KR20120021820A - Flame retardant photocurable resin composition and photocurable sheet material comprising same - Google Patents

Abstract

PURPOSE: A photo-curable resin composition with a superior fire retardant characteristic and a photo-curable sheet material including thereof are provided to be used as enforcement or repair materials, insulating material, or heat insulating material while maintaining excellent fire retardant characteristic. CONSTITUTION: A photo-curable resin composition comprises 18-40 parts by weight of epoxy acrylate resin, 23-53 parts by weight of more than 2 types of flame retardants selected from halogen based flame retardant, phosphorus based flame retardant, nitrogen-based flame retardant, and inorganic flame retardant, 0.001-1 parts by weight of phosphine based photo initiator, 0.001-1 parts by weight of alpha-hydroxy ketone based photo initiator, 0.001-1 parts by weight of fumed silica, 20-50 parts by weight of glass fiber, 0.001-1 parts by weight of viscosity depressant, 0.001-1 parts by weight of antifoaming agent, 0.001-0.5 parts by weight of reactive diluents, and 0.001-0.5 parts by weight of silane coupling agent.

Description

Flame retardant photocurable resin composition and photocurable sheet material comprising the same

The present invention relates to concrete, iron, GRP, FRP, PVC, glass, such as concrete storage facilities, ground or underground pipelines, roofs, etc. of chemical storage tanks, oil tanks, banks, food plants, pharmaceutical plants, and electronic materials-related plants. The present invention relates to a flame retardant photocurable resin composition having excellent high strength and workability and flame retardancy and to a photocurable sheet material including the same, which are coated on a wooden structure and used as a reinforcing material, a corrosion resistance material, a lining material, a heat insulating material, a heat insulating material, and the like. Flame retardant photocurable resin composition prepared by impregnating a glass fiber mat with a photocurable resin composition comprising a rate-based resin, a mixed photoinitiator and a mixed flame retardant, or by adding glass fiber to the photocurable resin composition It relates to a sum sheet material.

Means for storing and transporting or transporting gaseous or liquid chemicals, such as chemical storage tanks, oil tanks and pipelines, as well as concrete facilities and coastal barriers in food factories, pharmaceutical factories, and electronic materials factories, for their durability and corrosion protection. Not only concrete, steel, stainless steel, and reinforced plastics are used, but these materials are also used in a wide range of infrastructure facilities such as water and sewage, crude oil, chemicals, and city gas, which are closely related to our lives.

However, for example, steel pipes are mainly used in crude oil transportation, but corrosion of pipes may occur due to corrosive impurities contained in petroleum, and crude oil may leak. In addition, although concrete fume pipes are mainly used in water supply and sewerage, physical damage due to external pressure may occur due to long-term burial use, and in particular, in sewage, sulfurous acid generated by sulfur dioxide and sulfur dioxide caused by decomposition of contaminants. Corrosion and aging from the inner surface of concrete pipes are a problem due to the generation of ions, and there is a problem of reinforcement and repair of existing buried pipes.

In addition, there are cases where corrosion prevention coating or lining is installed inside the pipe as a local repair of existing buried pipe as well as improvement of corrosion resistance of new buried pipe, but there is a life limit of existing buried pipe, and strength and durability to strengthen the strength of existing pipe In addition, a method of newly inserting a corrosion resistant plastic pipe into an old pipe has been attempted, but there is a problem in that the repair of the existing pipe has a limitation in cost and a shaving limit in terms of large construction.

As a repair method that can be installed in the field, which is currently attracting the most attention, a method of inserting an FRP prepreg impregnated with a thixotropic imparting agent in advance into an old pipe or pressing it out of an old facility and curing it with hot water or hot air (P. Chaneliere, U.Bultjer, Diegrabenlose Sanierungｖon Abwasserleitungen.Ein interessanntes Einsatzgebiet fur ungesattigtePolyesterharze.Composites 3, 18 (1992), D.Johnson et al., 45 th.SPI, 12-D (1990)) The prepreg used in the method is impregnated with an unsaturated polyester, vinyl ester resin or epoxy resin in a cylindrical felt or fabric in which reinforcing fibers such as woven strand mat and nonwoven fabric are bonded to one side of an extensible film to an impregnated resin composition. The laminated film is laminated on the outside of the cylinder, and it is pasted in the pipe and pressed to the pipe wall by water pressure or air pressure, and the hot water or hot air. It is characterized by hardening and reinforcing.

However, the above-described method exhibits performance that combines reinforcement hardening in addition to anticorrosion hardening because the cylindrical prepreg is flexible, and can be installed in the field and hardened in a state of being pressed against the tube wall. Since an epoxy resin containing a chemical resin or a curing agent is used, there is a disadvantage in that the pot life or storage time as a prepreg is short, and a large amount of heat medium and a large amount of heat are required for curing.

On the other hand, a method of using ultraviolet rays as a curing means using a composite material impregnated with an unsaturated polyester resin in a glass fiber or a glass mat (Kunststoffe German Plastics. 83 (10), 55 (1993)) is known, but this method is a heat medium and While heat is unnecessary, when the FRP layer is thickened to improve anticorrosion, UV transmission becomes difficult and uncured or cracks due to differences in curing rates are very likely to lower corrosion resistance. In order to ensure permeability, only a small amount of filler or filler can be added, which is disadvantageous in terms of dimensional stability and cost of the cured product.

Further, Japanese Laid-Open Patent Publication No. 63-186744 discloses a photocurable prepreg formed by laminating a transparent sheet on one surface. The photocurable prepreg smoothes the surface of the cured product by the transparent sheet and can clean the appearance. However, it is necessary to apply a primer for adhesion of the base material, there is a fear that sufficient adhesiveness may not be secured depending on the base material, and there is a disadvantage in that construction work is cumbersome.

Japanese Laid-Open Patent Publication No. 57-99375 discloses that a curable molding material layer is adhered to a thin steel sheet using a photocurable epoxyvinyl ester resin containing a specific dibasic acid or oligoester in a resin skeleton, followed by light irradiation to cure the thin film. A method of reinforcing a steel sheet is disclosed. Although this method can improve the adhesive strength of the curable molding material layer to a thin steel sheet to some extent, there is a possibility that sufficient adhesiveness may not be secured depending on the substrate. Defects may not be sufficiently suppressed or construction work may be complicated.

