a polythiol component represented by the general formula:R-(-SH)m, where Rrepresents a polyvalent organic group and m represents an integer of 2 or more and having a ratio of functional equivalent of total (A)+(B)/functional equivalent of the (C) component of 3 to 0.5 and a ratio of functional equivalent of the (A) component/functional equivalent of the (B) component of 9 to 0.1.SELECTED DRAWING: None

Description

  The present invention relates to a curable resin composition, and in particular, curability that can be formed into a transparent self-supporting article having high heat resistance of 300 ° C. or higher, flexibility, and antibacterial properties. The present invention relates to a resin composition.

  Conventionally, vinyl monomers such as methyl acrylate and methyl methacrylate are generally used for producing a transparent resin molded product by photopolymerization or forming a film (coating). However, there are still problems with heat resistance, durability, oxygen inhibition, residual stress of the cured product, and the like. That is, when a vinyl monomer system is used, polymerization is inhibited by oxygen dissolved in the polymerization composition or oxygen in the atmosphere, and since it does not cure in the atmosphere, a method of introducing an inert gas is employed. . However, this method has the disadvantage of being costly. In the case of an acrylic composition, there is also a drawback that yellowing proceeds with time. This drawback is solved at the expense of cost by mixing additives such as bluing agents. Furthermore, a resin molded product and a film obtained from a photopolymerizable composition using a vinyl monomer system have low heat resistance. Therefore, various photopolymerizable compositions that do not use a vinyl monomer system have been proposed.

Patent Document 1 (Japanese Patent No. 3300670) describes a transparent curable resin composition using a polycarbonate and a polythiol as monomer components. The composition described in this patent is:
(A) General formula (I):
R—O—CO — [— O—R ¹ —O—CO—] n—O—R (I)
[Wherein, R represents an unsaturated group, R ¹ represents a divalent aliphatic or aromatic group, and n represents a number of 1 to 9],
(B) General formula (II):
R ² -(-SH) m (II)
[Wherein R ² represents a polyvalent organic group, m represents an integer of 2 or more],
(C) It comprises a photopolymerization initiator, and (A) and (B) are subjected to an ene / thiol reaction with ultraviolet rays to obtain a resin composition. By using this ene / thiol reaction, the problems of oxygen inhibition and residual stress of the cured product are solved. The cured product obtained from this resin composition has high transparency and excellent mechanical strength. However, the cured product obtained from this resin composition is not flexible and is difficult to use for film applications. Further, the heat resistance of the cured product is about 230 ° C. and cannot be used at a temperature exceeding 300 ° C.

  Patent Document 2 (Japanese Patent Laid-Open No. 2000-318113) describes a resin composition for producing an antibacterial decorative sheet having a permanently stable antibacterial effect and excellent in abrasion resistance, weather resistance and elasticity. ing. The resin composition described in this patent comprises at least one diallyl phthalate component and pentaerythritol tetra (3-mercaptopropionate). This resin composition is applied on a support, UV cured, and used as an antibacterial resin coating layer. However, it is not described whether this coating layer has self-supporting property or flexibility.

  Patent Document 3 (Japanese Patent Laid-Open No. 2000-344278) also describes uses as packaging materials and buffer materials for storing and preserving fresh foods and the like of the same resin composition as described above. In this patent, the resin composition is impregnated and applied to a composite material base material. The use of the same resin composition as a coating agent for antibacterial spectacle frames is described in Patent Document 4 (Japanese Patent Laid-Open No. 2001-133732), and the use of the same resin composition as an antibacterial adhesive roll is disclosed in Patent Document 5 (Japanese Patent Laid-Open No. 2002-085323). Gazette).

  The curable resin composition having flexibility, antibacterial properties and adhesiveness using polyallyl ester and polythiol described in Patent Documents 2 to 5 as monomer components is diallyl orthophthalate, diallyl isophthalate or diallyl as polyallyl ester. A terephthalate monomer is used, pentaerythritol tetrakis (3-mercaptopropionate) is used as a polythiol, and the mixture of both is irradiated with ultraviolet rays to undergo an ene / thiol reaction and cured. The cured resin composition has adhesiveness, flexibility and antibacterial properties, and has a heat resistance of about 300 ° C., but has a drawback that mechanical strength such as tensile strength is weak.

