MX2008015949A - Radical polymerizable resin composition. - Google Patents

Abstract

It is intended to provide a radical polymerizable resin composition that gives a cured article having excellent impact resistance, corrosion resistance and transparency. The radical polymerizable resin composition is characterized by comprising (A) a vinyl ester resin having a weight average molecular weight of 500 to 6000, and (B) a urethane (meth)acrylate resin obtained by reacting an isocyanate compound having at least two isocyanate groups in one molecule, a (meth)acrylate compound having at least one hydroxyl group in one molecule and polyethylene glycol.

Description

TECHNICAL FIELD OF RESIN COMPOSITIONS The present invention relates to a composition of radically polymerizable resin. More specifically, the present invention relates to a radically polymerizable resin composition that can be used in FRP molded products and FRP coatings such as pressure vessels that require corrosion resistance, transparency and impact resistance.

BACKGROUND TECHNIQUE In general, radical polymerizable resins typified by unsaturated polyester resins, vinyl ester resins, urethane methacrylate resins, polyester methacrylate resins, methacrylate resins, etc., are materials that provide cured products that have excellent mechanical resistance, water resistance, etc. With respect to such radically polymerizable resins, a period of curing time can be adjusted without being influenced by atmospheric temperature by adjusting a curing agent or a promoter. Therefore, its cure does not take a long period of time and poor healing does not occur when the resins are treated especially at low temperatures, different from epoxy resins. Then, radical polymerizable resins have been widely used in common in coating materials, adhesives, fiber reinforced plastic materials (FRP), etc.

Among the radical polymerizable resins, the vinyl ester resins provide cured products that have excellent resistance to Acids, alkali resistance and cold cure properties and therefore are widely used for various applications, for example, FRP molded products such as corrosion resistant tanks and corrosion resistant FRP liners. In addition, the cured products obtained from vinyl ester resins are transparent. Therefore, when the cured products are used as containers such as tanks, there is a merit in that the remaining amount of liquid or the like in the container can be easily confirmed. However, these containers such as tanks manufactured using vinyl ester resins do not have sufficient hardness (impact resistance) that makes them capable of withstanding pressures such as external and internal pressures and impacts from the outside, resulting in the so-called problems of the appearance of fracture due to pressure or impact. On the contrary, in order to increase the resistance to impact of the cured products, several studies have been carried out. For example, a resin composition containing an epoxy vinyl ester resin, a vinyl ester urethane resin and a coreactive monomer such as a styrene is known (eg, Patent Document 1). In this resin composition, the impact strength is improved with a second phase of the vinyl ester urethane resin which is formed in a dispersed manner (i.e., separated by microphases) in the epoxy vinyl ester resin at the time of healing.

However, this resin composition has a problem, since a clear cured product can not be obtained due to the turbidity resulting from microphase separation, which occurs during the time of curing. In addition, methacrylic resins (eg, Patent Document 2) obtained by copolymerization of methyl methacrylate are also known. and a specific compound and resin compositions (eg, Patent Document 3) containing an acid-modified epoxy acrylate that is obtained by the addition of polybasic acid anhydride to a part or all of a hydroxy group present in epoxy acrylate , a thermoplastic polymer, a compound having two or more double bonds in a molecule and a reactive monomer having a single double bond in a molecule. Although such resins and resin compositions can provide transparent cured products with excellent impact resistance, there are problems since the cured products have insufficient corrosion resistance and can not be used for containers such as tanks that require resistance to corrosion. As described above, conventional resins or resin compositions can not successfully provide cured products excellent in all properties of impact resistance, corrosion resistance and transparency. Patent Document 1: JP 2001 -500177 T Patent Document 2: JP 2003-128729 A Patent Document 3: JP 2002-138121 A INVENTION PROBLEMS TO BE RESOLVED BY THE INVENTION The present invention has been carried out in order to solve the aforementioned problems and has the object of providing a radical polymerizable resin that provides an excellent cured product in all the properties of resistance to impact, resistance to corrosion and transparency.

MEANS FOR RESOLVING THE PROBLEMS The present invention provides a radical polymerizable resin composition, characterized in that it comprises: (A) a vinyl ester resin having a weight average molecular weight of 500 to 6,000 and (B) a methacrylate resin of urethane obtained by the reaction of an isocyanate compound having two or more isocyanate groups in a molecule, a methacrylic compound having one or more hydroxy groups in a molecule and polyethylene glycol. EFFECTS OF THE INVENTION The present invention can provide a radical polymerizable resin composition that provides an excellent cured product in all properties of impact resistance, corrosion resistance and transparency. BEST MODE FOR CARRYING OUT THE INVENTION The radical polymerizable resin composition of the present invention comprises a vinyl ester resin (A) having a given weight average molecular weight and a given urethane-methacrylic resin (B).