Japanese Laid-Open Patent Publication No. 59-1250 discloses a method of adhering to a prepreg steel sheet which applies a curable and lipophilic primer to the curable prepreg, and then adheres the coated surface to the steel sheet, and then cures the prepreg and the primer. In this sticking method, the prepreg is slightly swelled with a primer, whereby poor adhesion to the prepreg steel sheet is suppressed to some extent. However, depending on the substrate, there is a possibility that sufficient adhesiveness may not be secured, and adhesion failure may not be sufficiently suppressed in terms of limited construction time or inability to sufficiently adhere the prepreg to the substrate because the prepreg or primer is cured during construction. There is a concern, there is a disadvantage that the construction work is complicated because it is necessary to use a primer.

As described above, in the conventional thermosetting resin composition, there is a problem in pot life or storage stability as a prepreg, and in the case of site construction, it is necessary to secure a large amount of heat medium in order to uniformly harden the facility. Or there was a restriction on the length of the pipe, the facility area or the pipe diameter, and the conventional UV curable resin composition does not require a large amount of heat source or auxiliary equipment for uniformizing the heat distribution indispensable when using the thermosetting resin composition. However, there was a problem that it is difficult to secure the thickness of the FRP layer required for reinforcement and corrosion at the time of ultraviolet curing.

In addition, the conventional thermosetting resin composition or the photocurable resin composition as described above are not considered flame retardant, and due to the weak flame retardant properties, the use of the flame retardant facilities such as the electronic component field is very limited due to the risk of fire. Until now, after applying a photocurable insulating resin composition or sheet material for flame retardancy, a flame retardant powder material was applied by powder coating to impart flame retardancy. At this time, although the thermosetting epoxy resin composition is used as the coating material, it is used as a wax due to various problems such as defective rate, waste generation, and evasion of the worker's job. However, wax has a low flash point, which increases the risk of fire in the manufacturing process, and heat resistance is a problem even when the finished product is used.

On the other hand, generally, the method of imparting flame retardancy to a resin may be divided into an additional flame retardant method in which a flame retardant and a flame retardant aid are added, and a polymerization flame retardant method in which a resin is prepared using a special compound containing a flame retardant atom during polymerization. Since the polymerization polymerization flame retardant method has a high cost and difficulty in achieving flame retardancy, most commercialized flame retardant resins are prepared by an additional flame retardant method in which a flame retardant containing halogen or phosphorus is added during mixing.

In the additive flame retardant method, a halogen organic compound may be added to impart flame retardance to the photocurable resin composition. However, halogenated organic compounds are mainly bromine or chlorine compounds, and when added thereto, flame retardancy is very excellent, but transparency is deteriorated, photocuring reactivity is deteriorated, and there is a problem in mechanical properties and adhesion due to an increase in the viscosity of the composition, and occurs during combustion. Toxic and corrosiveness of the smoke is a problem.

Therefore, it is applied to various surface conditions or complex shapes of various substrates, and after curing, it has excellent mechanical and chemical properties such as adhesive strength and durability, and is quickly cured.It can be used as reinforcement or repairing material, insulation, and heat insulating material while maintaining excellent flame resistance. There has been a great demand for the development of a photocurable resin composition and a photocurable sheet material including the same.

Accordingly, the present inventors have studied and tried to impart flame retardancy to the photocurable resin composition, and as a result, by adding a mixed photoinitiator and a mixed flame retardant to a resin based on epoxy acrylate, the mechanical and chemical properties such as adhesive strength and durability of the cured photocurable resin were improved. The present invention has been completed by preparing a flame retardant photocurable resin composition which can be used as a reinforcing or repairing material, a heat insulating material, and a heat insulating material while maintaining excellent flame resistance and excellent photocurability.

The present invention to solve the above problems, 18 to 40 parts by weight of epoxy acrylate resin; 23 to 53 parts by weight of two or more flame retardants selected from halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, and inorganic flame retardants; 0.001 to 1 part by weight of a phosphine-based photoinitiator; 0.001 to 1 part by weight of an alpha hydroxy ketone (α-Hydroxyketone) photoinitiator; 20 to 50 parts by weight of glass fiber; 0.001 to 3 parts by weight of fumed silica; 0.001-0.5 parts by weight of silane coupling agent; 0.001 to 1 part by weight of a viscosity reducing agent; 0.001-1 weight part of antifoamers; It is set as the solution means of providing a flame-retardant photocurable resin composition characterized by including 0.001-0.5 weight part of reactive diluents.

In addition, the epoxy acrylate resin is to provide a flame-retardant photocurable resin composition having a number average molecular weight of 500 ~ 10,000 g / mol as a means for solving the problem.

In addition, the epoxy acrylate resin is a flame retardant photocurable resin composition characterized in that the mixed epoxy acrylate resin mixed with 15 to 30 parts by weight of bisphenol A-type epoxy acrylate and 3 to 10 parts by weight of a novolak type epoxy acrylate. It is a solution to the problem.

In addition, the flame retardant is a mixed flame retardant mixture of 20 to 45 parts by weight of inorganic flame retardant and 3 to 8 parts by weight of halogen flame retardant is to provide a flame retardant photocurable resin composition characterized in that the solution.

In addition, the inorganic flame retardant is a metal-based inorganic oxide is antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimony carbonate, metal antimony, antimony trichloride, antimony pentachloride, barium borate, zirconium oxide, zinc borate, zinc stannate, magnesium hydroxide, Selected from aluminum hydroxide, and the halogen-based flame retardant is ethylene bistetrabromophthalimide, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, pentabromodiphenylethane, octabromodiphenylethane or It is a solution to the problem to provide a flame retardant photocurable resin composition characterized in that it is selected from decabromodiphenyl ethane.

In addition, the halogen flame retardant is ethylene bistetrabromophthalimide, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, pentabromodiphenylethane, octabromodiphenylethane or decabromophenyl The solution to the problem is to provide a flame retardant photocurable resin composition which is selected from ethane.

In addition, the fumed silica powder has a specific surface area of 25 m 2 / g, and provides a flame-retardant photocurable resin composition characterized in that the ultrafine powder having an average particle size of 20 ~ 30nm to solve the problem.

Another object of the present invention is to provide a photocurable sheet material comprising a flame-retardant photocurable resin composition comprising a light-blocking release film layer, an flame-retardant photocurable resin composition layer on the upper surface, and a light-blocking release film layer on the lower surface. It is to solve the problem.