Therefore, this resin composition is suitable for coating applications in which it is applied and cured on a substrate, but when the resin composition itself is molded into a film and used, "film tearing" easily occurs. Therefore, it is not suitable for use as a film.
Furthermore, when using the curable resin composition of patent documents 2-5 for a coating use, it is necessary to consider the combination with the physical property of a base material side, and the heat resistance and flexibility which a resin composition has -Excellent properties such as antibacterial properties cannot always be fully exhibited.

  In many applications, there is a demand for a transparent self-supporting resin film having flexibility and heat resistance, and a self-supporting transparent resin film having flexibility and antibacterial properties.

Japanese Patent No. 3300670 JP 2000-318113 A JP 2000-344278 A JP 2001-133732 A JP 2002-085323 A

The object of the present invention is to maintain the properties of a material excellent in flexibility, heat resistance, antibacterial properties and transparency obtained by reacting a composition comprising polyallyl ester and polythiol described in Patent Documents 2 to 5. Accordingly, an object of the present invention is to provide a curable resin composition that can be molded into a self-supporting flexible article by improving its mechanical strength.
Another object of the present invention is to provide a self-supporting article, particularly a film, which is excellent in flexibility, heat resistance, antibacterial properties, and transparency without causing "film tearing".
The curable resin composition of the present invention is characterized in that it can be used in the form of a film, and its use is not limited to coating.

The present inventor has found that the above object can be achieved by reacting two types of polyenes with polythiol instead of one type of polyene and ene / thiol, and has completed the present invention based on this finding. is there.
Surprisingly, by adjusting the blending ratio of the two types of polyenes to a certain ratio, the antibacterial property is maintained as in the case of Patent Documents 2 to 5 even though different types of polyenes are added. The inventor has found that this is done. In addition to the Escherichia coli and Staphylococcus aureus described in Patent Documents 2 to 5, the present inventors have newly found that methicillin-resistant Staphylococcus aureus (MRSA) is also active.

That is, this invention exists in the curable resin composition characterized by including the following (A), (B) and (C):
(A) at least one compound selected from monomers or oligomers of diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate,
(B) At least one compound selected from triallyl isocyanurate, triallyl cyanurate, or a polycarbonate represented by the general formula (I):
R—O—CO — [— O—R ¹ —O—CO—] n—O—R (I)
[Wherein, R represents a monovalent unsaturated group, R ¹ represents a divalent aliphatic or aromatic group, and n represents a number of 1 to 9]
(C) Polythiol represented by the general formula (II):
R ² -(-SH) m (II)
[Wherein R ² represents a polyvalent organic group, and m represents an integer of 2 or more]

  Since the curable resin composition of the present invention has little oxygen inhibition and is polymerized in the air, purging with an inert gas is unnecessary during production, and the resin can be produced with a relatively simple apparatus. Further, it can be easily molded into a free shape and utilized as an elastomer excellent in various properties such as transparency, flexibility, heat resistance and antibacterial properties. The curable resin composition of the present invention can be suitably used as various industrial and consumer molded articles and coating agents, such as cap liners, hoses, tubes, various packings, cushioning materials, protective materials, protective films. It can be used for a slightly adhesive transparent film, a medical / nursing film, a flexible printed circuit (FPC) substrate film, a transparent conductive film, a touch panel protecting transparent film, and the like.

  The curable resin composition of the present invention contains the three types of monomers (A), (B) and (C) as essential components.

  Component (A) is diallyl phthalate, which is selected from diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate monomers or oligomers. These compounds can be used commercially.

  The purpose of blending the component (B) in the curable resin composition of the present invention is to improve the mechanical strength of the cured composition. Among the components (B), triallyl isocyanurate is most preferable from the viewpoint of mechanical strength and heat resistance of the cured resin composition. Among the polycarbonates represented by the general formula (I), diethylene glycol bis (allyl carbonate) is preferable from the viewpoint of mechanical strength although it is slightly inferior in heat resistance.