The vinyl ester resin (A) used in the present invention is generally a resin obtained by dissolving, in a radical polymerizable unsaturated monomer, a compound (vinyl ester) having an unsaturated polymerizable bond and obtained by an opening reaction of the ring of a compound containing a glycidyl group (epoxy group) and a carboxyl compound having a polymerizable unsaturated bond, such as acrylic acid. Such a vinyl ester resin (A) is described for example in "Polyester resin handbook" (Nikkan Kogyo Shimbun, Ltd., published in 1988) or "Toryo Yogo Jiten" (edited by Sikizai Kyokai, published in 1993). Such a vinyl ester resin (A) has a weight average molecular weight of from 500 to 6,000 and preferably from 1,000 to 5,000. When the weight average molecular weight of the vinyl ester resin (A) is less than 500, strength can not be obtained to withstand the use in practice. On the contrary, when the weight average molecular weight exceeds 6,000, the desired storage stability and malleability may not be obtained. The vinyl ester used as a raw material of the vinyl ester resin (A) is not particularly limited and is produced by known methods. Specifically, the vinyl ester is an epoxy methacrylate obtained by reaction of unsaturated monobasic acid, for example, acrylic acid or methacrylic acid, with an epoxy resin. Examples of the epoxy resin include aliphatic glycidyl ethers such as bisphenol A, diglycidyl ether and high molecular weight homologs thereof, polyglycidyl novolac ether and high molecular weight homologs thereof and 6-hexanediol diglycidyl ether . Among these, the epoxy resin of bisphenol A, the polyglycidyl-novolac ether and bromides thereof are preferred from the point of view of hardness. In addition, from the viewpoint of providing flexibility, saturated dibasic acids such as adipic acid, sebacic acid and dimer acid can be reacted with the epoxy resin. The unsaturated radical polymerizable monomer used as a material for the vinyl ester resin (A) is not particularly limited and conventionally known monomers can be used. Examples of the radical-polymerizable unsaturated monomer include: monomers based on styrene such as styrene monomer, a-, o-, m- and p-alkylene, nitro, cyano, amide, styrene ester derivatives, chlorostyrene, vinyltoluene and divinylbenzene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; methacrylates such as ethyl methacrylate, methyl methacrylate, n-propyl methacrylate, i-propyl methacrylate hexyl methacrylate 2-ethylhexyl methacrylate, lauryl methacrylate, dodecyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, tetrahydrofuryl methacrylate , acetoacetoxyethyl methacrylate, dicyclopentyloxyethyl methacrylate and methacrylate and phenoxyethyl; methacrylic acid amides such as methacrylic acid amide and N, N-dimethyl-amide-methacrylic acid; vinyl compounds such as methacrylic acid anilide; diesters of unsaturated dicarboxylic acid such as diethyl citraconic acid; monomaleimide compounds such as N-phenyl-maleimide; and N-methacryloyl-phthalimide. In addition, methacrylate compounds may also be used which each have two or more methacryloyl groups in a molecule such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and 1,6-hexanediol dimethacrylate. These radical-polymerizable unsaturated monomers can be used alone or in combination. In addition, among these, styrene is preferred from the points of view of malleability, cost and healing properties. The content of the radical-polymerizable unsaturated monomer in the vinyl ester resin (A) is preferably 20 to 60% by weight and more preferably 30 to 50% by weight. When the content of the radically polymerizable unsaturated monomer is less than 20% by weight, the workability can be decreased by an increase in the viscosity in the resin. On the contrary, when the content of the unsaturated monomer polymerizable by The radicals exceed 60% by weight, the desired hardness of a cured product may not be obtained. The urethane methacrylate resin (B) used in the present invention is a resin obtained by dissolving a given urethane methacrylate in the unsaturated radical polymerizable monomer. The urethane methacrylate used as a raw material of the urethane methacrylate resin (B) is obtained by reaction of an isocyanate compound having two or more isocyanate groups in one molecule, a methacrylic compound having one or more hydroxy groups in one molecule and polyethylene glycol. There is no limitation on the isocyanate compound having two or more isocyanate groups in a molecule and conventionally known isocyanate compounds can be used. Examples of such isocyanate compounds include diphenylmethane diisocyanate, 2,4-tolylene diisocyanate and isomers thereof, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and triphenylmethane triisocyanate. These isocyanate compounds can be used alone or in combination. Among these isocyanate compounds, diphenylmethane diisocyanate is preferred which is excellent in reactivity and less harmful to the human body. The mixed amount of the isocyanate compound is preferably from 5 to 90 parts by weight and more preferably from 10 to 50 parts by weight, based on 100 parts by weight of the total amount of the urethane methacrylate raw materials. When the mixed amount of the isocyanate compound is less than 5 parts by weight, the desired strength may not be obtained. In contrast, when the mixed amount of the isocyanate compound exceeds 90 parts in weight, the desired flexibility may not be obtained. The methacrylic compound having one or more hydroxy groups in a molecule is not particularly limited and conventionally known compounds can be used. Examples of the methacrylic compound include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, tris (hydroxyethyl) isocyanurate dimethacrylate and pentaerythritol trimethacrylate. These methacrylic compounds can be used alone or in combination. In addition, among these methacrylic compounds, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate are preferred from the cost and safety point of view. The mixed amount of the methacrylic compound is preferably from 5 to 90 parts by weight and more preferably from 10 to 50 parts by weight, based on 100 parts by weight of the total amount of urethane methacrylate raw materials. When the mixed amount of the methacrylic compound is less than 5 parts by weight, the desired strength may not be obtained. On the