The flame retardant photocurable resin composition according to the present invention has excellent mechanical and chemical properties such as adhesive strength and durability of a cured photocurable resin by adding a mixed photoinitiator and a mixed flame retardant to a resin based on epoxy acrylate, and is rapidly cured. In addition to being able to produce flame retardant photocurable resin compositions that can be used as reinforcement or repairing materials, insulating materials, and insulating materials while maintaining flame retardancy, they can be fabricated in any size or shape for ease of construction with flexibility and sufficient pot life and working time before curing. It is applied to various surface conditions or complex shapes of various substrates such as metal, plastic, rubber, glass, ceramics, stone, wood, etc. by various cutting with scissors, knives, etc. It is excellent in various buildings, machinery, automobiles, ships, household There is a distinctive effect that can be used as structural members, piping, reinforcement or repair materials, insulation, insulation, such as lining material, such as.

18 to 40 parts by weight of the epoxy acrylate resin; 23 to 53 parts by weight of two or more flame retardants selected from halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, and inorganic flame retardants; 0.001 to 1 part by weight of a phosphine-based photoinitiator; 0.001 to 1 part by weight of an alpha hydroxy ketone (α-Hydroxyketone) photoinitiator; 20 to 50 parts by weight of glass fiber; 0.001 to 3 parts by weight of fumed silica; 0.001-0.5 parts by weight of silane coupling agent; 0.001 to 1 part by weight of a viscosity reducing agent; 0.001-1 weight part of antifoamers; A flame retardant photocurable resin composition comprising 0.001 to 0.5 parts by weight of a reactive diluent is characterized by a technical configuration.

In addition, the epoxy acrylate resin has a flame retardant photocurable resin composition having a number average molecular weight of 500 ~ 10,000 g / mol as a feature of the technical configuration.

In addition, the epoxy acrylate resin is a flame retardant photocurable resin composition which is a mixed epoxy acrylate resin mixed with 15 to 30 parts by weight of bisphenol A type epoxy acrylate and 3 to 10 parts by weight of a novolak type epoxy acrylate as a technical feature. do.

The flame retardant is a flame retardant photocurable resin composition which is a mixed flame retardant in which 20 to 45 parts by weight of an inorganic flame retardant and 3 to 8 parts by weight of a halogen flame retardant are mixed.

In addition, the inorganic flame retardant is a metal-based inorganic oxide is antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimony carbonate, metal antimony, antimony trichloride, antimony pentachloride, barium borate, zirconium oxide, zinc borate, zinc stannate, magnesium hydroxide, Selected from aluminum hydroxide, and the halogen-based flame retardant is ethylene bistetrabromophthalimide, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, pentabromodiphenylethane, octabromodiphenylethane or A flame retardant photocurable resin composition selected from decabromodiphenyl ethane is characterized by a technical configuration.

In addition, the halogen flame retardant is ethylene bistetrabromophthalimide, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, pentabromodiphenylethane, octabromodiphenylethane or decabromophenyl A flame retardant photocurable resin composition selected from ethane is characterized by a technical configuration.

In addition, the fumed silica powder has a specific surface area of 25 m 2 / g, and the flame retardant photocurable resin composition having an ultrafine powder having an average particle size of 20 to 30 nm is characterized by a technical configuration.

In addition, the present invention is a photocurable sheet material comprising a flame-retardant photocurable resin composition comprising a light-blocking release film layer on the upper surface, the flame-retardant photocurable resin composition layer and a light-blocking release film layer on the lower surface of the technical configuration. It is done.

Hereinafter will be described in detail to be easily carried out by those skilled in the art. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

First of all, epoxy resins are generally used in various fields such as surface coating, electrical insulation, laminated structures, construction, adhesives, etc. because they have excellent heat resistance, chemical resistance, solvent resistance, adhesion, and abrasion resistance, and excellent electrical and mechanical properties. Representatively, bisvenol-A epoxy is known and free rotation is difficult because of the benzene nucleus (Bisphenol A). This improves chemical resistance and adhesive toughness high temperature characteristics. It also has Ether group in the molecule, so it has excellent chemical resistance and plasticity. Hydrophilic hydroxyl group and hydrophobic hydrocarbon group are arranged regularly, and excellent adhesiveness. However, yellowing occurs, the curing time is long, PE, PP, silicone, acrylic without the crystalline polymer or polarity has a disadvantage of poor adhesion and the use of the main curing agent is impossible to use for photocuring.

Epoxy acrylate photo-curable resins having photosensitivity by introducing acrylic groups having double bonds in such epoxy resins are used in many business fields due to the energy saving and environmentally friendly characteristics required in the modern society. It is difficult to apply to structure and expensive, but unlike general thermosetting reaction, it cures rapidly at low temperature, saves energy, has excellent curing properties, and is a liquid form using reactive acrylic monomer instead of solvent as diluent. There is an advantage that does not cause environmental problems due to pollution, and because of this advantage, UV-curable coatings or adhesives are used in a large number of top coating or adhesive applications such as wood, plastic, flooring, metal, etc. Applications and numbers of precision materials It has been growing rapidly.

As such, the epoxy acrylate resin is excellent in curability, has a relatively small effect on oxygen, and is excellent in strength, hardness, flexibility, corrosion resistance, etc., and thus is more effective than conventional photocurable resins used in the art. Specifically, for example, epoxy acrylate obtained by reaction of bisphenol F type, A type, and AF type epoxy resin, novolak type epoxy resin, alicyclic epoxy resin, and acrylic acid may be used. For controlling the workability and physical properties of defoaming, etc., the number average molecular weight is preferably in the range of 500 to 10,000 g / mol, preferably in the range of 500 to 3,000 g / mol. If the number average molecular weight is less than 500 g / mol, the resin composition solidifies at low temperature and exceeds 10,000 g / mol, so that the viscosity of the composition becomes high, which makes it difficult to handle the composition.

Bisphenol A epoxy acrylate, which is generally used, has the advantages of excellent chemical resistance, heat resistance, corrosion resistance and hardness, fast curing speed, and relatively low price, but it is easy to yellow, easy to break, and high in viscosity. Since there is a limit in terms of physical properties to use alone for photocuring, the present invention uses a mixture of novolak-type epoxy acrylate, novolak-type epoxy acrylate has a high corrosion resistance, ultra-heat resistance, high heat deformation temperature, mechanical Mixed epoxy acrylate is used because it has excellent properties and does not break.

Bisphenol A epoxy acrylate is a resin having a polymerizable double bond produced by a ring-opening reaction by a compound having an aromatic epoxy group and a carboxyl group such as acrylic acid, and specifically, an epoxy resin and acrylic acid or methacrylic acid can be obtained as a component. Aromatic epoxy compounds containing α, β-unsaturated carboxylic acid ester groups are reacted with polyesters of terminal carboxyl groups obtained from epoxy (meth) acrylates or from saturated dicarboxylic acids and / or unsaturated dicarboxylic acids and polyhydric alcohols. You can get it.

