Compositions, expoxidized compositions, a heat-curable resin composition, an epoxy resin composition, radically polymerized composition, a curable resin composition and a polymer having epoxy groups

Abstract: Compositions(I), (II) and (III) comprising compounds having vinyl groups as side chains and epoxidized compositions(XI), (XII) and (XIII) thereof, which can be prepared by the various reaction combinations of (a) with (b) or (b)+(c), and or (d), are disclosed. (a) is at least one compound having at least one vinyl group and one epoxy group in the molecule; (b) is at least one of a polybasic compound, an anhydride thereof, a polymer having carboxylic groups at terminals and a polymer having carboxylic groups as side chains; (c) is at least one organic compound having at least one active hydrogen atom; and (d) is at least one of an unsaturated monocarboxylic compound or an unsaturated monocarboxylic ester having a hydroxyl group. Heat curable compositions and epoxy resin compositions can be made which comprise the above-mentioned compositions and a radical initiator or a curing agent, a polymer composition obtained by radically (co)polymerizing the compositions(III) or the epoxidized compositions(XIII) thereof. The epoxidized compositions(XI) and (XII) can provide a coating layer or a formed article having excellent properties such as heat resistance, outdoor durability and further electric properties.

Description: FIELD OF THE INVENTION The present invention relates to novel compositions comprising a compound having vinyl groups as side chains and epoxidized compositions thereof. Furthermore, the present invention also relates to heat curable resin compositions which comprise the above-mentioned compositions and a radical initiator, an epoxy resin composition and a curing agent. Still further, the present invention relates to another compositions comprising compounds having vinyl groups as side chains, epoxidized compositions thereof, radically polymerized compositions, curable resin compositions prepared by the epoxidized compositions, and a polymer having epoxy groups. BACKGROUND OF THE INVENTION Epoxy resins which have been widely used industrially include the so-called epi-bis type epoxy resins which are produced by reacting bisphenol A with epichlorohydrin. These resins have advantages, e.g., various products can be obtained, which can vary from liquid to solid state, and they can be cured at room temperatures with polyamines because of the high reactivity of the epoxy resins. However, cured products thereof are defective in that outdoor durability is poor; electric properties such as anti-tracking property, etc., are poor; and the heat distortion temperature is low, although they do have desirable the characteristics of good water resistance and strength. Recently, epoxy resins prepared by reacting a phenolic resin or a novolak resin with epichlorohydrin have been used as resins for encapsulating VLSI(very large scale integrated circuit), a light emitting or receiving device, etc. But, chlorine contained in the resins, typically in an amount of several hundreds ppm, causes the problem of a deterioration of the electric properties of such electronic devices. Epoxy resins having excellent electric properties and heat resistance, and which do not contain chlorine are known. These include certain alicyclic epoxy resins which are produced by an epoxidation reaction of a compound having a 5-membered or 6-membered cycloalkenyl structure. The epoxy group in these resins is a so-called, inner epoxy group, and curing is usually carried out with acid anhydride by heating. However, since their reactivity is low, they cannot be cured with polyamines at room temperature, and therefore, the use of the alicyclic epoxy resins has so far been technically restricted. As alicyclic epoxy resins, those having a structure represented by formula (X-I) or (X-II) are presently used commercially. (X-I) is used as a heat resistant epoxy diluent, because of its very low viscosity. However, it has the disadvantage of possessing high toxicity and causes the problem of poisoning upon contact with the skin of the human body. (X-II) contains only a small amount of impurities and has a low color hue, and the cured products produced therewith have a high heat distortion temperature. However, many epoxy resins suffer from the problem of poor water resistance due to the presence of ester bonds. In addition, because epoxy resins (X-I) and (X-II) have low viscosity, it is impossible to apply molding systems for solid epoxy resins, such as transfer molding, etc., thereto. From the above viewpoint, novel alicyclic epoxy resins having oxycyclohexane units and ether bonds were taught in Japanese Patent Examined Publication (kokoku) Nos. 31493/1989, 10471/1992 (equivalent to US 4,565,859). However, the above epoxy resins have lower softening temperatures. In addition, not only the overcoming of the above described problems, but also the number of methods or objects involving the use of epoxy resins have grown, and so have the desired characteristics of such epoxy resins; for example, a demand for epoxy resins having excellent various properties has increased. From the above viewpoint, and as a result of intensive studies by the present inventors, it was found that softening temperatures of epoxy resins can be readily adjusted in a wide range by incorporating ester units in place of ether units into main chain of the molecule. Furthermore, unsaturated carboxylic esters having vinyl