contrary, when the mixed amount of the isocyanate compound exceeds 90 parts by weight, the desired flexibility may not be obtained. There is no limitation on polyethylene glycol and polyethylene glycols having a weight average molecular weight of 200 to 2,000 and more preferably 400 to 1,500 are preferred. When the weight average molecular weight is less than 200, desired viscosity and physical properties in a resin composition may not be obtained. Conversely, when the weight average molecular weight exceeds 2,000, the molecular weight of a urethane methacrylate resin exceeds 7,000, resulting in that it can not be obtain the desired compatibility with a vinyl ester resin. The mixed amount of polyethylene glycol is preferably 0.1 to 90 parts by weight and more preferably 5 to 50 parts by weight, based on 100 parts by weight of the total amount of urethane methacrylate raw materials. When the mixed amount of polyethylene glycol is less than 0.1 part by weight, the desired compatibility may not be obtained. On the contrary, when the mixed amount of polyethylene glycol exceeds 90 parts by weight, the desired properties of water resistance may not be obtained. In the production of a urethane methacrylate, it is possible to add, as an optional component, polyether polyol and / or adipate-polyester polyol. There is no limitation on the polyether polyol and polyether polyols having a weight average molecular weight of 500 to 1,500 are preferable and those having 800 to 1,200 are more preferable. When the weight average molecular weight is less than 500, the desired physical and viscosity properties in a resin composition may not be obtained. On the other hand, when the weight average molecular weight exceeds 1.500, the molecular weight of a urethane methacrylate resin exceeds 7,000, resulting in that the desired compatibility with a vinyl ester resin can not be obtained. When the polyether polyol is added, the mixed amount of polyether polyol is preferably from 5 to 90 parts by weight and more preferably from 20 to 60 parts by weight, based on 100 parts by weight of the total amount of raw materials of urethane methacrylate. When the mixed amount of polyether polyol is less than 5 parts by weight, the desired flexibility may not be obtained. On the contrary, when the mixed amount of polyether polyol exceeds 90 parts by weight, the desired compatibility may not be obtained. There is no limitation on the adipate-polyester polyol and adipate-polyester polyols having a weight average molecular weight of 600 to 3,000 are preferred and those having 800 to 2,500 are more preferable. When the weight average molecular weight is less than 600, the desired physical and viscosity properties in a resin composition may not be obtained. In contrast, when the weight average molecular weight exceeds 3,000, the molecular weight of a urethane methacrylate resin exceeds 7,000, resulting in that the desired compatibility with a vinyl ester resin can not be obtained. When the adipate-polyester polyol is added, the mixed amount of adipate-polyester polyol is preferably from 0.1 to 90 parts by weight and more preferably from 5 to 50 parts by weight, based on 100 parts by weight of the total amount of raw materials of urethane methacrylate. When the mixed amount of adipate-polyester polyol is less than 0.1 part by weight, the desired compatibility may not be obtained. On the other hand, when the mixed amount of adipate-polyester polyol exceeds 90 parts by weight, the desired water resistance properties may not be obtained. The method of producing urethane methacrylate is not particularly limited and urethane methacrylate can be produced by known methods using the aforementioned ingredients. For example, urethane methacrylate can be produced by mixing an isocyanate compound having two or more isocyanate groups in one molecule and polyethylene glycol to react, in order to generate a terminal prepolymer containing isocyanate and subsequently adding the methacrylic compound having one. or several hydroxy groups in a molecule to the prepolymer to react. It should be noted that, in the aforementioned reaction, it is also possible to add catalysts such as dibutyltin dilaurate tertiary amines and phosphones. When the catalyst is added, the mixed amount of the catalyst is preferably from 0.0001 to one part by weight and more preferably from 0.001 to 0.5 part by weight based on 100 parts by weight of the total amount of urethane methacrylate raw materials. When the mixed amount of the catalyst is less than 0.0001 part by weight, the reaction may not proceed sufficiently. On the contrary, when the mixed amount of the catalyst exceeds 1 part by weight, it may be difficult to control the reaction. In the reaction, the reaction temperature is preferably 40 to 120 ° C. The reaction time is preferably 1 to 24 hours. When the reaction temperature is lower than 40 ° C or the reaction time is less than 1 hour, the reaction does not proceed sufficiently and the desired urethane methacrylate may not be obtained. On the other hand, when the reaction temperature exceeds 120 ° C or the reaction time exceeds 24 hours, undesirable problems can occur in terms of cost or control of the reaction. There is no limitation on the radically polymerizable unsaturated monomer used as a raw material of the urethane methacrylate resin (B) and conventionally known radical polymerizable unsaturated monomers can be used. Examples of the radical-polymerizable unsaturated monomers are the same as those in the vinyl ester resin (A) mentioned above. The content of the radical-polymerizable unsaturated monomer in the urethane methacrylate resin (B) is preferably from 20 to 60% by weight and more preferably from 30 to 50% by weight. When the content of the radically polymerizable unsaturated monomer is less than 20% by weight, the workability can be decreased by increasing the viscosity of the resin. On the contrary, when the content of the radically polymerizable unsaturated monomer exceeds 60% by weight, the desired hardness of a cured product may not be obtained. The urethane methacrylate resin (B) obtained in this way has a weight average molecular weight preferably from 2,000 to 8,000 and more preferably from 3,000 to 6,500. In the case of the urethane methacrylate methacrylate resin (B) having a weight average molecular weight in the aforementioned range, the resin becomes