The unsaturated carboxylic acid reacted with the epoxy resin is acrylic acid or methacrylic acid, and other unsaturated dicarboxylic acids such as fumaric acid, maleic anhydride, maleic acid and itaconic acid may be used in combination in small amounts, or may be used alone or in combination of two or more thereof. The unsaturated monobasic acid used as one of the reactants of the photopolymerization epoxy acrylate may be preferably methyl (meth) acrylic acid in view of the polymerization rate.

The reaction ratio of the aromatic epoxy resin and (meth) acrylic acid is usually in the range of 0.9 to 1.1: 1.1 to 0.9 in molar ratio, and the reaction is usually performed at 110 to 130 ° C., and a styrene monomer or a diluent is used. Acryl monomer is used, and tertiary amines such as triethylamine, dimethylaniline, tris (dimethylaminomethyl) phenol, trimethylbenzyl ammonium chloride, triethylbenzyl ammonium chloride and pyridinium as polycondensation reaction accelerators and esterification catalysts. Quaternary ammonium salts such as chromide or inorganic salts such as lithium hydroxide and lithium chloride are used.

Moreover, a polymerization inhibitor is used as needed, As a polymerization inhibitor, hydroquinones, such as hydroquinone and methyl hydroquinone, benzoquinones, such as benzoquinone and methyl-p- benzoquinone, and catechins, such as t-butyl catechol And phenols such as cols, 2,6-di-t-butyl-4-methylphenol, and 4-methoxyphenol, phenothiazine, and the like.

The bisphenol A epoxy acrylate is prepared by reacting 30 to 60 parts by weight of bisphenol A type epoxy resin with 10 to 30 parts by weight of bisphenol A and 0.1 to 3 parts by weight of a polycondensation reaction accelerator at 150 ° C. under a nitrogen atmosphere for 2 hours. Cool down to 110 degreeC, methyl methacrylate 15-35 weight part, maleic acid 0.1-5 weight part, esterification catalyst 0.1-3 weight part, polymerization inhibitor 0.01-0.1 weight part, thickener 0.1-5 weight part, diluent Was prepared by diluting 35 parts by weight per 100 parts by weight of the total composition, blowing air and reacting at 110 to 130 ° C. for 3 to 4 hours.

In addition, the novolak-type epoxy acrylate is reacted by adding acrylic acid or methacrylic acid to the novolak-type epoxy resin, but the equivalent ratio of (meth) acrylic acid / novolak-type epoxy resin is 1? A novolac-type epoxy acrylate having an acid value of 20 or less can be prepared by mixing and reacting the catalyst with acrylic acid or methacrylic acid.

More specifically, epoxy equivalent 100? 500 novolac type epoxy resin 30? 60 parts by weight, 80? After raising temperature to 120 degreeC, and adding a polymerization inhibitor, the equivalence ratio of (meth) acrylic acid / epoxy resin is 1? The mixed solution which mixed acrylic acid or methacrylic acid, and the reaction catalyst so that it may become 1.5 is mixed and reacted with the said novolak-type epoxy resin, and after completion | finish of reaction it is 90? The novolak type epoxy acrylate with an acid value of 20 or less is manufactured by isothermal reaction by raising temperature at 150 degreeC.

Here, as the polymerization inhibitor, hydroquinone, toluhydroquinone, hydroquinone methyl ether, p-benzoquinone, dimethyl-p-benzoquinone, p-tertiarybutylcatechol, and the like may be used, and the reaction catalyst is triethyl Amines, ethyltrimethyl ammonium bromide, dimethylbenzylamine, di-n-butylamine, dimethylphenylbenzyl ammonium chloride, chromium acetylacetate, triphenylstivin, tetramethyl amnonium chloride, triphenylphosphine and the like can be used.

The content of the epoxy acrylate used in the present invention is preferably 18 to 40 parts by weight of the total photocurable resin composition, less than 18 parts by weight of the chemical resistance of the cured product (especially resistant to high concentration acetic acid) It is not preferable to lower the content to more than 40 parts by weight because the viscosity of the resin composition is increased, so that uniform impregnation of reinforcing fibers such as glass fibers is difficult and workability as a sheet reinforcing material is lowered.

In addition, it is preferable to mix 15-30 parts by weight of bisphenol A-type epoxy acrylate and 3-10 parts by weight of novolak-type epoxy acrylate in the epoxy acrylate resin. Chemical resistance, heat resistance, corrosion resistance and hardness is lowered, and if it exceeds 30 parts by weight, there is a disadvantage that yellowing and cracking or viscosity increases, in the case of the novolak type, mechanical properties are lowered if less than 3 parts by weight, if more than 10 parts by weight There is a problem that the viscosity rises.

The flame retardant used in the flame retardant photocurable resin composition of the present invention uses two or more mixed flame retardants selected from halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, and inorganic flame retardants.

In general, halogen-based flame retardant impedes the flame retardancy of the resin by preventing the decomposition in the condensed phase during combustion to increase the carbonization rate, in particular, it is known to be very effective for resins with high oxygen content. These halogen-based flame retardants generate HX by thermal decomposition and capture OH and H, which are active radicals, which play a role of combustion propulsion in the combustion process, and are highly used in flame retardants of many resins. In the present invention, the halogen-based flame retardant has an ability to effectively remove radicals, and the bromine-based compound having excellent heat resistance and light resistance but having low oxygen blocking effect is selected and used.

Representative halogen flame retardants include ethylene bistetrabromophthalimide, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, pentabromodiphenylethane, octabromodiphenylethane or decabromodiphenylethane Compounds with a high bromine content are preferred.

In addition, the inorganic flame retardant is a metal inorganic oxide selected from antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimony carbonate, metal antimony, antimony trichloride, antimony pentachloride, barium metaborate, zirconium oxide, zinc borate, zinc stannate, and hydroxide Metal-based inorganic hydroxides selected from magnesium and aluminum hydroxide can be used.

Antimony trioxide (Sb ₂ O ₃ ) in the inorganic flame retardant is used alone to exhibit flame retardancy is limited to the case of polyvinyl chloride (PVC) in which the halogen is contained in the molecular structure, generally used in combination with halogen flame retardant Flame retardant synergy.

In other words, when only halogen-based flame retardant is applied alone, halogen-based compounds may be decomposed and consumed at one time under certain conditions according to the binding energy. Create an environment that exists. In addition, the high specific gravity of the produced SbX ₃ is able to stay in the combustion region for a long time without volatilization, and thus the halogen radicals dissociate continuously at a high temperature to generate hydrogen halide (HX), indicating a synergistic effect of flame retardancy.