groups are useful as, for example, curing agents for an acrylic rubber. Allyl methacrylate is known as a typical unsaturated carboxylic ester having vinyl groups. However, in the case that allyl methacrylate is used as a curing agent for an acrylic rubber, there is a tendency of easy gelation to because of its high reactivity. On the other hand, glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate are known as an unsaturated carboxylic ester having epoxy groups. Recently in particular, it has been taught that 3,4-epoxycyclohexylmethyl (meth)acrylate can be used as a coating composition to be cured by a cationic curing reaction, for example, in Japanese Patent Unexamined Publication (Kokai) Nos.108048/1988, 108049/1988(equivalent to US Patent 4772672), (Kokai) Nos.123814/1989, 123817/1989(equivalent to US Patent 4923945), (Kokai) Nos.129018/1989, 129019/1989(equivalent to US Patent 4927884), etc. However, the reaction control is difficult because 3,4-epoxycyclohexylmethyl (meth)acrylate has an epoxy group directly bonded to the cyclohexane ring resulting in high reactivity with the cationic curing agent. In the above-mentioned prior arts, the problem is solved by using a macromonomer in which 3,4-epoxycyclohexylmethyl (meth)acrylate is radically polymerized with a monomer having silicone atoms, etc. On the other hand, glycidyl (meth)acrylate often shows a too low reactivity even by combination with various curing agents. Furthermore, glycidyl (meth)acrylate includes chlorine because of the use of epichlorohydrin as a starting material, whereby cured articles or coating layers therefrom have a tendency of being adversely affected. From the above viewpoint, and as a result of intensive studies by the present inventors, it was found that the problem can be solved by an unsaturated carboxylic ester or ether composition having epoxy groups. SUMMARY OF THE INVENTION An object of the present invention is to provide novel compositions comprising compounds having vinyl groups as a side chains and epoxidized compositions thereof. These novel compositions are useful as powder coating compositions, radically polymerized compositions, epoxy resin compositions, compositions for encapsulating, compositions for solder resist inks and (photo)curable compositions. The present compositions can be prepared by a reaction of (a) with (d) described below, and by an epoxidation reaction thereof; wherein (a) is a compound having at least one vinyl group and one epoxy group in the molecule; (d) is at least one of an unsaturated monocarboxylic compound or an unsaturated monocarboxylic ester having a hydroxyl group. The composition comprising compounds having vinyl groups as side chains is useful as an unsaturated monomer which is capable of copolymerizing with other monomers. Furthermore, the epoxidized composition is useful for a curable resin composition, inks, various coatings and insulating varnishes, etc. DETAILED DESCRIPTION OF THE INVENTION The present invention is described hereinafter in more detail. According to a first aspect of the present invention, there is provided a composition(III) comprising compounds having vinyl groups as side chains. The composition(III) comprising compounds having vinyl groups as side chains can be obtained by a reaction of (a) with (d); wherein (a) is a compound having at least one vinyl group and one epoxy group in the molecule (d) is at least one of an untsaturated monocarboxylic compound or an unsaturated monocarboxylic ester having a hydroxyl group. The compound(a) having at least one vinyl group and one epoxy group in the molecule, which is a common starting material in the first, second and third aspects of the present invention, can be mainly represented by general chemical formula described below; 〈 wherein, n is an integer of from 1 to 5, R 1 and R 4 are a hydrogen atom or an alkyl group or substituted phenyl group having carbon numbers of from 1 to 5, R 2 and R 3 are a hydrogen atom or an alkyl group having carbon numbers of from 1 to 50, and R 2 and R 3 may be taken together to form a ring structure 〉. Specific illustrative examples of the compound (a) include 4-vinylcyclohexene-1-oxide,5-vinylbicyclo[2.2.1]hepto-2-en-2-oxide,limonene monoxide, trivinylcyclohexane monoxide, divinylbenzene monoxide, butadiene monoxide and 2-epoxy-9-decene. Furthermore, allylglycidylether which is represented by general formula described below; in which n1 and n2 are an integer of from 0 to 30, respectively, glycidylstyryl ether which is represented by general formula as described below; in which n is an integer of from 0 to 30, are also included. Still further, the following compounds; in which n is an integer of from 0 to 30, in which n1, n2 and n3 are an integer of from 0 to 30, respectively, n1+n2+n3 is an integer of from 1 to 30, can be also used as a compound(a) having at least one vinyl group and one epoxy group in the molecule. One or more of the above-mentioned compounds(a) can be used. It is noted that there can be additionally used a monoepoxide such as ethylene oxide, propylene oxide, cyclohexeneoxide, styrene oxide, alphaolefin epoxide, etc. and or a diepoxide such as vinylcyclohexenediepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc., together with the compound(a) having at least one vinyl group and one epoxy group in the molecule. And successively, the compound(d) is described below. The compound(d) is at least one selected from the group consisting of an unsaturated monocarboxylic compound or an unsaturated monocarboxylic