excellent in compatibility with the vinyl ester resin (A). Therefore, when a resin composition is produced using the resin, the urethane methacrylate resin (B) is not separated by microbases in the vinyl ester resin (A) at the time of cure. Therefore, such a resin composition provides a clear cured product. The radical polymerizable resin composition of the present invention can be produced by mixing the vinyl ester resin (A) and the urethane methacrylate resin (B). In its production, the mixing method is not particularly limited and conventionally known methods can be used. The weight ratio of the vinyl ester resin (A) to the urethane methacrylate resin (B) is preferably from 20:80 to 80:20 and more preferably from 25:65 to 65:25. When the weight ratio of the vinyl ester resin (A) to the urethane methacrylate resin (B) is excessively low, the strength to withstand practical use may not be obtained. For him In contrast, when the weight ratio of the vinyl ester resin (A) to the urethane methacrylate resin (B) is excessively high, the desired hardness may not be obtained. In addition, to the radical polymerizable resin composition of the present invention, an organic cobalt salt can be added from the viewpoint of promoting the cure and distribution of drying properties. The organic cobalt salt is not particularly limited and conventionally known organic cobalt salts can be used. Examples of organic cobalt salts include cobalt octylate, cobalt naphthenate and cobalt hydroxide. The organic cobalt salts can be used individually or in combination. Among these, cobalt octylate is preferable from the point of view of curing properties. When organic cobalt salt is added, the mixed amount thereof is preferably from 0.02 to 10 parts by weight, more preferably from 0.1 to 5.0 parts by weight and more preferably from 0.1 to 3.0 parts by weight, based on 100 parts. by weight of the total amount of the vinyl ester resin (A) and the urethane methacrylate resin (B). When the mixed amount of the cobalt organic salt is less than 0.02 part by weight, the desired cure time period and the desired cured state may not be obtained, possibly resulting in poor drying at low temperatures. Conversely, when the mixed amount of the cobalt organic salt exceeds 10 parts by weight, the desired shelf life and storage stability may not be obtained. In addition, to the radical polymerizable resin composition of the present invention, an organic peroxide can be added as an initiator of radical polymerization. There is no limitation on the organic peroxide and conventionally known organic peroxides can be used. Examples of organic peroxide include ketone peroxide, perbenzoate, hydroperoxide, diacylperoxide, peroxyketal, diallyl peroxide, peroxy ester and peroxy bicarbonate. Azo compounds and the like can also be used. More specifically, methylethyl ketone peroxide, eumenal hydroperoxide, t-butyl perbenzoate, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 1, can be used. 1-bis (t-butylperoxy) -3,3,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide , dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxy dicarbonate, diisopropylperoxy dicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, azobisisobutyronitrile, azobiscarbonamide, or the like. These organic peroxides can be used alone or in combination. In addition, among these, ketone peroxide, t-butyl perbenzoate, benzoyl peroxide, and eumeno hydroperoxide are preferred from the point of view of cost, easy availability and stability. When the organic peroxide is added, the mixed amount is preferably from 0.1 to 7 parts by weight and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total amount of the vinyl ester resin (A) and the urethane methacrylate resin (B). When the mixed amount of the organic peroxide is less than 0.1 part by weight, the desired curing properties may not be obtained. On the other hand, when the mixed amount of the organic peroxide exceeds 7 parts by weight, it is economically disadvantageous and the physical properties may not be achieved. desired in the cured product. In addition, an aromatic tertiary amine may be added to the radical polymerizable resin composition of the present invention. There is no limitation on the aromatic tertiary amine and conventionally known aromatic tertiary amines can be used. Examples of the aromatic tertiary amines include N, N-dimethylaniline,?,? - diethylaniline, N, N-dimethyl-p-toluidine, N-methyl-Np-hydroxyethylaniline, N-butyl-N- -hydroxyethylaniline, N-methyl-N- -hydroxyethyl-p-toluidine , N-butyl-Np-hydroxyethyl-p-toluidine, N-methyl-N- -hydroxypropylaniline, N-methyl-N- -hydroxypropyl-p-toluidine, N, N-di (-hydroxyethyl) aniline, N, N- di (P-hydroxypropyl) aniline, N, N-di (-hydroxyethyl) -p-toluidine, N, N-di (p-hydroxypropyl) -p-toluidine and N, N-diisopropyrrole-p-toluidine. These aromatic tertiary amines can be used alone or in combination. Among these,?,? - dimethylaniline, N, N-dimethyl-p-toluidine, N, N-di (p-hydroxyethyl) -p-toluidine, N, N-di (-hydroxypropyl) -p-toluidine and N , N-diisopropyrrole-p-toluidine are preferred from the point of view of healing properties. When an aromatic tertiary amine is added, the mixed amount is preferably from 0.02 to 10 parts by weight and more preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the vinyl ester resin ( A) and the urethane methacrylate resin (B). When the mixed amount of the aromatic tertiary amine is less than 0.02 part by weight, the desired curing properties at low temperatures may not be obtained. On the other hand, when a mixed amount of the aromatic tertiary amine exceeds 10 parts by weight, it is economically disadvantageous and the desired storage stability may not be achieved. In addition, to the radical polymerizable resin composition of the present invention, in the range where the properties of the radical polymerizable resin is not damaged, a silane coupling agent and a wetting agent can be added to improve the adhesiveness with glass fiber; an ingredient of mold release agent such as zinc stearate can be added to improve the release properties of the mold; and a paraffin wax and an organic manganese salt can be added to further improve the drying properties and properties of a cured product. EXAMPLES Hereinafter, the present invention will be described in more detail with reference to the Examples, but is not limited thereto.