In addition, Al (OH) 3 or Mg (OH) 2 in the inorganic flame retardant has the effect of suppressing the flame by generating water at high temperature without generating toxic gas. Especially, aluminum hydroxide is dehydrated during combustion. The pyrolysis rate is lowered by the cooling effect, the incombustible layer is formed after dehydration, and the flame retardancy is known to be caused by the extinguishing power through the dilution of the flammable gas due to the generation of H 2 O at the decomposition temperature. However, these flame retardants are filled with a large amount of flammable resins to achieve flame retardancy, and since the amount of smoke is very low during combustion, it is a good flame retardant technique in terms of environment.However, the flame retardant must be added at least 50% by weight in order to have an effect. It is a disadvantage that the physical properties are lowered.

Phosphorus-based flame retardants are attracting the most attention as non-halogen flame-retardant systems that respond to environmental problems. Phosphorus-containing compounds that are applied include red, phosphazene, and phosphate-based compounds.The red phosphorus is a surface-treated one due to the possibility of generating phosphine (PH ₃ ), which is known as a toxic substance during processing. It is limited to interior parts using nylon and PBT resin. Common phosphorus flame retardants are phosphates. The chemical structure is stable and has an effect of imparting plasticity, which facilitates the processing of the flame retardant resin, and the usability and weather resistance are good, but the heat resistance is deteriorated.

Representative phosphorus flame retardants include phosphorus ester or phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene, and the like.

Nitrogen-based flame retardant is a structure containing nitrogen alone or nitrogen and phosphorus, melamine, melamine cyanurate, triphenylisocyanurate, melamine phosphate, melamine pyrophosphate ( Typical examples include melamine pyrophosphate, ammonium polyphosphate, alkyl amine phosphate, piperazine acid polyphosphate, and ammonium phosphinate.

Among these flame retardants, magnesium oxide, phosphorus flame retardant, and reactive phosphorus flame retardant 3- (hydroxyphenyl phosphinyl) propanoic acid are very limited in use because they affect the hardenability when Cobalt and MEKPO, which are general vinyl ester and unsaturated ester curing systems, are used. In particular, in the case of the phosphorus-based flame retardant, there is a problem in the flame retardancy when used less, and when used a lot, there is a problem that does not use the phosphorus + nitrogen-based, phosphorus + halogen-based flame retardant when used in combination to reduce the curability.

In addition, phosphorus-based flame retardants have the advantage of generating non-toxic, non-corrosive volatiles during the combustion process, compared to the halogen element, the production of polyphosphoric acid and subsequent formation of char to prevent the combustion of the polymer It is the main mechanism. On the other hand, the introduction of a flame retardant as an additive has the advantage of simplicity of the process, but has the disadvantage that the accompanying mechanical degradation. In particular, halogen-based flame retardant is a problem of toxic and corrosiveness of the smoke generated during combustion.

As described above, the flame retardant has different thermal properties according to its type and properties and its effect on flame retardancy. That is, the highly volatile flame retardant is effective in imparting flame retardancy at the beginning of combustion, and the effect may be reduced in terms of flame retardancy if combustion continues. Therefore, when a highly volatile flame retardant and a low volatile flame retardant are mixed, an effective flame retardant resin composition can be formed, and a flame retardant having a different structure can be mixed and flame retardancy can be improved.

In particular, when halogen-based flame retardant is used alone as a flame retardant of the photocurable resin composition, it is not easy to obtain sufficient flame retardancy. However, when a mixture of different flame retardants is used, an expandable char layer is formed due to synergy between two flame retardants. Flame retardancy increases as the active radicals, which are propellants of combustion, are extinguished while the divergence is suppressed, and the viscosity of the composition does not increase, thereby obtaining a flame retardant photocurable resin composition having excellent appearance characteristics, thickness, and physical properties.

Therefore, in the present invention, when using two or more types of mixed flame retardants selected from halogen-based flame retardants, phosphorus flame retardants, nitrogen-based flame retardants, inorganic flame retardants, there is a synergistic effect of the flame retardant, in particular, in the flame retardant photocurable resin composition of the present invention The present invention has been accomplished by finding that a photocurable resin composition having excellent flame retardancy and physical properties can be obtained by using a flame retardant and a halogen flame retardant in combination, or by mixing an inorganic flame retardant with a halogen flame retardant.

In the present invention, when mixing the mixed flame retardant and photocurable resin composition, 23 to 53 parts by weight of the mixed flame retardant relative to the total photocurable resin composition, preferably 20 to 45 parts by weight of inorganic flame retardant and 3 to 8 weight of halogen flame retardant Mix wealth.

If the content of the inorganic flame retardant is less than 20 parts by weight, the effect as a flame retardant is not sufficiently exhibited. If the content of the inorganic flame retardant exceeds 45 parts by weight, the appearance of poor viscosity and mechanical properties are greatly reduced due to the increase in viscosity. If the content of less than 3 parts by weight can not solve the problem of flame retardancy, when the content of more than 8 parts by weight is not preferable because the degradation of the photocuring performance and viscosity increases, the physical properties and mechanical properties of the cured product is lowered.

Optionally, the epoxy acrylate resin used in the present invention can be used that includes a reactive phosphorus flame retardant, the epoxy acrylate resin containing a reactive phosphorus flame retardant is a flame retardant resin with a phosphorus content of 3% or more, The phosphoric acid derivative, which is a reactive flame retardant, may be prepared by axial polymerization reaction to a resin. Phosphoric acid derivatives, which are the reactive flame retardants, have a phosphorus content of 9 to 15%, have 1 to 2 functional groups, and each have a hydroxy (OH) or an acid (Acid) group. Phosphoric acid derivatives have a powder or liquid form, and the powder has a melting point in the range of 120 to 250 ° C. In the case where the melting point is more than 200 ° C the reaction is not easy and the possibility of gelation (gel) during the resin production is not suitable for application. In particular, in the present invention, it is preferable to use 3-Hydroxy phenyl phosphinyl propanoic acid.

Epoxy acrylate resin used in the present invention may contain 0.001 to 20 parts by weight of a reactive phosphorus flame retardant, if less than 0.001 parts by weight is insufficient to exhibit flame retardant properties, if more than 20 parts by weight further improve the flame retardant properties. It is not expected to be very effective, and various difficulties are involved in controlling viscosity, molecular weight, price, and acid value.