ester having a hydroxyl group. The specific examples of the compound(d) include acrylic acid, methacrylic acid, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate modified by epsilon-caprolactone, 4-hydroxybutyl(meth)acrylate modified by epsilon-caprolactone. It is noted that although acrylic acid, methacrylic acid, 2-hydroxyethyl(meth)acrylate are included in the above-mentioned compound(c) as a compound having at least one active hydrogen atom, these compounds have a different role in compound(d). Furthermore successively, there is described a preparation process of a composition(III) comprising compounds having vinyl groups as side chains. In the preparation process, the compound(a) is allowed to react with the compound(d) in the mixing molar ratio of (a)/(d) from 0.1 to 100, preferably from 1 to 5. Where the mixing ratio of (a)/(d) is less than 0.1, the resulting. composition inevitably includes only minor amounts of the compounds having vinyl groups as side chains. On the other hand, where the mixing ratio of (a)/(d) is more than 100, the resulting composition inevitably includes the compounds having a higher molecular weight. The preparation process includes an esterification reaction in which the compound(a) is allowed to react with an unsaturated monocarboxylic compound, and an etherification reaction in which the compound(a) is allowed to react with an unsaturated monocarboxylic ester having a hydroxyl group. In the esterification reaction, there may be preferably used catalysts described below. Catalysts include tertiary amines such as triethylamine, benzyldimethylamine, quaternary ammonium salts such as tetrabutyl ammonium chloride or tetrabutyl ammonium bromide, and the like; secondary amine salts such as acetic or formic salts of diethylamine; hydroxides of alkali metals or alkali earth metals such as KOH, NaOH, Ca(OH) 3 and the like; alkali salts or alkali earth salts such as sodium acetate, calcium acetate; cyclic compounds having nitrogens such as imidazoles or diazabicycloundecene, and the like; phosphorous compounds such as triphenylphosphine or tributylphosphine and the like. In the etherification reaction, there may be preferably used catalysts described below. Catalysts include amines such as methylamine, ethylamine, propylamine, piperazine, and the like; organic bases such as pyrizines, imidazoles, and the like; organic acids such as quaternary ammonium salts such as tetrabutyl ammonium bromide, and the like; formic acid, acetic acid, propionic acid and the like; inorganic acids such as sulfuric acid, hydrochloric acid, and the like; alcoholates of alkali metals such as sodium methylate and the like; alkalis such as KOH, NaOH, and the like; Lewis acids such as BF 3 , ZnCl 2 , AlCl 3 , SnCl 4 , and the like; or complex compounds of the Lewis acids, and organometallic compounds such as triethyl aluminum, diethyl zinc, and the like. These catalysts are used in a concentration of from 0.01 to 10 % by weight, and preferably from 0.1 to 5 %, based on the weight of the starting materials. The esterification reaction can be carried out at the temperature of from 5° to 150 °C, preferably from 80° to 120 °C. The etherification reaction can be carried out at the temperature of from -20° to 150 °C, preferably from 0° to 150 °C. The esterification and etherification reactions can be also carried out in the presence of solvent. A solvent having active hydrogen atoms cannot be used, e.g., ketones such as acetone, ethyl ethyl ketone, methyl isobutyl ketone, and the like. On the other hand, aromatic solvents such as benzene, toluene, xylene, and the like and others, aliphatic hydrocarbons, and esters can be used. Furthermore, the esterification or etherification reaction in order to prepare the composition(III) can be also preferably carried out in the presence of a polymerization inhibitor for the purpose of preventing radically thermal polymerization of (meth)acrylic groups. It is generally known that molecular state oxygen can be used as the radically thermal polymerization inhibitor for (meth)acrylic group. Furthermore, two groups of specific polymerization inhibitors can be more effectively used together with molecular state oxygen. The first group of the polymerization inhibitor includes hydroquinone, hydroquinone monomethylether, p-benzoquinone, cresol, t-butyl catechol, 2,4-dimethyl-6-t-butylphenol, 2-tert-butyl-4-methoxy phenol, 3-tert-butyl-4-methoxy phenol, 2,6-di-tert-butyl-p-cresol, 2,5-dihydroxy-p-quinone, piperidine, ethanolamine, alpha-nitroso-beta-Naphtol, diphenylamine, phenothiazine, N-nitrosophenylhydroxyl amine, N,N-diethylhydroxyl amine, etc. The second group of the polymerization inhibitor includes phosphoric acid, potassium phosphate, sodium phosphate, ammonium hydrogen phosphate, pyrophosphoric acid, potassium pyrophosphate, sodium pyrophosphate, 2-ethylhexyl pyrophosphate, potassium 2-ethylhexyl phosphate, sodium 2-ethylhexyl phosphate, tripolyphosphoric acid, potassium tripolyphosphate, and sodium tripolyphosphate. Although one or more of the first or second polymerization inhibitors can be used, more preferably, both of the first compound and second compound can be, in combination, used together with molecular oxygen, resulting in generating a synergistic effect. An example of specific molecular state oxygen is air. Air may be introduced into either liquid phase or gas phase in the reaction vessel. Furthermore nitrogen gas is generally introduced into the reaction vessel in order to prevent forming an explosive