Preparation of vinyl ester resin (A) Synthesis example I In a reactor equipped with a stirrer, a reflux condenser, a gas introduction tube and a thermometer, 1.890 grams of Epikote 828 (epoxy resin manufactured by Yuka-Shell Epoxy Co., Ltd., epoxy equivalent = 189), 570 g of bisphenol A and 12.3 g of triethylamine. The mixture was reacted at 150 ° C for 2 hours under a nitrogen atmosphere. After completion of the reaction, the resulting product was cooled to 90 ° C. Subsequently, to the reagent, 430 grams of methacrylic acid, 9 grams of tetradecyl-dimethyl-benzyl ammonium chloride, 0.9 grams of hydroquinone and 1, 000 grams of styrene were added. The mixture was then reacted at 90 ° C for 20 hours while blowing air. Then, the reaction was terminated when the acid number reached 10 mg KOH / gram to thereby obtain the vinyl ester. Subsequently, to the vinyl ester, 1.890 grams of styrene were added to obtain a resin of vinyl ester and bisphenol A (VE - 1), with a viscosity of 25 ° C to 0.5 Pa.s and a solids content of 50% by weight. The weight average molecular weight of VE-1 was 4,300. Here, the weight average molecular weight was measured using a 21 Shodex GPC system. It should be noted that the measurement of the weight average molecular weight in the Synthesis Examples and the Comparative Synthesis Examples described below was carried out using the same apparatus. Example of Comparative Synthesis II In a reactor equipped with a stirrer, a reflux condenser, a gas introduction tube and a thermometer, 1.890 grams of Epikote 828 (epoxy resin manufactured by Yuka-Shell Epoxy Co., Ltd) were placed. ., epoxy equivalent = 189), 798 grams of bisphenol A and 12.3 grams of triethylamine. The mixture was reacted at 150 ° C for 2 hours under a nitrogen atmosphere. After completion of the reaction, the resulting product was cooled to 90 ° C. Subsequently, to the reagent, 258 grams of methacrylic acid, 9 grams of tetradecyl-dimethyl-benzyl ammonium chloride, 0.9 grams of hydroquinone and 1, 000 grams of styrene were added. The mixture was further reacted at 90 ° C for 20 hours while blowing air. Subsequently, the reaction was terminated when the acid number reached 10 mg KOH / gram to obtain vinyl ester. Subsequently, to the vinyl ester, 1.890 grams of styrene were added to obtain a resin of vinyl ester and bisphenol A (VE-2) having a viscosity at 25 ° C of 1.0 Pa.s and a solids content. 50% by weight. The weight average molecular weight of VE-2 was 6,800. Preparation of urethane methacrylate resin (B) Synthesis Example 1 In a 3-liter, four-necked flask equipped with a stirrer, a reflux condensing tube, a gas introduction tube and a Thermometer, 500 grams of diphenylmethane isocyanate, 700 grams of Actcol P-22 (polyether polyol manufactured by MITSUI TAKEDA CHEMICAL, INC .: weight average molecular weight = 1, 000), 180 grams of polyethylene glycol TOHO # 600 ( polyethylene glycol manufactured by TOHO Chemical Industry Co., Ltd .: weight average molecular weight = 600) and 0.2 grams of dibutyltin dilaurate. The mixture was reacted while stirring at 60 ° C for 4 hours. Later, the reagent was stirred while 260 grams of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. After completion of the dropwise addition, the resulting product was reacted with stirring for 5 hours to obtain urethane methacrylate. Then, to the urethane methacrylate, 1.093 grams of styrene monomer was added to obtain a urethane methacrylate resin (U-). The weight average molecular weight of the urethane methacrylate resin (U-1) was 5.315. Synthesis Example 2 In a three-liter, four-necked flask equipped with a stirrer, a reflux condenser tube, a gas introduction tube and a thermometer, 500 grams of diphenylmethane isocyanate, 500 grams of Actcol P were placed. -22 (polyether polyol manufactured by MITSUI TAKEDA CHEMICAL, INC .: average molecular weight by weight = 1, 000), 60 grams of polyethylene glycol TOHO # 600 (polyethylene glycol manufactured by TOHO Chemical Industry Co., Ltd .: average molecular weight in weight = 600), 400 grams of Kuraray P-1010 polyol (adipate-polyester polyol manufactured by Kuraray Co., Ltd .: weight-average molecular weight = 1, 000) and 0.15 grams of dibutyltin dilaurate. The mixture was reacted while stirring at 60 ° C for 4 hours. Subsequently, the reagent was stirred while adding drip for 2 hours 260 grams of 2-hydroxyethyl methacrylate. After completion of the dropwise addition, the resulting product was reacted with stirring for 5 hours to obtain urethane methacrylate. Then, to the urethane methacrylate, 1. 150 grams of styrene monomer was added to obtain a urethane methacrylate resin (U-2). The weight average molecular weight of the urethane methacrylate resin (U-2) was 5.821. Synthesis Example 3 500 grams of diphenylmethane diisocyanate, 800 grams of Actcol P were placed in a 3-liter four-necked flask equipped with a stirrer, a reflux condenser tube, a gas introduction tube and a thermometer. -22 (polyether polyol manufactured by MITSUI TAKEDA CHEMICAL, INC .: weight average molecular weight = 1, 000), 90 grams of polyethylene glycol TOHO # 600 (polyethylene glycol manufactured by TOHO Chemical Industry Co., Ltd.: average molecular weight in weight = 600), 100 grams of Kuraray P-2010 polyol (adipate-polyester polyol manufactured by Kuraray Co., Ltd .: weight average molecular weight = 2,000) and 0.15 grams of dibutyl tin dilaurate. The mixture was reacted while stirring at 60 ° C for 4 hours. Subsequently, the reagent was stirred while 260 grams of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. After completion of the dropwise addition, the resulting product was reacted with stirring for 5 hours to obtain urethane methacrylate. Subsequently, to the urethane methacrylate, 1.160 grams of styrene monomer was added to obtain a urethane methacrylate resin (U-3). The weight average molecular weight of the urethane methacrylate resin (U-3) was 6.890. Synthesis Example 4 In a 3-liter four-necked flask equipped with a stirrer, a reflux condenser tube, a tube for. introduction of gas and a Thermometer, 500 grams of diphenylmethane isocyanate, 600 grams of polyethylene glycol TOHO # 600 (polyethylene glycol manufactured by TOHO Chemical Industry Co., Ltd .: weight average molecular weight = 600) and 0.1 gram of dibutyltin dilaurate were placed. The mixture was reacted while stirring at 60 ° C for 4 hours. Subsequently, the reagent was stirred while 260 grams of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. After completion of the dropwise addition, the resulting product was reacted with stirring for 5 hours to obtain urethane methacrylate. Next, to the urethane methacrylate, 900 grams of styrene monomer were added to obtain a urethane methacrylate resin (U-4). The weight average molecular weight of the urethane methacrylate resin (U-4) was 3.902. Comparative Synthesis Example 1 In Comparative Synthesis Example 1, a urethane methacrylate resin was prepared without using polyethylene glycol. 500 grams of diphenylmethane isocyanate, 1,000 grams of Actcol P-22 were placed in a three-liter four-necked flask equipped with a stirrer, a reflux condenser tube, a gas introduction tube and a thermometer. (polyether polyol manufactured by MITSUI TAKEDA CHEMICAL, INC .: weight average molecular weight = 1, 000) and 0. 5 grams of dibutyltin dilaurate. The mixture was reacted while stirring at 60 ° C for 4 hours. Subsequently, the reagent was stirred while 260 grams of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. After the completion of the dropwise addition, the resulting product was reacted by stirring for 5 hours to obtain urethane methacrylate. Next, at urethane methacrylate, 1.170 grams of styrene monomer were added to obtain a urethane methacrylate resin (U-5). The weight average molecular weight of the urethane methacrylate resin (U-5) was 5.918. Example of Comparative Synthesis 2 In Comparative Synthesis Example 2, a urethane methacrylate resin was prepared using propylene glycol instead of polyethylene glycol. 500 grams of diphenylmethane diisocyanate, 76 grams of propylene glycol and 0.5 grams of dilaurate were placed in a 3-liter four-necked flask equipped with a stirrer, a reflux condenser tube, a gas introduction tube and a thermometer. of dibutyl tin. The mixture was reacted while stirring at 60 ° C for 4 hours. Subsequently, the reagent was stirred while 260 grams of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. After completion of the dropwise addition, the resulting product was reacted with stirring for 5 hours to obtain urethane methacrylate. Then, to the urethane methacrylate, 560 grams of styrene monomer were added to obtain a urethane methacrylate resin (U-6). The weight average molecular weight of the urethane methacrylate resin (U-6) was 1, 403. Example of Comparative Synthesis 3 In Comparative Synthesis Example 3, a urethane methacrylate resin was prepared in the same manner as in Comparative Synthesis Example 1 without using polyethylene glycol. In a 3 liter four-necked flask equipped with a stirrer, a reflux condensing tube, a gas introduction tube and a thermometer, 500 grams of diphenylmethane diisocyanate, 700 grams of Actcol were placed.