On the other hand, the photoinitiator used in the flame retardant photocurable resin composition of the present invention has no yellowing phenomenon, and it is particularly advantageous to use a photoinitiator in which an acid or base is liberated at high temperature and high humidity so that no black spots or corrosion occurs. That is, in the case of using an alpha-hydroxyketone photoinitiator, which is a photoinitiator generally used for UV curing, yellowing occurs, an acylphosphine-based photoinitiator is used in combination with a long-wavelength region for excellent photosensitivity.

Since the phosphine-based photoinitiator is excellent in light transmittance, and generates acyl radicals and phosphinoyl radicals by light irradiation, photopolymerization efficiency is higher than that of conventional photoinitiators, and is advantageous for internal curing. Problems such as the limitation of the amount can be solved.

Therefore, it is preferable to use the alpha-hydroxyketone photoinitiator which is an ultraviolet photoinitiator, and the acylphosphine photoinitiator which is a visible light initiator favorable for internal hardening for the flame-retardant photocuring resin composition of this invention.

Examples of commonly used ultraviolet photoinitiators include benzoin ether isopropylbenzoin ether, isobutyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, benzyl ketal hydrocyclohexyl phenyl ketone, benzyl dimethyl ketal, Benzyl of ketone benzophenone type, methyl-O- benzoin benzoate, 2-chloro thioxanthone, methyl thioxanthone, benzophenone / tertiary amine of benzophenone type, 2, 2- diethoxy acetphenone, (alpha) -Hydroxyisobutylphenone, acylophosphine oxide, bisacylphosphine oxide, camphorquinone, etc. are mentioned as a representative example.

Moreover, although an acyl phosphine oxide compound is effective as a visible photoinitiator, Bis (2, 6- dichloro benzoyl)-phenyl phosphine oxide and bis (2, 6- dichloro benzoyl)-2, 5- dimethyl are mentioned as an example. Phenylphosphine oxide, bis (2,6-dichlorbenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorbenzoyl) -4-propylphenylphosphine oxide, bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like.

The combined amount of photoinitiator is used in 0.002 ~ 2 parts by weight of the composition according to the curing conditions. If it is less than 0.002 parts by weight, no complete curing occurs, and if it exceeds 2 parts by weight, surface black spots or corrosion may occur in high temperature and high humidity reliability. In addition, the acylphosphine-based photoinitiator is useful for internal curing, but if it exceeds 50% by weight of the total photoinitiator may cause a lot of black spots or corrosion.

The reinforcing fibers used in the present invention are not particularly limited, but may be used by mixing reinforcing fibers or impregnating the composition with reinforcing fibers, for example inorganic fibers such as glass fibers, carbon fibers, metal fibers, ceramic fibers, and the like; Organic fibers composed of aramid, polyester, vinylon, phenol, teflon and the like; Natural fibers and the like. In addition, the form of these fibers is not particularly limited, and may include, for example, mat shapes such as cross (woven) shapes, chopped strand mats, preformable mats, continuous strand mats, surfacing mats, and the like; Chopped strand shape; Roving shape; Nonwoven fabric shape etc. are mentioned. These may be used independently or may use 2 or more types together. Among these, glass fiber is preferable.

The glass fiber is particularly preferably used by mixing E-glass fiber or E-glass fiber mat of 17-25 micro diameters with C-glass fiber or C-glass fiber mat of 17-25 micro diameters. Because E-glass fiber or E-glass fiber mat is advantageous in physical properties such as electrical properties, durability, strength, and C-glass fiber or C-glass fiber mat is resistant to chemical properties such as acid erosion, It is important for physical properties.

The amount of the glass fiber or glass fiber mat is preferably used in an amount of 20 to 50 parts by weight in the total resin composition, since even if less than 20 parts by weight, the basic performance of the cured product may be lowered.

Fumed silica has the function of a reinforcing filler, and fumed silica having a particle diameter of 20 to 30 nm is used in the range of 0.001 to 3 parts by weight in the resin composition. Problems inferior in flame retardancy and reinforcing effect is generated, and when used in excess of 3 parts by weight there is a problem inferior sheet material workability. The fumed silica powder has a specific surface area of 25 m 2 / g, an ultrafine powder having an average particle size of 20 to 30 nm, and has a particle size in the above range, so that the fumed silica powder is easily dispersed in a flame retardant resin composition, and has surface activity due to the specific surface area. This is excellent.

In the present invention, the silane coupling agent is for improving the adhesion of the photocurable resin composition, and a silane compound (functional silane coupling agent) having a reactive substituent such as carboxyl group, methacryloyl group, isocyanate group, epoxy group, etc. may be used. Can be. Specific examples of such functional silane coupling agents include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like, and the amount of used is 0.001 to 0.5 parts by weight in the photocurable resin composition, and 0.5 weight In the case of using over part, the adhesiveness may be lowered rather.

In the present invention, the antifoaming agent may include, for example, compounds such as silicone, fluorine, and acrylic, and the amount of the antifoaming agent is used in an amount of 0.001 to 1 part by weight, and a viscosity reducing agent is used in an amount of 0.001 to 1 part by weight. Other additives may also be used, but thixotropy-imparting agents, leveling agents, plasticizers, antioxidants, and the like may be added to the extent that the hardness of the cured product is not impaired as necessary. A thixotropic imparting agent can add well-known thixotropic imparting agents, such as a silica, mica, and a calcium carbonate, For example, As another additive, For example, calcium carbonate, talc, mud, glass powder, silica, Inorganic additives such as aluminum hydroxide, barium sulfate, titanium oxide and the like may also be used. The amount of use may be adjusted according to impregnation, foaming, fluidity or adhesion during molding.

Reactive diluents typically have a lower molecular weight than the resin component, and have a low viscosity monomer or a plurality of functional groups that include one functional group that reduces the viscosity of the resin and can polymerize when exposed to actinic radiation. , The amount used is 0.001 to 0.5 parts by weight. As the typical reactive diluent, an alkylene monomer may be used, and the alkylene monomer may be a styrene compound, an ester compound, a compound having an allyl group, or the like. The styrene compound may be styrene, divinylbenzene, methyl styrene, etc., and the ester compound may be 2-hydroxy ethyl (meth) acrylate, trimetholpropane tri (meth) acrylate, 1,6-hexane. (Meth) acrylic acid, such as diol di (meth) acrylate, can be used.

The light wavelength used for curing the sheet material using the flame-retardant photocurable resin composition of the present invention is in the range of 380 to 1200 nm. The ultraviolet region shorter than 380 nm is extremely undesired because the light transmittance is extremely degraded and the safety is a problem, and the region having a wavelength longer than 1200 nm is degraded. Examples of the light source of the light wavelength include halogen lamps, xenon lamps, mercury lamps, metal halide lamps, sunlight, and the like, and among them, metal halide lamps or halogen lamps for visible light are preferable, which are alpha- of the present invention. It is preferable because it radiates an effective wavelength for the decomposition of a hydroxyketone photoinitiator and an acylphosphine photoinitiator, and at the same time, increases the temperature of the irradiated object by the action of heat rays to promote a curing reaction.