gas mixture. Although higher oxygen/nitrogen volume ratio is more effective for the purpose of preventing radical polymerization of (meth)acrylic group, it is more than 0.01 %, preferably from 3 to 5 % depending upon the kind of solvent. Furthermore, although oxygen and nitrogen may be independently introduced, it is important that equipment in the reaction vessel are arranged safely so that an explosive gas mixture is not even partially formed. The amount used of the first polymerization inhibitors ranges generally from 0.005 to 5 %, more preferably from 0.001 to 0.1 % by weight based on the unsaturated carboxylic acid or the ester thereof depending upon the kinds of starting materials and various reaction conditions. The amount used of the second polymerization inhibitors ranges generally from 0.001 to 1 %, more preferably from 0.01 to 0.2 % by weight. The polymerization inhibitors may be charged either in the form of powders or a solution with solvents. It is noted that the polymerization inhibitors can be also preferably used in the epoxidation reaction of the composition(III) described hereinafter. Furthermore, it is noted that in the case of using 2-hydroxyethylacrylate as an unsaturated carboxylic ester having a hydroxyl group which is an initiator, the composition(III) having vinyl groups as side chains can be represented by the general chemical formula as shown below; CH 2 =CHCOOCH 2 CH 2 (Y) r OH 〈 wherein, r is an integer of from 1 to 100 which depends upon the mixing ratio of 2-hydroxyethylacrylate with respect to the compound(a) having at least one vinyl group and one epoxy group in one molecule, Y is a residual group which has at least one vinyl group as a side chain derived from the compound (a) 〉. According to a further aspect of the present invention, there is provided an epoxy composition(XIII) in which there arc epoxidized vinyl groups as side chains in the above-mentioned composition prepared by the reaction of (a) with (d). The epoxy composition aspect can be prepared by the epoxidation reactions of the respective composition (III) comprising compounds having vinyl groups as side chains with an epoxidation agent. An epoxidation agent such as a peracid or various hydroperoxides can be used in the epoxidation. For example, the peracids include performic acid, peracetic acid, perpropionic acid, perbenzoic acid, trifluoroperacetic acid, etc. Of these, peracetic acid is the preferred epoxidation agent, because it is prepared on an industrial basis at an economical price and has high stability. The hydroperoxides include hydroperoxide, tertiarybutylhydroperoxide, cumeneperoxide, metachloroperbenzoic acid, etc. When carrying out the epoxidation reaction, a catalyst can optionally be used. For example, an alkali such as sodium carbonate, or an acid such as sulfuric acid, can be used as a catalyst in the case of using peracetic acid. Furthermore, it is possible to obtain a catalytic effect, for example, using a mixture of tungstic acid and sodium hydroxide together with hydrogen peroxide, or hexacarbonylmolybdenum together with tertiary butyl hydroperoxide in the case of using hydroperoxides. The epoxidation reaction is carried out in the absence or the presence of a solvent, while adjusting the reaction temperature according to the apparatus and the properties of the raw materials. The temperature range of the reaction can be selected according to the reactivity of the epoxidation agents to be used. In the case of peracetic acid which is a preferred epoxidation agent, the preferred temperature range is from 0 to 70 °C. If it is under 0 °C, the reaction velocity is slow, and if it is over 70 °C, a decomposition of peracetic acid tends to occur. Furthermore, in the case of tertiarybutylhydroperoxide/molybdenum dioxide diacetyl acetate which is an example of a hydroperoxide, it is preferably from 20 °C to 150 °C, based on the same reason. The use of solvents is effective for lowering the velocity of reaction of the raw materials and stabilizing the epoxidation agent by dilution. In the case of peracetic acid, preferred solvents include aromatic compounds, ether compounds and ester compounds. In particular, ethyl acetate or xylene are the preferred solvents. For example, in the case of peracetic acid, there can be also used an alkali such as sodium carbonate and an acid such as sulfuric acid as a catalyst. The molar ratio of the epoxidation agent to be used with respect to the unsaturated bonds is selected according to the proportion of the unsaturated bonds to be desirably retained. When preparing compositions having many epoxy groups, an equal or higher molar ratio of the epoxidation agents to the unsaturated bonds is preferably used. However, a polar ratio of more than 10 to the unsaturated bonds is disadvantageous, because of economy and of the side reactions described hereinafter, in the case of peracetic acid, a preferable molar ratio is 1 to 5. Substituted groups are produced by the side reaction between epoxy groups and acetic acid is by-produced and contained in the desired product, depending upon the epoxidation conditions together with the epoxidation of double bonds. At least one of additives as described hereinafter can be added in order to prevent such adverse affects: phosphoric acid, potassium phosphate, sodium phosphate, ammonium hydrogenphosphate, pyrophosphoric acid, potassium pyrophosphate, sodium pyrophosphate, potassium 2-ethylhexyl pyrophosphate, sodium 2-ethylhexyl tripolyphosphate, potassium 2-ethylhexyl