P-22 (polyether polyol manufactured by MITSUI TAKEDA CHEMICAL, INC .: weight average molecular weight = 1, 000), 300 grams of Kuraray C-1090 polyol (polyester carbonate polyol manufactured by Kuraray Co., Ltd .: weight average molecular weight = 1, 000) and 0.2 grams of dibutyltin dilaurate. The mixture was reacted while stirring at 60 ° C for 4 hours. Subsequently, the reagent was stirred while 260 grams of 2-hydroxyethyl methacrylate were added dropwise over 2 hours. After the completion of the dropwise addition, the resulting product was reacted by stirring for 5 hours to obtain urethane methacrylate. Then, to the urethane methacrylate, 1.093 grams of styrene monomer was added to obtain a urethane methacrylate resin (U-7). The weight average molecular weight of the urethane methacrylate resin (U-7) was 6.473. Preparation of the radical polymerizable resin composition Examples 1 to 5 and Comparative Examples 1 to 4 Radical polymerizable resin compositions were prepared using the ingredients in the proportions shown in Table 1. It should be noted that the unit of the amount of each The ingredient shown in Table 1 is parts by weight. The radical polymerizable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated for compatibility and curing properties. In addition, the cured products obtained from the radical polymerizable resin compositions were evaluated for transparency and impact resistance. Here, the cured product was produced by emptying the radical polymerizable resin composition between glass plates placed in such a way that the thickness was adjusted to 3. mm, leaving the resulting product to stand for one day to be cured at room temperature and then subjected to post-cure at 120 ° C for 2 hours. At the time of evaluation, the cured product was cut to be used as a sample. Each evaluation was carried out following the procedures described below. Compatibility 80 grams of the resin composition prepared by each of Examples 1 to 5 and Comparative Examples 1 to 4 were placed in a 100 cc threaded bottle and the compatibility of the resin composition was evaluated by visual observation when the bottle was stored at 23 ° C and 4 ° C for 3 months. In Table 1, O shows that the resin composition was transparent without turbidity separation and X shows that the resin composition indicates separation and turbidity. Healing Properties The curing properties were measured according to JIS K 6901 standard (Liquid Unsaturated Polyester Resin Test Method) and the gel time at 25 ° C and the gel time at 80 ° C were measured. Transparency The transparency of the cured product was evaluated by visually observing the cured product. In Table 1, O shows that the cured products were clear and X shows that the cured product was unclear. Impact resistance Impact resistance was measured according to standard JIS K 691 1 (General test method of thermosetting plastic).