  As the component (C) of the curable resin composition of the present invention, it is preferable to use a polythiol represented by the above general formula (II). The polythiol used in the present invention is a substance having an average molecular weight of 50 to 15000 having two or more thiol groups per molecule, and the average molecular weight is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less, more Preferably it is 900 or less, More preferably, it is 800 or less. When the polythiol is an oligomer, the molecular weight means a number average molecular weight in terms of styrene.

  Preferred polythiols include mercapto group-substituted alkyl compounds such as dimercaptobutane and trimercaptohexane, mercapto group-substituted allyl compounds such as dimercaptobenzene, polyhydric alcohol esters such as thioglycolic acid and thiopropionic acid, and alkylenes of polyhydric alcohols. Examples include a reaction product of an oxide adduct and hydrogen sulfide. Examples of the polythiol include an aliphatic polythiol that may contain a heteroatom and an aromatic polythiol that may contain a heteroatom. Examples of the aliphatic polythiol that may contain a hetero atom include, for example, a polythiol other than a thiol group, such as an alkanedithiol having 2 to 20 carbon atoms, and a halogen atom of a halohydrin adduct of alcohol. Thioglycolic acid ester obtained by esterification of polythiol substituted with thiol group, polythiol composed of hydrogen sulfide reaction product of polyepoxide compound, polyhydric alcohol having 2-6 hydroxyl groups in the molecule and thioglycolic acid Contains a mercapto fatty acid esterified product obtained by esterification of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and a mercapto fatty acid, a thiol isocyanurate compound obtained by reacting an isocyanurate compound and a thiol, and a polysulfide group Thiol Silicone modified with a thiol group, modified silsesquioxane and the like are also mentioned thiol group. Examples of the polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule include alkanediol having 2 to 20 carbon atoms, poly (oxyalkylene) glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, and pentaerythritol. And dipentaerythritol.

Examples of polythiols include the following:
(1) Methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, 1,2-cyclohexanedithiol, bis (2-mercaptoethyl) ether, tetrakis (mercaptomethyl) methane, diethylene glycol bis (2 -Mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (2-mercaptoacetate), tri Methylolpropane tris (3-mercaptopropionate), trimethylolethane tris (2-mercaptoacetate), trimethylolethanetris (3-mercaptopropionate), pentaerythritol tetrakis ( -Mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) Sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2-mercaptoethyl) Thio) ethane, 1,2-bis (3-mercaptopropylthio) ethane, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2, , 3-Tris (3-Mercaptopropi Ruthio) propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-di Mercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane , Tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, 2,5-dimercaptomethyl-1,4-dithiane, 2 5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, and thiogs thereof Esters of cholic acid and mercaptopropionic acid, hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3 -Mercaptopropionate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide bis (3-mercapto) Propionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), Odiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester) 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetrakis (mercaptomethylthio) ethane, 4,6-bis (mercaptomethylthio) -1,3-dithiane, tris (mercapto) Aliphatic polythiols such as methylthio) methane, tris (mercaptoethylthio) methane;

(2) 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) benzene, , 4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,3,5-tri Mercaptobenzene, 1,3,5-tris (mercaptomethyl) benzene, 1,3,5-tris (mercaptomethyleneoxy) benzene, 1,3,5-tris (mercaptoethyleneoxy) benzene, 2,5-toluenedithiol , Aromatic polythiols such as 3,4-toluenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol;
(3) 2-methylamino-4,6-dithiol-sym-triazine, 3,4-thiophenedithiol, bismuthiol, 4,6-bis (mercaptomethylthio) -1,3-dithiane, 2- (2,2- Heterocyclic polythiol compounds such as bis (mercaptomethylthio) ethyl) -1,3-dithietane.

  Examples of commercially available products include TMTP, PETP (manufactured by Sakai Chemical Co., Ltd.), TMMP, PEMP, EGMP-4, DPMP (manufactured by SC Organic Chemical Co., Ltd.) and the like, but are not limited thereto. These compounds may be used alone or in combination of two or more.