tripolyphosphate, tripolyphosphoric acid, potassium tripolyphosphate and or sodium tripolyphosphate, sodium 2-ethylhexyl tetrapolyphosphate, potassium 2-ethylhexyl tetrapolyphosphate. The addition amount is generally from 10 ppm to 10,000 ppm, and preferably from 50 ppm to 1,000 ppm. It is noted that such additives are described hereinabove as one of polymerization inhibitors for the composition(III). It generally appears that the addition effect depends upon inactivation of metals derived from the reaction vessel or materials by chelating. Flushing with water is preferably carried out for the purpose of removing minor amounts of impure components in the reaction. The amount of water used in flushing is generally from 0.1 to 10-folds amounts, preferably from 1 to 5-folds amounts, based on the reaction crude solution volume. Furthermore, an aqueous alkali solution can be used in order to remove minor amounts of acids, and further water can be used in order to wash. An aqueous solution of an alkalis material such as NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , KHCO 3 , NaHCO 3 and NH 3 can be used. Of them, aqueous solutions of NaOH, Na 2 CO 3 , NaHCO 3 can be preferably used from the view point of solutions separability and economy. The concentration used can optionally be selected over a broad range. The aqueous alkali flushing and water flushing can be carried out in a temperature of generally from 10° to 90 °C, and preferably is from 10° to 50 °C. After water flushing and settling, the organic layer in which desired epoxidized products are included is separated from the water layer, followed by removing materials having low boiling points, to obtain the product. For example, low boiling materials such as solvents are removed by distillation. The distillation condition for removing the low boiling components is from 50° to 200 °C, and preferably from 80° to 160 °C. Furthermore, the degree of pressure reduction can be allowed to react by adjusting depending upon the boiling points of the solvents. The reactions can be carried out by various processes such as a continuous process or a batch process. In the case of the batch process, the starting materials and additives are preferably charged firstly into a reaction vessel, and then an epoxidizing agent is supplied dropwise. In the case of the continuous process, the starting materials, art epoxidation agent and additives are supplied continuously into the reaction vessel, and product is continuously taken out of the vessel. The reaction vessel includes various types such as a completely mixable type or a piston flow type, etc. The desired epoxidized products can be separated from reaction crude solutions by various engineering procedures. According to a further aspect of the present invention, there is provided a radically (co)polymerized composition which comprises in which the compositions (III) as described hereinabove is radically (co)polymerized in the presence of a polymerization initiator, and optionally at least one vinyl monomer. According to a further aspect of the present invention, there is provided a radically (co)polymerized composition which comprises in which the compositions (XIII) as described hereinabove are radically (co)polymerized in the presence of a polymerization initiator, and optionally at least one vinyl monomer. The radical (co)polymerizations can be carried out, for example, by a solution (co)polymerization in the presence of solvents or a suspension (co)polymerization in the presence of dispersion media while stirring, at a temperatures range of from 60 to 180 °C, a polymerization period of from 1 to 40 hours and under the presence of a radical (co)polymerization initiator, which are conventionally known radical (co)polymerization processes. For example, examples of the solvents include hydrocarbons such as heptane, toluene, xylene, octane; esters such as ethyl acetate, n-butyl acetate, isopropyl acetate, methylcellosolve acetate, butylcarbitol acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and diisobutylketone, and the like; alcohols such as ethanol, n-butanol, sec-butanol, isobutanol, and the like; ethers such as n-butylether, dioxane, ethylenegiycol monomethylether, ethyleneglycol monoethylether, and the like. One or more solvents can be used. Examples of the radical polymerization initiators include peroxides such as benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, and the like; azo compounds such as azobis-isobutyro nitrile, azobis-dimethyl varelonitrile, and the like, which are conventionally known radical polymerization initiators. According to a further aspect of the present invention, there is provided an epoxidized polymer composition obtained by epoxidizing a radically (co)polymerized composition as described above, with an epoxidation agent. The examples of the epoxidation agents include the epoxidation agents such as the various peracids. And, the epoxidation reaction conditions can be also carried out as previously-mentioned. According to an further aspect of the present invention, there is provided a curable resin composition which comprises a (co)polymer obtained by (co)polymerizing an epoxy composition(XIII) as described hereinabove, a cationic polymerizing initiator and optionally other epoxy resin having at least one epoxy group. Examples of the cationic polymerizing initiator include cation-generating substances, various curing agents other than carboxyl terminated polyester resins and organic acid anhydrides. Specifically, there are