The results of the evaluation are shown in Table 1 Table 1 Example Example Example Example Example Example Example Example 1 2 3 4 5 Comparative Comparative Comparative Comparative 1 2 3 4 VE-1 70 70 70 70 60 70 60 57 VE-2 60 U-1 30 40 U-2 30 U-3 30 U-4 30 U-5 30 30 U-6 40 U-7 43 Methyl-peroxide-1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 ethyl-ketone ') Perbenzoate of t- 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 butito21 Cobalt octylate 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 N.N-dimethylaniline 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 4 ° C O O O O O X X X X Compatibility 23 ° C O O O O O X X O X Transparency O O O O O X X X X Impact value 36.1 34.3 43.4 33.0 30.0 18.0 21.0 19.3 21.3 Izod (KJ / mm2) Time of 25 ° C 13 11 12 15 10 13 12 9 14 qualification,. 80 ° C 3.2 3.0 3.1 3.4 2.9 3.3 3.2 2.5 3.2 (min.) 1) Kayamek M [manufactured by Kayaku Akzo Corporation] 2) Kayabutil B [manufactured by Kayaku Akzo Corporation] As shown in Table 1, even though the radical polymerizable resin compositions of Examples 1 to 5 were stored at a low temperature (4 ° C) and at room temperature (23 ° C), the radical polymerizable resin compositions were free of separation and turbidity and were of excellent compatibility. In contrast, when the radical polymerizable resin compositions of Comparative Examples 1 to 4 were stored at a low temperature (4 ° C), the radical polymerizable resin compositions showed separation or turbidity. In addition, when the radical polymerizable resin compositions of Comparative Examples 1, 2 and 4 were stored at room temperature (23 ° C), the radical polymerizable resin compositions showed separation or turbidity as well. In addition, the radical polymerizable resin compositions of Examples 1 to 5 were free of cure delay or the like and had excellent curing properties. In addition, the cured products obtained from the radical polymerizable resin compositions of Examples 1 to 5 were clear. In contrast, the cured products obtained from the radical polymerizable resin compositions of Comparative Examples 1 to 4 became unclear. In addition, the cured products obtained from the radical polymerizable resin compositions of Examples 1 to 5 had Izod impact values much greater than the cured products obtained from the radical polymerizable resin compositions of Comparative Examples 1 to Four.