In addition, the manufacture of the flame-retardant photo-curable sheet material of the present invention is prepared by mixing the reinforcing fibers such as glass fibers in the composition, or impregnating the composition in the reinforcing fiber mat, and then laminating the release material on both sides, the release material is processed or It has the effect of shading (shielding properties) so that workability is not impaired by hardening the composition during construction, and also has the flexibility to sufficiently process or construct the sheet material, and prevents photocuring of the sheet material by the release material. The time can be taken sufficiently, and the sheet member can be quickly cured by removing the release material after construction.

Although it does not specifically limit as a form of the said release material, For example, the film etc. which vapor-deposited, coated, or disperse | distributed the light shielding material to paper or a resin material are mentioned, These may be laminated | stacked. For example, a film in which a light-shielding material is deposited on such a paper or a resin material may be a film in which a deposition film made of metal such as aluminum is formed on one or both sides thereof. It may be a light shielding film coated on one or both sides, or manufactured by dispersing the light shielding material.

Although it does not specifically limit as said paper, For example, what was formed from natural fiber, a synthetic fiber, an inorganic fiber, etc. is mentioned, What was surface-treated by silicone processing, etc., What press-processed, embossed, etc. may be performed, The said film The strength is not particularly limited as long as the strength and flexibility to not impair the workability and durability to the monomers or diluents contained in the composition.

Although it does not specifically limit as said film resin material, For example, Polyolefin, such as polyethylene, a polypropylene, polybutene, a polystyrene, ethylene-alpha-olefin copolymer; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and the like; Fluororesins such as tetrafluoroethylene, polyvinylidene fluoride, polymonochlorotrifluoroethylene and the like; Polybutadiene, polycarbonate, polyacetal, polyamide, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyurethane, polyimide, polyether ether ketone, polymethylpentene, ionomer resin, polyvinyl butyral, Polyvinyl alcohol, cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, etc. These may be used alone or in combination of two or more thereof.

Although it does not specifically limit as thickness of the said film, For example, it is preferable that it is 5-2000 micrometers. When it is less than 5 micrometers, there exists a possibility that a mold release material may not have sufficient strength to withstand peeling, and when it exceeds 2000 micrometers, since the workability of a sheet material may be impaired, preferable thickness is 10-500 micrometers.

The flame-retardant photocurable sheet material of the present invention has sufficient plasticity and flexibility to be processed or constructed well before curing, and has sufficient strength and durability after curing, such as sufficient bending strength and bending elastic modulus, and according to the type of resin, additive or filler, It is preferable that it is a photocurable SMC sheet or a prepreg sheet which has sufficient basic performances, such as water resistance, abrasion resistance, and high electrical characteristics, and the thickness of the sheet material depends on the substrate to be coated or repaired, but is usually 0.1 to 10 mm. Do. When it is less than 0.1 mm, there exists a possibility that hardened | cured material may not have sufficient intensity | strength, and when it exceeds 10 mm, workability and workability will fall, and there exists a possibility that photocurability may fall especially. Of course, it can be used by laminating on the sheet material in order to secure an additional thickness.

Synthesis Example 1 (Synthesis of Bisphenol A Epoxyacrylate)

35 parts by weight of bisphenol A-type epoxy resin, 20 parts by weight of bisphenol A, and 1 part by weight of triethylamine as a promoter for the polycondensation reaction in a reactor equipped with a stirrer, a reflux condenser, a nitrogen gas introduction tube, and a thermometer at 150 ° C under a nitrogen atmosphere. After reacting for 2 hours, the mixture was cooled to 110 ° C, 35 parts by weight of methyl methacrylate, 3 parts by weight of maleic acid, and 1 part by weight of Ancamin K-54 [tris (dimethylaminomethyl) phenol] as an esterification catalyst and a polymerization inhibitor. 0.1 parts by weight of hydroquinone as a component, 0.1 parts by weight of 4,4-methylenediphenyl diisocyanate as a thickener, and 10 parts by weight of styrene monomer as a diluent per 100 parts by weight of the total composition. It was made to react for 4 hours, reaction was complete | finished when the acid value became 5 or less, and 25 weight part of styrene monomers were added, and the bisphenol A epoxy acrylate was synthesize | combined.

Synthesis Example 2 (Synthesis of Novolac Epoxyacrylate)

30 parts by weight of a noblock resin (Dow Chemical USA, DEN438) was added to a reactor equipped with a stirrer, a thermometer, a dropping device, a charge cooler, and heated to check flow. After the temperature was raised while stirring at a temperature of 120 ° C., 0.05 parts by weight of hydroquinone monomethyl ether and 0.05 parts by weight of toluhydroquinone were added, and 20 parts by weight of acrylic acid and 0.5 parts by weight of dimethylbenzylamine were added within 5 minutes after closing the lid of the reactor. After the reaction, 90? The reaction temperature was raised to 150 ° C. to continue the reaction to synthesize a novolac epoxy acrylate having an acid value of 20 or less.

Example 1

30 parts by weight of bisphenol A epoxy acrylate obtained in Synthesis Example 1, 10 parts by weight of novolac type epoxy acrylate obtained in Synthesis Example 2, 0.3 parts by weight of silane coupling agent KBM-503 (3-Methacryloxypropyltrimethoxysilane) and 0.5 parts by weight of a reactive diluent 8 parts by weight of decabromodiphenyl ether and 45 parts by weight of antimony trioxide were mixed in a resin composition at room temperature using an MX-201 mixer. After sufficiently stabilizing, the alpha hydroxy ketone photoinitiator Ir-184? Product) 0.5 parts by weight and phosphine oxide-based photoinitiator TPO? (From Lambert, Italy) 0.5 parts by weight, fumed silica powder 3 parts by weight, viscosity reducing agent BYK-103 (Phosphoric acid esters) 0.5 parts by weight, antifoaming agent BYK-A515 (Solution of foam-destroying polymers, silicone free) 1 part by weight was mixed to prepare a flame retardant photocurable resin composition.

Next, the composition was impregnated with a glass fiber layer laminated with 25 parts by weight of a 25 micro-diameter E-glass fiber mat and 25 parts by weight of a 25 micro-diameter C-glass fiber mat in a flame retardant photocurable resin composition, and having a thickness of 10 mm and 1 m x. After producing a 1 m flame retardant photocured sheet, the sheet surface was irradiated with a 2 kW metal halide lamp at a distance of 1 m for 5 minutes, and the results are shown in Table 1.