  In this invention, it is preferable to use the compound shown by the following general formula (III) in polythiol.

〔式中、Ｒ³ は２価の有機基を表し、Ｒ⁴ は多価の有機基を表し、ｍは２以上の整数を表す〕

[Wherein R ³ represents a divalent organic group, R ⁴ represents a polyvalent organic group, and m represents an integer of 2 or more.]

  This compound is an ester of polythiol, examples of which are ethylene glycol bis (thioglycolate), ethylene glycol bis (3-mercaptopropionate), trimethylolpropane tris (thioglycolate), trimethylolpropane tris (3 -Mercaptopropionate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), di And pentaerythritol hexakis (3-mercaptopropionate).

  In the curable resin composition of the present invention, (A) and (B) are combined to form a polyene component, and this polyene component is cured by an ene / thiol reaction with the polythiol component of (C). In practice, the reaction proceeds by mixing the components (A), (B) and (C).

The reaction mechanism of the curable resin composition of the present invention is considered as follows:
(1) Radical generation Radical generation by light irradiation or heating.
(2) Initiation reaction A radical abstracts hydrogen from the thiol group of polythiol to produce a thiyl radical.
RSH-> RS ・
(3) Growth reaction Addition reaction of thiyl radical and polyene.
RS · + CH ₂ ═CH—CH ₂ —R ′ −> RS—CH ₂ —CH—CH ₂ —R ′
The intermediate draws hydrogen from the thiol group, forming a thiyl radical and chaining.
_{RS-CH 2 -CH-CH 2} -R '+ RSH -> RS-CH 2 -CH 2 -CH 2 -R' + RS ·

  The characteristic of the curable resin composition of this invention can be adjusted with the compounding ratio of the (A) component and (B) component which comprise a polyene component. When the component (A) is increased, the resin becomes more flexible / adhesive. On the other hand, when the component (B) is increased, a resin having higher transparency / mechanical strength and lower adhesiveness is obtained.

  The blending ratio of the (A) component and the (B) component in the polyene component is the ratio of the respective functional group equivalents, that is, (number of functional groups of component A) :( number of functional groups of component B) is 9: 1. It mix | blends so that it may become the range of 0.1: 1, preferably the range of 6: 1 to 0.28: 1. Among these, the suitable range of the said ratio is 2.5: 1-0.4: 1.

  In order to develop antibacterial properties in the cured resin, it is necessary to blend so that the number of functional groups of the component (A) in the polyene component is at least 40% of the number of functional groups of the component (B). . Therefore, the ratio of the number of functional groups of component (A) / number of functional groups of component (B) is in the range of 9 to 0.4, preferably in the range of 6 to 0.6, more preferably in the range of 1.2 to 0.8. In the range.

The reason why the composition of the present invention has antibacterial activity, particularly activity against methicillin-resistant Staphylococcus aureus (MRSA) is currently unknown. Possible reasons include but are not limited to a specific theory:
1) It originates in the sulfide structure which the allyl group and thiol group of diallyl orthophthalate (DAP) reacted.
2) Unreacted thiol group (SH group) of polythiol remains and has antibacterial properties.
3) The disulfide structure in which polythiols are combined to form an SS bond has antibacterial properties.

  The polyene component (A + B) and the polythiol component (C) in this ene / thiol reaction have a ratio of functional group equivalents, that is, (number of functional groups of the polyene component) :( number of thiol groups of the polythiol component) is 3. : It mix | blends so that it may become the range of 1-0.5: 1. When the polythiol component is less than this range, the polymerization is insufficient, and when the amount of the polythiol component is more than this range, a polymer having a strong monomer odor is obtained after the polymerization. Among these, the preferable range of (number of functional groups of the polyene component) :( number of thiol groups of the polythiol component) is in the range of 3: 1 to 0.5: 1, preferably 2.5: 1 to 0.6. : 1 range, more preferably 1.2: 1 to 0.8: 1.