As shown by the results described above, the radical polymerizable resin composition of the present invention can provide excellent cured products in all properties of impact resistance, corrosion resistance and transparency.

Claims (10)

1. CLAIMS 1. Radical polymerizable resin composition, comprising: (A) a vinyl ester resin having a weight average molecular weight of 500 to 6,000; and (B) a urethane methacrylate resin obtained by the reaction of an isocyanate compound having two or more isocyanate groups in a molecule, a methacrylic compound having one or more hydroxy groups in a molecule and polyethylene glycol.
2. 2. The radical polymerizable resin composition according to claim 1, wherein the urethane methacrylate resin (B) is obtained by reaction of an isocyanate compound having two or more isocyanate groups in a molecule, a methacrylic compound having one or various hydroxy groups in one molecule, polyethylene glycol and polyether polyol and / or adipate-polyester polyol.
3. 3. Radical polymerizable resin composition according to claim 1 or 2, wherein the isocyanate compound having two or more isocyanate groups in a molecule is diphenylmethane diisocyanate.
4. The radical polymerizable resin composition according to any of claims 1 to 3, wherein the methacrylic compound having one or more hydroxy groups in a molecule is 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, or a mixture of the same.
5. The radical polymerizable resin composition according to any of claims 1 to 4, wherein the vinyl ester resin (A) is a resin of vinyl ester and bisphenol, a resin of vinyl ester-novolac, a resin of vinyl or brominated ester, or a mixture thereof.
6. 6. Composition of radical polymerizable resin according to any of claims 1 to 5, wherein the vinyl ester resin (A) and the urethane methacrylate resin (B) contain from 20 to 60% by weight of styrene.
7. 7. Radical polymerizable resin composition according to any of claims 1 to 6, wherein the weight average molecular weight of the 5 urethane methacrylate resin (B) is from 2,000 to 8,000.
8. 8. The radical polymerizable resin composition according to any of claims 1 to 7, wherein the weight ratio of the vinyl ester resin (A) to the urethane methacrylate resin (B) is from 20:80 to 80. :twenty.
9. 9. A radical polymerizable resin composition according to any one of claims 1 to 8, further comprising an organic peroxide, an organic cobalt salt, an aromatic tertiary amine or a mixture thereof.
10. 10. The radical polymerizable resin composition according to any of claims 1 to 9, wherein the radically polymerizable resin is used in an FPR liner or an FPR molded product. twenty 5