JPH07103215B2 - Active energy ray curable resin - Google Patents

Description

TECHNICAL FIELD The present invention has a comb structure in which a side chain is introduced into a main chain obtained by modifying an epoxy resin, or a sloppy structure,
It is curable by active energy rays, has excellent fluidity and curability, and can provide a coating film with excellent film physical properties such as water resistance and durability, and is not only useful as a paint vehicle, but also an adhesive, The present invention relates to a new resin that can be used in a wide range of fields such as a printing plate material, a lithographic material, and a coating material for optical fibers.

Conventional technology Resin that cures by irradiation with active energy rays or high energy rays can be cured in seconds, can use electrical energy, and since there is almost no evaporation of solvent, low pollution can be achieved. Since it does not require high temperature for curing, there is no thermal deformation of the coated object, the curing device can be downsized, space can be saved, and the wavelength of the energy beam is short, so there are various advantages such as good image reproducibility. Having, for example, ultraviolet curable paint, electron beam curable paint, photoresist,
As electron beam resist, X-ray resist, plate-making material, etc.
Widely used in paints, printing industry, electronics industry, etc. These resins are in a liquid state before being cured by irradiation with high energy rays, and unlike ordinary thermosetting resin compositions,
In general, it is usually used without a volatile solvent so that volatilization or setting is not necessary for the solvent due to temperature rise, so the viscosity must be such that sufficient workability can be obtained without the solvent.

Epoxy resins have excellent physical properties such as adhesion to metals, corrosion resistance, chemical resistance, and electrical insulation properties, and are used in a wide variety of fields, and the amount used has been increasing more and more in recent years. The epoxy resin is usually used as it is, or if desired, dissolved in an organic solvent and used. Especially in the field of active energy ray-curable resins, an epoxy (meth) acrylate resin obtained by ring-opening reaction of acrylic acid or methacrylic acid with an epoxy group of the epoxy resin. Is widely used. However, the commonly used epoxy acrylate resin has a drawback that it is hard and brittle, and when it is used as, for example, an ultraviolet curable coating material, it has a drawback that it can be broken even by a simple bending process.

Therefore, in order to give flexibility to the epoxy resin, a side chain having a primary alcoholic hydroxyl group at the terminal is introduced by ring-opening polymerization of, for example, ε-caprolactone with respect to the alcoholic hydroxyl group in the epoxy resin, and A curable resin composition containing a lactone-modified epoxy (meth) acrylate resin obtained by reacting all or part of epoxy groups with acrylic acid or methacrylic acid has been proposed (Japanese Patent Publication No. 61-108618) and attracted attention. There is. Such resins are excellent in flexibility, have a low viscosity, have a good balance between the hardness of epoxy resin and the flexibility of the side chain resin, and can be cured by irradiation with radiation such as ultraviolet electron beams, so coatings, adhesives, printing fields Although it is useful in various fields, it cannot be said that it is still sufficient in terms of water resistance because of the presence of unreacted hydroxyl groups in the resin, and the ethylenic group present at one or both ends of the epoxy resin Since it is only a crosslink derived from an unsaturated group, the physical properties of the film after the curing reaction are particularly insufficient in terms of toughness, and further improvement is desired.

Problems to be Solved by the Invention Therefore, excellent physical properties peculiar to epoxy resin are retained, flexibility and flexibility are moderately balanced, viscosity is low, and not only curing by irradiation with active energy rays but also water resistance It is an object of the present invention to provide a modified epoxy resin capable of providing further improved film properties in terms of durability and toughness. Further, it is one of the objects of the present invention to provide an active energy ray-curable resin whose curing reactivity and crosslink density can be easily controlled.