included organic bases, organic acids inorganic acids, alkalis, alkolates, organic metals, Lewis acids, complexes thereof, diazonium salts, sulfonium salts, iodonium salts, sulfonium acetone compounds, silanol group-generating silicone compounds, aluminum compounds, etc. Examples of other epoxy resin having at least one epoxy group which is an optional component, include various epoxy resins such as, epi-bis type epoxy resins, novolak type epoxy resins, imide type epoxy resins, urethane type epoxy resins, epoxidized polybutadienes, various alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, a lactone-adduct thereof, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-cyclohexanecarboxylate, a lactone-adduct thereof, 4-vinylcyclohexene-1-oxide, 5-vinylbicyclo[2.2.1]hepto-2-ene-2-oxide, limonene oxide, trivinylcycyclohexanemonoxide, divinylbenzenemonoxide, butadiene monoxide, 2-epoxy-9-decene, allylglycidyl ether, glycidylstyrylether, styrene oxide, etc. The use amount of the cationic polymerizing initiator is generally from 0.001 to 20 parts by weight, preferably from 0.1 to 5 % by weight based on the total amount of the compositions. Furthermore, the use amount of the other epoxy resin which is an optional component is generally from 0 to 95 % by weight, preferably from 10 to 80 % by weight based on the total amount of the compositions. The present invention is specifically illustrated by the following Examples. Example 1 [Preparation of an unsaturated carboxylic et her composition(III) comprising compounds having vinyl groups] 130 g (1.0 mol) of 2-hydroxyethylmethacrylate as a compound(d), 372 g (3.0 moles) of 4-vinylcyclohexene-1-oxide as a compound (a) were charged into a jacketed reaction vessel having a capacity of 2 liter equipped with a reflux condenser, a dropwise funnel, a stirrer and a tube for supplying nitrogen gas. Successively, 10 % ethyl acetate solution containing 3.6 g of BF 3 etherate was added dropwise over 2 hours to allow to react while maintaining the reaction vessel at 50 °C. After completion of dropwise addition, it was confirmed by a gaschromatography that 4-vinylcyclohexene-1-oxide almost disappeared. Successively, 480 g of ethyl acetate was further added into a reaction solution, followed by washing with 500 g of water twice to obtain 958 g of ethyl acetate solution containing a solid content of 46.3 %. It was confirmed by a gas-chromatography that 2.1 % of 2-hydroxyethylmethacrylate was contained in the reaction solution obtained. Successively, 50 g of ethyl acetate solution obtained was charged into a round-bottom flask to be attached to a rotary evaporator to evaporate low boiling components under reduced pressures and jacket temperature of 50 °C to obtain 23 g of an unsaturated carboxylic composition(III) having vinyl groups which is a desired viscous composition having a viscosity of 3600 cp/25 °C. The composition was designated as [A-9]. The composition[A-9] obtained was analyzed by GPC [C-R4A: manufactured by Shimadzu Seisakusyo, Ltd. It was confirmed that the composition[A-9] obtained is a mixture having a distribution composed of 2-hydroxyethylmethacrylate(n=0) not added by 4-vinylcyclohexeneoxide, a compound(n=1) added by 1 mol of 4-vinylcyclohexeneoxide, a compound(n=2) added by 2 mol of 4-vinylcyclohexeneoxide, ..........., and having MN=564 (Standardization with polystyrene standard) and MW/MN=1.35, by the GPC analysis. Furthermore, 1 H-NMR, 13 C-NMR and IR analysis were carried out. 1 H-NMR, 13 C-NMR analysis were carried out in CDCl 3 and at room temperatures, with JNM-EX90 analyzer manufactured by Nihon Denshi, Ltd. The IR analysis was carried out by coating on a NaCl plate with IR-435 analyzer manufactured by Shimadzu Seisakusyo, Ltd. The spectra are assigned as described below. 〈 1 H-NMR spectra 〉 delta 1.0-2.1(22.2 H) due to proton of CH 2 in cyclohexane ring delta 1.96(3.0 H) due to proton of CH 3 in methacrylic group delta 2.1-2.7(3.7 H) due to proton of CH to which a vinyl group bonds, in cyclohexane ring delta 2.7-2.9(1.0 H) due to proton of OH delta 3.1-4.1(9.4 H) due to proton of CH to which oxygen bonds, in cyclohexane ring due to proton of methylene group to which oxygen bonds, in CH 2 CH 2 O delta 4.2-4.4(2.0 H) due to proton of CH 2 in ester bond delta 4.8-5.2(7.4 H) due to proton of CH 2 in vinyl group delta 5.5-6.1(7.4 H) due to proton of CH in vinyl group delta 5.58(1.0 H) due to one proton of CH 2 = in methacrylic group delta 6.14(1.0 H) due to another proton of CH 2 = in methacrylic group 〈 13 C-NMR spectra 〉 delta 18.2 due to carbon of CH 3 in methacrylic group delta 24-37 due to carbon of CH and CH 2 to which oxygen does not bond, in cyclohexane ring delta 61-72 due to carbon of CH 2 CH 2 O by ester bond delta 72-84 due to carbon of CH to which oxygen bonds, in cyclohexane ring delta 112-115 due to carbon of CH 2 in vinyl group delta 125.7 due to one carbon of CH 2 = in methacrylic group delta 136.1 due to another carbon of CH 2 = in methacrylic group delta 141-145 due to carbon of CH in vinyl group delta 167.3 due to carbon in ester group 〈 IR spectra 〉 903 cm -1 absorption due to vinyl group 1718 cm -1 absorption due to ester group in methacryl ester n=approximately 3.7 was confirmed by the 1 H-NMR spectra assignments. n is an average mol number of 4-vinylcyclohexene-1-oxide added to 2-hydroxyethylmethacrylate. Example 2 [Preparation of an epoxidized composition(XIII)] 400 g ethyl acetate solution containing 46.3 % of the composition[A-9] obtained in Example 1 was charged into a