Here, a method of calculating the “number of functional groups” of each component will be described. In the present invention, the relative ratio of each component in the composition is defined by the ratio of the number of functional groups. The ratio of the “number of functional groups” of each component can be calculated from the functional group equivalent and the number of functional groups of each component.
The values calculated for the “number of functional groups” in the case of the components (A, B, C) used in the examples by “weight of each component (g) × molecular weight per functional group” are shown below as examples.

  The curable resin composition of the present invention includes, in addition to the above components (A) to (C), precipitated calcium carbonate, mica, graphite, silica and the like as long as the object of the present invention is not impaired. An inorganic filler, an ultraviolet absorber, a leveling agent, an antistatic agent, a conductive filler, an antioxidant, a flame retardant, a dye, a pigment, and the like may be included.

  When an inorganic filler is used, it is preferably added in an amount of 0.1 to 20% by weight based on the total of components (A) to (C). When using an ultraviolet absorber, it is preferable to add the ultraviolet absorber in an amount of 0.01 to 3.0% by weight based on the total of the components (A) to (C). If the added amount of the UV absorber is less than 0.01% by weight, a sufficient UV absorbing effect cannot be obtained, and if it exceeds 3.0% by weight, it becomes saturated and does not dissolve.

  The ultraviolet absorber is not particularly limited as long as it is soluble in one or both of the monomers, and various types can be used, for example, benzophenone such as 2-hydroxybenzophenone and 2,4-hydroxybenzophenone. , Salicylates such as phenyl salicylate, (2′-hydroxyphenyl) benzotriazole, (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], and cyanoacrylate ultraviolet absorbers such as ethyl 2-cyano-3,3-diphenylacrylate. These can be used alone or in combination of two or more.

  The curable resin composition of the present invention can be formed into a self-supporting article, particularly a film. As this molding method, any known method can be used as a molding method for the curable resin composition. In general, the mixture can be produced by pouring (coating) a mixture of the above-described components (A) to (C) with additives used as necessary onto a mold, curing, and peeling the mixture from the mold.

  The curable resin composition of this invention can be used also for the use which coats on a base material and uses it as a membrane | film | coat. In this case, examples of the substrate include plastics such as polyethylene and polyester, metals, wood, concrete, glass, ceramics, paper, and the like.

  In the case of a coating application, the curable resin composition of the present invention can be diluted with a solvent for the purpose of improving applicability, adjusting viscosity, and uniformly mixing each component. The solvent is not particularly limited, and various solvents can be used. For example, aliphatic hydrocarbons such as n-pentane, n-hexane, and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. , Diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monoethyl ether, diethylene glycol mono -Β-chloroethyl ether, diethylene glycol monochlorohydrin, diethylene glycol monobutyl ether, diethylene Ethers such as recall mono-n-hexyl ether and diethylene glycol monomethyl ether, ketones such as ethyl methyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, formamide, N, N-dimethylformamide, N, N-dimethyl Examples include acetamide and N-methyl-2-pyrrolidone.

  Curing of the curable resin composition of the present invention can be performed by irradiation with actinic rays such as an electron beam or ultraviolet rays or by heat. When it is cured by ultraviolet rays, it may contain a photopolymerization initiator, and when it is cured by heat, it may contain a thermal polymerization initiator.

  When using a photoinitiator, it is preferable to mix | blend a photoinitiator in the ratio of 0.008 to 1.0 weight% with respect to the sum total of (A)-(C) component. When the amount of the photopolymerization initiator is less than 0.008% by weight of the total monomer, sufficient polymerization / curing reaction is not performed, and when it exceeds 1.0% by weight, transparency such as yellowing or clouding is achieved. The adverse effect of increases.