Means for Solving the Problems According to the present invention, the above object of the present invention is to provide an epoxy resin having at least one hydroxyl group and having an epoxy equivalent of 100 to 6000 as a main chain portion, and at least a part of the hydroxyl groups having a molecular weight of 100.
A linear oligomer having an active hydrogen-containing end group of ˜7000 is introduced as a side chain portion, and at least a part of the side chain has an ester bond, a urethane bond, an acyl urethane bond, a urea bond, or an acyl urea bond. This can be achieved by an active energy ray-curable resin in which an ethylenically unsaturated group is supported via the above, and the molecular weight ratio of the main chain portion to the side chain portion is 0.1 to 10.

The active energy ray-curable resin according to the present invention contains at least one hydroxyl group and has an epoxy equivalent of 100 to 6000.
Ring-opening polymerization of lactone, cyclic ether, or lactam to the epoxy resin of, or reaction of polyester, polyether, acryl, polylactone or polylactam having active hydrogen-containing groups at both ends with diisocyanate compound, or A diisocyanate compound is reacted, and then polyester, polyether, acrylic having active hydrogen-containing groups at both ends,
By reacting a polylactone or polylactam, a molecular weight of 100-7000 with an active hydrogen-containing group at the terminal
Introducing the linear oligomer of, and further reacting the vinyl isocyanate compound having an ethylenically unsaturated group and an isocyanate group, or first reacting a diisocyanate compound, then reacting a compound having an active hydrogen group and an ethylenically unsaturated group Then, at least a part of the terminal of the linear oligomer is ester bond, urethane bond,
It is a modified epoxy resin having a novel comb-type structure or sudare-type structure which can be conveniently produced by introducing an ethylenically unsaturated group through any of an acylurethane bond, a urea bond and an acylurea bond.

Since the modified epoxy resin of the present invention has a structure in which a side chain is introduced into the main chain, it becomes clear that it can be inferred from the free volume theory that when compared at the same molecular weight level, the viscosity becomes lower than that of the linear polymer, and It has the characteristic of having a high degree of freedom in design. The low resin viscosity and easy handling are extremely advantageous in terms of coating workability. In addition, a linear oligomer having a flexible structure is introduced into the side chain to maintain the balance between the hardness of the epoxy resin and the flexibility of the side chain. Furthermore, a feature of the resin according to the present invention is that a reactive ethylenically unsaturated bond is bonded to not only the terminal of the epoxy resin but also the side chain terminal. Compared to the case of introducing an ethylenically unsaturated group at the end of a rigid main chain, the introduction of an ethylenically unsaturated group at the side chain end, which is a flexible segment, makes the reactivity of the ethylenically unsaturated group by irradiation of active energy rays higher. Is high and the reaction can be carried out efficiently. It is considered that this is because the mobility of the ethylenically unsaturated group at the side of the side chain is greater during the curing reaction. Regarding the physical properties of the film after the reaction, the film obtained from the resin oligomer having an ethylenically unsaturated group at the side chain terminal not only gives a so-called tough film that is hard and stretches well, but also has good adhesion to metal. Also in this phenomenon, the skeleton of the film is formed by the cross-linking of the flexible terminal functional groups, and the rigid epoxy resin main chain forms an oriented structure, or forms a domain, so that such curing occurs. It is presumed that

Preferred Embodiment Raw Epoxy Resin: A linear epoxy resin having epoxy groups at both ends and an alcoholic hydroxyl group in the main chain can be used. Typical examples of these are bisphenol epoxy resins such as bisphenol A, bisphenol S, and bisphenol F, but diglycidyl ethers of glycols such as butanediol, hexanediol, and hydrogenated bisphenol A; polyethylene glycol, polypropylene glycol, Diglycidyl ethers of polyoxyalkylene glycols such as adducts of bisphenol and alkylene oxides; diglycidyl esters of dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, adipic acid; paraoxybenzoic acid, metahydroxybenzoic acid, etc. There are glycidyl ethers and esters of hydroxycarboxylic acids.