jacketed reaction vessel having a capacity of 2 liter equipped with a reflux condenser, a dropwise funnel from which peracetic acid is charged, a stirrer and a tube for supplying nitrogen gas. Successively, the dropwise funnel was charged with 280 g of ethyl acetate solution containing 30 % of peracetic acid and 0.2 g of sodium 2-ethylhexyl tripolyphosphate was added to dissolve. The ethyl acetate solution of peracetic acid was added dropwise into the reaction vessel over approximately 4 hours while maintaining the reaction temperature of 50 °C, additionally followed by maintaining at 50 °C over 6 hours. Successively, 680 g of purified water was added and stirred for 30 minutes, followed by settling at 50 °C to separate into two solution layers. After maintaining for 30 minutes at 50 °C, the separated lower solution layer was gradually removed, followed by adding 300 g of ethyl acetate and 800 g of a purified water. After stirring for 30 minutes and settling for 30 minutes at 50 °C, followed by removing lower solution layer. Further, 700 g of a purified water was added and stirred for 30 minutes at 50 °C, followed by settling for 30 minutes at 50 °C to separate into two solution layers. The separated lower solution layer was gradually removed to obtain 650 g of ethyl acetate solution having solid content of 30.1 %. It was confirmed by a gas-chromatography analysis that 0.9 % of unreacted 2-hydroxyethylmetacrylate remained in the ethyl acetate solution obtained. Successively, the upper layer solution was charged into a thin-layer evaporator under the conditions of 50 °C, from 20 to 50 mm Hg and 300 cc/hour to obtain 1.80 g of an unsaturated carboxylic ester composition having epoxy groups which is a desired product. The unsaturated carboxylic ester composition having the following properties was designated as [B-12] APHA 50 oxirane oxygen 7.03 acid value(mg KOH/g) 0.9 viscosity(cc/25 °C) 9900 The unsaturated carboxylic ester composition having epoxy groups [B-12] was analyzed by NMR and IR to obtain the following spectra. The spectra are assigned as described below. 〈 1 H-NMR spectra 〉 delta 1.0-2.2 ppm (29.7 H) due to proton of CH 2 in cyclohexane ring and proton of CH to which an epoxy group bonds, in cyclohexane ring delta 1.95 ppm (3.0 H) due to proton of CH 3 in methacrylic group delta 2.2-3.0 ppm (10.5 H) due to proton of CH to which a vinyl group bonds, in cyclohexane ring delta 3.0-4.1 ppm (10.8 H) due to proton of CH to which oxygen bonds, in cyclohexane ring due to proton of methylene group to which oxygen bonds, in CH 2 CH 2 O and due to OH group delta 4.2-4.4 ppm (2.0 H) due to proton of CH 2 in ester bond delta 4.8-5.2 ppm (1.2 H) due to proton of CH 2 in vinyl group delta 5.5-6.1 ppm (0.6 H) due to proton of CH in vinyl group delta 5.58 ppm (1.0 H) due to one proton of CH 2 = in methacrylic group delta 6.12 ppm (1.0 H) due to another proton of CH 2 = in methacrylic group 〈 13 C-NMR spectra 〉 delta 18.2 ppm due to carbon of CH 3 in methacrylic group delta 22-36 ppm due to carbon of CH and CH 2 to which oxygen does not bond, in cyclohexane ring delta 45-47 ppm due to carbon of CH 2 in epoxy group delta 54-57 ppm due to carbon of CH in epoxy group delta 61-72 ppm due to carbon of CH 2 CH 2 O by ester bond delta 72-84 ppm due to carbon of CH to which oxygen bonds, in cyclohexane ring delta 112-115 ppm due to carbon of CH 2 in vinyl group delta 125.6 ppm due to one carbon of CH 2 = in methacrylic group delta 136.2 ppm due to another carbon of CH 2 = in methacrylic group delta 141-145 ppm due to carbon of CH in vinyl group delta 167.2 ppm due to carbon of ester group 〈 IR spectra 〉 859 cm -1 absorption due to epoxy group 1715 cm -1 absorption due to ester group in methacrylic ester It was confirmed by the assignments of 1 H-NMR spectra that averaged additional mol numbers of cyclohexene-1-oxide units having substituted groups to 2-hydroxyethylmethacrylate are approximately 3.9. Furthermore, the conversion of vinyl group to epoxy group was approximately 85 %. Example 3 [Preparation of an unsaturated carboxylic ether composition(III) comprising compounds having vinyl groups and then an epoxidized composition(XIII)] 300 g of toluene and 14 g of benzyl triethyl ammonium as a catalyst were charged into a flask equipped with a stirrer, a tube for supplying nitrogen gas and a dropwise funnel, followed by heating at 80 °C. 200 g of 1,2-epoxy-9-decene, 112 g of methacrylic acid and 0.1 g of p-methoxy phenol were charged into the dropwise funnel, followed by dropwise addition into the flask while maintaining at 80 °C over 10 hours to allow to react. The reaction was stopped at an epoxide conversion of 95 % , followed by washing and separating with 200 g of water twice to obtain 534 g of an unsaturated carboxylic composition(III) having vinyl groups. Successively, 500 g of the composition obtained above was charged into a 2-liter reaction vessel equipped with a condenser, a tube for supplying nitrogen gas and a dropwise funnel in which 300 g of ethyl acetate solution containing 30 % of peracetic acid in which 0.2 g of sodium 2-ethylhexyl tripolyphosphate was dissolved were charged, followed by dropwise addition while heating at 50 °C over 4 hours, and then aging for 5 hours to complete the reaction, followed by washing and separating with 800 g of water thrice and evaporating an organic solution layer with a thin-layer evaporator to obtain 262 g of an unsaturated carboxylic composition(XIII) having epoxy groups. THe composition exhibited the following