  The photopolymerization initiator is not particularly limited, and various types can be used. For example, benzoin, benzyl, benzoin methyl ether, acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butan-1-one, benzophenone, 4,4′-bis (dimethylamino) Benzophenone, 4,4′-bis (diethylamino) benzophenone, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 1-chloroanthraquinone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trichloromethyl-s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -4'-methoxyphenyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2-p-methoxystyryl-4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2,2'-bis (o-chlorophenyl) -4,4', 5 , 5′-tetraphenylbisimidazolyl, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra- (p-methoxyphenyl) bisimidazolyl, 2,4,6-trimethylbenzoyl Diphenylphosphine oxide, bisacylphosphine oxide, triphenylphosphine, triphenylphosphite, trilauryl-trithiophosphite, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, (η5-2, 4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methyl) Ethyl) benzene] - Iron (1 +) - hexafluorophosphate (1-) and the like, can be used alone or in combinations of two or more.

  When using a thermal polymerization initiator, it is preferable to mix | blend a thermal polymerization initiator in the ratio of 0.05 to 2.0 weight% with respect to the sum total of (A)-(C) component. Examples of the thermal polymerization initiator include azo polymerization initiators such as peroxydicarbonate and azobisisobutyronitrile, and these can be used alone or in combination of two or more.

  Since the curable resin composition of the present invention has little oxygen inhibition, there is an advantage that the polymerization reaction proceeds stably even in the air. In addition, a polymer excellent in various properties such as flexibility, antibacterial properties, transparency, and heat resistance can be obtained without causing deformation or distortion in the molded product during the polymerization reaction. Therefore, an article obtained by curing the curable resin composition of the present invention can be suitably used as a high heat resistant transparent film, antibacterial film, coating agent and the like having various functions in a well-balanced manner.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not restrict | limited by this.

Example 1
(A) Component 25.1 g diallyl phthalate, Component (B) 20.3 g triallyl isocyanurate, Component (C) pentaerythritol tetrakis (3-mercaptopropionate) 54.6 g, Photopolymerization initiator 2- 0.4 g of methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one was mixed in the dark. The obtained composition was uniformly applied onto a PET substrate film whose surface was peeled using a bar coater, and irradiated with ultraviolet rays for 120 seconds with a metal halide lamp with an output of 100 W. After forming a resin layer having a thickness of 150 μm, the resin layer was peeled from the base material to produce a resin composition film of the present invention.
The properties of the obtained film are shown in [Table 1]. This characteristic was exactly the same even after 6 months after film formation.

Example 2
The above components (A) to (C) were changed, and 25.1 g of diallyl phthalate was used as the component (A), and 26.4 g of diethylene glycol bis (allyl carbonate) where n = 1 in the general formula (I) as the component (B). The resin composition film was prepared by using 48.4 g of pentaerythritol tetrakis (3-mercaptopropionate) as the component (C) and operating the photopolymerization initiator and the like in the same manner as in Example 1.

Example 3
Components (A) to (C) are blended in the same manner as in Example 1. After adding and mixing 1.0 g of 2,2′-azobis-isobutyronitrile as a thermal polymerization initiator, the components are the same as in Example 1. After application to the material, it was heated to 100 degrees, peeled off after the resin layer was formed, and a resin composition film was produced.

Example 4
The photopolymerization initiator was changed to 43.9 g of diallyl phthalate as component (A), 5.1 g of triallyl isocyanurate as component (B), and 51.0 g of pentaerythritol tetrakis (3-mercaptopropionate) as component (C). Thereafter, the same operation as in Example 1 was carried out to produce a resin composition film.

Example 5
The photopolymerization initiator was changed to 6.3 g of diallyl phthalate as component (A), 35.4 g of triallyl isocyanurate as component (B), and 58.3 g of pentaerythritol tetrakis (3-mercaptopropionate) as component (C). Thereafter, the same operation as in Example 1 was carried out to produce a resin composition film.

Example 6
The photopolymerization initiator was changed to 25.1 g of diallyl phthalate as component (A), 20.3 g of triallyl isocyanurate as component (B), and 21.9 g of pentaerythritol tetrakis (3-mercaptopropionate) as component (C). Thereafter, the same operation as in Example 1 was carried out to produce a resin composition film.

Example 7
The photopolymerization initiator was changed to 25.1 g of diallyl phthalate as component (A), 20.3 g of triallyl isocyanurate as component (B), and 82.1 g of pentaerythritol tetrakis (3-mercaptopropionate) as component (C). Thereafter, the same operation as in Example 1 was carried out to produce a resin composition film.