Epoxy compounds without an alcoholic hydroxyl group in the main chain are chain-extended by reaction with a bifunctional active hydrogen-containing compound, and pre-modified epoxy with an alcoholic hydroxyl group formed by ring opening of the epoxy group in the main chain It can be used as a resin. The epoxy resin in the present invention also includes such chain-extended pre-modified epoxy resin. The bifunctional active hydrogen-containing compound used for chain extension is a compound having two amino groups, imino groups, hydroxyl groups and carboxyl groups in the molecule as active hydrogen-containing groups. Examples thereof are alkylene glycols such as ethylene glycol, trimethylene glycol, tetramethylene glycol, 1,6-hexanediol; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; n moles of adipic acid and n + 1 moles of ethylene glycol. Polyester diols such as reaction products with; bisphenol A, 1,1-bis (4-hydroxyphenyl) ethane, 2-methyl-1,1-bis (4
-Hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, bis (2-hydroxynaphthyl) methane, dihydric phenol such as 1,5-dihydroxynaphthalene; adipic acid, azelaine Acid, maleic anhydride, dicarboxylic acid such as phthalic anhydride and its anhydride; polyester dicarboxylic acid such as a reaction product of n mol ethylene glycol and n + 1 mol phthalic anhydride; N-methylethanolamine, N-
Alkanolamines such as methylpropanolamine, diethanolamine and dipropanolamine; diamines such as N, N'-dimethylethylenediamine and N, N'-dimethyltrimethyleneamine.

The epoxy equivalent of the raw material epoxy resin including the above-mentioned pre-modified epoxy resin is required to be 100 to 6000 in order to impart appropriate performance to the modified epoxy resin as the final product. Further, the raw material epoxy resin must have at least one alcoholic hydroxyl group serving as the introduction point of the side chain polymer chain, but it is preferably 50 or less.

Introduction of side chain Synthesis of linear polymer block: As a first step of introducing a side chain carrying an ethylenically unsaturated group into the main chain of a raw material epoxy resin, first, active hydrogen having a molecular weight of 100 to 7,000 is introduced into the alcoholic hydroxyl group. A linear oligomer having a containing end group is introduced as a linear polymer block part. In this case, there are a method of ring-opening polymerization of a lactone, a cyclic ether or a lactam with respect to the alcoholic hydroxyl group, and a method of reacting diisocyanate with a linear oligomer having an active hydrogen-containing group at the terminal.

The lactone that can be used has the general formula R is hydrogen or a methyl group, and n is 1
Represents an integer of 4; Specifically, β-propiolactone,
There are γ-butyrolactone, δ-valerolactone, ε-caprolactone, ε-enanthlactone and the like. Examples of cyclic ethers that can be used include ethylene oxide, propylene oxide and the like. Examples of lactams that can be used are ε-caprolactam, 1-methyl-ε-caprolactam, 3-methyl-ε-caprolactam, 5-ethyl-ε.
-Caprolactam and the like.

The ring-opening polymerization reaction with a lactone is performed in the presence or absence of a catalyst and a solvent at about 100 to 250 ° C., preferably about 120 to 200.
It can be performed at ° C. As the catalyst, tetrabutyl titanate, tetraethyl titanate, tetraisopropoxy titanate, butoxy titanium trichloride, titanium compounds such as titanium tetrachloride, triethyl aluminum,
Aluminum compounds such as ethyl aluminum chloride and aluminum trichloride, zinc compounds such as diethyl zinc and zinc chloride, tin compounds such as dibutyl tin oxide, dibutyl tin laurate and stannous chloride, trifluoroboric acid, p
-Toluenesulfonic acid, acids such as phosphoric acid, lithium,
Alkali metal or its complex such as sodium, sodium naphthalene and potassium benzophenone, alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal salt such as sodium carbonate and lithium acetate, lithium hydride and hydrogen Alkali metal hydrides such as sodium hydride and tertiary amines such as triethylamine, pyridine may be used. The ring-opening addition polymerization reaction of the cyclic ether and lactam can also be carried out by known methods.