properties. oxirane oxygen 6.20 acid value(mg KOH/g) 2.2 viscosity(cc/25 °C) 40 Example 4 [Preparation of a radically copolmerized composition comprising compounds having epoxy groups in which the composition(XIII) is copolymerized] 70 g of xylene and 3 g of perbutyl Z were charged into a flask equipped with a stirrer, a reflux condenser and a tube for supplying nitrogen gas, followed by heating at approximately 110 °C. Successively, a mixture composed of 50 g of the composition obtained in Example 2, 50 g of styrene as monomers and 2.5 g of perbutyl 0 as an initiator was added dropwise into the above xylene solution over 3 hours under nitrogen atmosphere, and further allowed to react for 10 hours to obtain 160 g of a desired copolymer solution. The copolymer solution was a transparent liquid having a number average molecular weight of 5200, an epoxy value of 720 equivalents and a solid content of 59 %. The copolymer solution was designated as resin solution [R-1]. Example 5 [Preparation of a radically copolymerized composition comprising compounds having epoxy groups in which the composition(XIII) is copolymerized] 67 g of xylene and 2.5 g of perbutyl Z were charged into a flask equipped with a stirrer, a reflux condenser and a tube for supplying nitrogen gas, followed by heating at from 110 to 120 °C. Successively, a mixture composed of 50 g of the composition obtained in Example 3, 38 g of methylmethacrylate, 12 g of ethylhexylacrylate as monomers and 2.5 g of perbutyl 0 as an initiator was added dropwise into the above xylene solution over 3 hours under nitrogen atmosphere, and further allowed to react for 7 hours to obtain 165 g of a desired copolymer solution. The copolymer solution was a transparent liquid having a number average molecular weight of 6500, an epoxy value of 860 equivalents and a solid content of 61 %. The copolymer solution was designated as resin solution [R-2]. Example 6 [Preparation of a radically polymerized composition comprising compounds having epoxy groups in which the composition(XIII) is polymer ized] 70 g of xylene and 2.5 g of perbutyl Z were charged into a flask equipped with a stirrer, a reflux condenser and a tube for supplying nitrogen gas, followed by heating at from 110 to 120 °C. Successively, a mixture composed of 100 g of the composition obtained in Example 3 as a monomer and 3 g of perbutyl 0 as an initiator was added dropwise into the above xylene solution over 3 hours under nitrogen atmosphere, and further allowed to react for 7 hours to obtain 165 g of a desired polymer solution. The polymer solution was a transparent liquid having a number average molecular weight of 4000, an epoxy value of 440 equivalents and a solid content of 60 %. The copolymer solution was designated as resin solution [R-3].

Claims: A composition (III) comprising compounds having vinyl groups as side chains, said compounds being obtainable by reaction of (a) with (d); wherein (a) is at least one compound having at least one vinyl group and one epoxy group in the molecule (d) at least one of an unsaturated monocarboxylic compound or an unsaturated monocarboxylic ester having a hydroxyl group. A composition as set forth in claim 1, wherein said compound (a) is selected from the group consisting of 4vinylcyclohexene-1-oxide, 5-vinylbicyclo[2.2.1]hepto-2-en-2-oxide and limoneneoxide. A composition as set forth in claim 1, wherein said compound (a) is a compound represented by the formula: wherein n is an integer of from 0 to 30. A composition as set forth in claim 1, wherein said compound (a) is a compound represented by the formula: wherein n1 and n2 are an integer of from 0 to 30, respectively. A composition as set forth in claim 1, wherein said compound (a) is a compound represented by the formula: wherein n is an integer of from 0 to 30. A composition as set forth in any of claims 1-5, wherein said compound (d) is at least one of acrylic acid, methacrylic acid, crotonic acid, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate and 2-hydroxybutyl(meth)acrylate. A composition as set forth in any of claims 1-5, wherein said compound (d) is at least one of a lactone-modified 2-hydroxyethyl(meth)acrylate, a lactone-modified 2-hydroxypropyl(moth)acrylate and a lactone-modified 2-hydroxybutyl(meth)acrylate. An epoxy composition (XIII) which is obtainable by epoxidizing a composition (III) as defined in any of claims 1-7. A polymer composition obtainable by radical (co)polymerization of a composition (III) as defined in any of claims 1-7 in the presence of a polymerization initiator and optionally at least one vinyl monomer. An epoxidized polymer composition obtainable by the epoxidation reaction of a polymer composition as set forth in claim 9 with an epoxidation agent. A polymer composition obtainable by radical (co)polymerization of an epoxy composition (XIII) as defined in claim 8 in the presence of a polymerization initiator and optionally at least one vinyl monomer. A curable resin composition which comprises a polymer composition obtainable by radical (co)polymerization of an epoxy composition (XIII) as defined in claim 8 in the presence of a cationic polymerization initiator and optionally an epoxy resin having at least one epoxy group.

Inventors: HARANO YOSHIYUKI, MAEDA KATSUYUKI, MURAI TAKAAKI, NAMAI SOZO, HARANO, YOSHIYUKI, MAEDA, KATSUYUKI, MURAI, TAKAAKI, NAMAI, SOZO
Applicants: DAICEL CHEM, DAICEL CHEMICAL INDUSTRIES, LTD.
Application year: 1992
Main classification: C08L63
IPC codes: C09D163, C09D167, C08G63, C08G65, C08G59