Example 8
Changed to 25.1 g of diallyl phthalate as component (A), 20.3 g of triallyl isocyanurate as component (B), and 59.6 g of trimethylolpropane tris (3-mercaptopropionate) as component (C), and started photopolymerization. Thereafter, the same procedure as in Example 1 was followed to prepare a resin composition film.
The characteristics of the films obtained in Examples 2 to 8 are also summarized in [Table 1]. This characteristic was exactly the same even after 6 months after film formation.

Comparative Example 1
Only 50.2 parts by weight of diallyl phthalate as a polyene component and 49.8 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) as a polythiol component were mixed, and the photopolymerization initiator and the following were operated in the same manner as in Example 1. A resin composition film was prepared.

Comparative Example 2
Only 40.5 parts by weight of triallyl isocyanurate as the polyene component and 59.5 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) as the polythiol component were mixed, and the photopolymerization initiator and the following were operated in the same manner as in Example 1. Thus, a resin composition film was produced.
The properties of the films obtained in Comparative Examples 1 and 2 are also summarized in [Table 1].

[Table 1] and [Table 2] summarize the blending ratios of the components used in Examples 1 to 8 and Comparative Examples 1 and 2, and the characteristics of the obtained films.
[Table 1] and [Table 2] show the measurement results of the following characteristics:
(1) Average transmittance of visible light (750 to 350 nm) of the resin composition measured with a Shimadzu UV-3100PC spectrophotometer,
(2) Tensile strength test result (JIS K 7161 compliant),
(3) Weight loss start temperature (TG-DTA),
(4) 180 ° bending test (in this 180 ° bending test, the number of cracks after the sample film was bent to 180 ° was visually determined, and “No crack” was indicated as “◯” and “With crack” as “X”).

Antibacterial activity test Examples 1 to 8 and Comparative Examples 1 and 2 were tested for antibacterial activity values against Escherichia coli, Staphylococcus aureus, and methicillin-resistant Staphylococcus aureus (MRSA) by JIS Z2801 film adhesion method [Table 2]. Shown in
In this antibacterial activity test, after inoculating bacteria on the film to be tested, the number of viable bacteria after 24 hours at 35 ° C. was confirmed. The notation.

Claims (7)

The following (A) to (C):
(A) at least one compound selected from monomers or oligomers of diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate,
(B) at least one compound selected from triallyl isocyanurate, triallyl cyanurate, or a polycarbonate represented by the general formula (I),
R—O—CO — [— O—R ¹ —O—CO—] n—O—R (I)
[Wherein, R represents a monovalent unsaturated group, R ¹ represents a divalent aliphatic or aromatic group, and n represents a number of 1 to 9]
(C) Polythiol represented by the general formula (II) R ² — (— SH) m (II)
[Wherein R ² represents a polyvalent organic group, and m represents an integer of 2 or more]
The ratio of the sum of the functional group equivalent of the component (A) and the functional group equivalent of the component (B) / the functional group equivalent of the component (C) is 3 to 0.5, and the functionality of the component (A) The ratio of group equivalent / functional group equivalent of (B) component is 9-0.1, The curable resin composition characterized by the above-mentioned.   2. The curable resin composition according to claim 1, wherein a ratio of the functional group equivalent of the component (A) / the functional group equivalent of the component (B) is 0.4 or more.   A transparent self-supporting article having high heat resistance of 300 ° C. or higher and flexibility obtained by curing the curable resin composition according to claim 1.   A transparent self-supporting article having a high heat resistance of 300 ° C. or higher, flexibility and antibacterial properties obtained by curing the curable resin composition according to claim 2.   The article of claim 4 having activity against methicillin-resistant Staphylococcus aureus (MRSA).   The article according to claim 3 or 4, which is a film for a flexible printed circuit (FPC) substrate.   The antibacterial article according to claim 4 or 5, which is a medical / nursing care film or a transparent film for touch panel protection.