Comparative Example 1

Except that 8 parts by weight of antimony trioxide (using only antimony trioxide) was used instead of 8 parts by weight of decabromodiphenyl ether in the flame retardant used in Example 1, and the results are shown in Table 1. .

Comparative Example 2

The same procedure as in Example 1 was repeated except that 45 parts by weight of decabromodiphenyl ether was used instead of 45 parts by weight of antimony trioxide in the flame retardant used in Example 1, and the results are shown in Table 1 below. Shown in

[Property evaluation]

① Flame retardant

Flame retardancy was measured by the UL94-V standard.

② Curability measurement

Hardness was measured by the Barcol hardness tester (model: GYXJ934-1), and the case where hardness was 50 or more was evaluated as favorable curability.

③ Surface drying time

Even if it pushed about 2-3 cm <2> of cotton wool at 20 degreeC room temperature to a sheet surface as a touch test, the time until cotton wool did not remain on a sheet surface by adhesion was measured.

④ tensile strength, tensile modulus

Tensile strength and tensile modulus were measured in accordance with JIS-K-7113 as the sheet hardened body properties.

⑤ bending strength, bending elastic modulus

As the sheet hardened body properties, the bending strength and the bending elastic modulus were measured in accordance with JIS-K-7203, respectively.

<Table of Property Measurement Results> division Example 1 Comparative Example 1 Comparative Example 2 Flammability V-O V-1 V-1 Curable Good Good Good Surface drying time (minutes) 10 12 12 Tensile Strength (Mpa) 95 85 75 Tensile Modulus (Mpa) 8,500 6,500 6,500 Flexural Strength (Mpa) 190 175 170 Flexural Modulus (Mpa) 7,000 5,500 6,000

As shown in Table 1, the flame-retardant photo-curing sheet material of the present invention exhibits excellent properties in hardenability, tensile strength, bending strength, etc. than the case of using an inorganic flame retardant or a halogen-based flame retardant alone, especially in the case of flame retardancy As mentioned above, due to the synergistic effect of flame retardancy, the flame retardancy was excellent.

Claims (12)

18 to 40 parts by weight of epoxy acrylate resin; 23 to 53 parts by weight of two or more flame retardants selected from halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, and inorganic flame retardants; 0.001 to 1 part by weight of a phosphine-based photoinitiator; 0.001 to 1 part by weight of an alpha hydroxy ketone (α-Hydroxyketone) photoinitiator; 20 to 50 parts by weight of glass fiber; 0.001 to 3 parts by weight of fumed silica; 0.001-0.5 parts by weight of silane coupling agent; 0.001 to 1 part by weight of a viscosity reducing agent; 0.001-1 weight part of antifoamers; Flame retardant photocurable resin composition comprising 0.001-0.5 parts by weight of reactive diluent
The method of claim 1
The epoxy acrylate resin has a number average molecular weight of 500 ~ 10,000 g / mol, flame-retardant photocurable resin composition
The method of claim 1,
The epoxy acrylate resin is a mixed epoxy acrylate resin mixed with 15 to 30 parts by weight of bisphenol A type epoxy acrylate and 3 to 10 parts by weight of a novolak type epoxy acrylate.
The method of claim 1,
The halogen flame retardant is selected from among ethylene bistetrabromophthalimide, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, pentabromodiphenylethane, octabromodiphenylethane or decabromodiphenylethane. Is chosen,
The phosphorus flame retardant is selected from phosphorus ester or phosphate, phosphonate, phosphinate, phosphine oxide, phosphazene,
The nitrogen-based flame retardant is melamine (melamine), melamine cyanurate (melamine cyanurate), triphenyl isocyanurate, melamine phosphate (melamine phosphate), melamine pyrophosphate (melamine pyrophosphate), ammonium polyphosphate (ammonium polyphosphate), Alkyl amine phosphate, piperazine acid polyphosphate, ammonium phosphinate,
The inorganic flame retardant is a metal-based inorganic oxide is antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate carbonate, antimony metal trioxide, antimony trichloride, antimony pentachloride, barium borate, zirconium oxide, zinc borate, zinc stannate, magnesium hydroxide, aluminum hydroxide Flame-retardant photocurable resin composition, characterized in that selected from
The method of claim 4, wherein
The flame retardant is a flame retardant photocurable resin composition characterized in that the mixed flame retardant 20 to 45 parts by weight of inorganic flame retardant and 3 to 8 parts by weight of halogen flame retardant
The method of claim 1,
The alpha hydroxy ketone (α-Hydroxyketone) photoinitiator is isopropyl benzoin ether of benzoin ether, isobutyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, benzyl ketal hydroxycyclohexyl phenyl ketone , Benzyl dimethyl ketal, ketone benzophenone series benzyl, methyl-O-benzoinbenzoate, 2-chlorothioxanthone, methyl thioxanthone, benzophenone series tertiary amine, 2,2-die Flame-retardant photocurable resin composition characterized in that at least one selected from oxyacetphenone, α-hydroxyisobutylphenone, acyl phosphine oxide, bisacylphosphine oxide, camphorquinone is used.
The method of claim 1,
The phosphine-based photoinitiator is bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorbenzoyl) -4-propylphenylphosphineoxide, bis (2,6-dimethoxybenzoyl) -2,4, Flame-retardant photocurable resin composition characterized in that at least one selected from 4-trimethylpentylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide is used.
The method of claim 1,
The fumed silica powder has a specific surface area of 25 m 2 / g, and is an ultrafine powder having an average particle size of 20 to 30 nm.
The method of claim 1
The glass fiber is a flame retardant photocurable resin composition, characterized in that 17-25 micro diameter E-glass fiber or E-glass fiber mat and 17-25 micro diameter C-glass fiber or C-glass fiber mat mixed
The flame-retardant light film according to any one of claims 1 to 9, comprising a light-blocking release film layer on the upper surface, a flame-retardant photocurable resin composition layer and a light-blocking release film layer on the lower surface, wherein the flame-retardant photocurable resin composition layer. A flame retardant photocurable sheet material comprising a cured resin composition
The method of claim 10,
The light-blocking release film is a film prepared by coating a light shielding material on one surface or both surfaces, or by dispersing the light shielding material, and having a film thickness of 10 to 500 µm.
The method of claim 10,
The flame retardant photocurable sheet member is a photocurable SMC sheet or prepreg sheet having a thickness of 0.1 to 10 mm.