The side chain can also be introduced using a diisocyanate compound and a linear oligomer having active hydrogen-containing groups at both ends. 2,4 as diisocyanate compounds that can be used
-Or 2,5-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like. As the side chain oligomer, a linear oligomer having an active hydrogen-containing group such as a hydroxyl group, an amino group and an arboxyl group at both ends such as polyester diol, polyether diol, acrylic polyol, polycaprolactone and polylactam can be used. Specifically, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, polycaprolactone and the like are suitable.

The bonding of the linear oligomer to the epoxy resin hydroxyl group by the diisocyanate compound is carried out by simultaneously reacting the three components, or by reacting the diisocyanate with the epoxy resin either one of the linear oligomers and then reacting with the other component. It can also be carried out in stages. The molecular weight of the linear oligomer per one hydroxyl group of the epoxy resin needs to be in the range of 100 to 7000, preferably 200 to 3000. Further, in the balance between the main chain portion and the side chain portion, the ratio of the main chain portion molecular weight to the side chain portion molecular weight needs to be in the range of 0.1 to 10, preferably 0.5 to 8. If the molecular weight of the linear oligomer or the ratio of the main chain portion and the side chain portion is not within this range, the effect of decreasing the viscosity due to the introduction of the side chain, the surfactant function, the effect of imparting flexibility, etc. may be insufficient,
Or it becomes excessive, which is not preferable.

Introduction of an ethylenically unsaturated group into a linear polymer block portion: The linear polymer block portion thus synthesized as the first step of introducing a side chain has a terminal ethylenically unsaturated group at the end thereof. The chain polymer blocks are linked by the following method to introduce an ethylenically unsaturated group-carrying side chain.

In the first method, a vinyl isocyanate compound having a reactive ethylenically unsaturated group and an isocyanate group, such as isocyanate ethyl methacrylate, isocyanate acrylate, or isocyanate methyl acrylate, is directly reacted to react a group having active hydrogen with an isocyanate group. A method for obtaining a linear polymer block having a reactive ethylenically unsaturated group through a urethane bond, an acyl urethane bond, a urea bond or an acyl urea bond.

The second method is to react a compound having at least two isocyanate groups having different reactivities to bond a segment having a terminal isocyanate group through a urethane bond, an acyl urethane bond, a urea bond, or an acyl urea bond, and then to leave this residue. The isocyanate group is reacted with a compound having an α, β-ethylenically unsaturated group and a group having active hydrogen, such as 2-hydroxyethyl (meth) acrylate or (meth) acrylamide, and the active hydrogen and the isocyanate group are reacted. Is a method of introducing a terminal ethylenically unsaturated group by the reaction of. It should be noted that the reaction between the isocyanate group and the group having active hydrogen proceeds extremely easily at room temperature, and IR and NMR
It can be easily confirmed by, for example, disappearance of an isocyanate group or measurement of an amide bond.

The third method has a carboxylic acid at the terminal --OH group (meth).
This is a method of introducing an ethylenically unsaturated group into the end of a linear polymer through an ester bond by a reaction with an acrylate.

Other modification method of side chain The step of the second step is not performed for all the active hydrogen-containing groups at the end of the side chain introduced in the first step of introduction of the side chain, and the remaining active hydrogen-containing groups are treated as follows. A blocked isocyanate group can be introduced by reacting with a half-blocked diisocyanate compound. As a result, the surface active function, compatibility, dispersion stability and the like are further improved, and curability can be imparted to the resin. As the diisocyanate compound, those mentioned above can be used, and as the blocking agent, an aliphatic alcohol such as n-butanol, 2-ethylhexanol or stearyl alcohol; phenylcarbinol,
Aromatic alkanols such as methylphenylcarbinol; glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; phenols such as phenol and cresol; oximes such as acetone oxime and methyl ethyl ketoxime; lactams such as caprolactam; Dialkylaminoalkanols such as dimethylaminoethanol and 2-diethylaminoethanol can be used.

The amount of modification of the side chain terminal with half-blocked isocyanate is good to modify 20 to 100% of all side chain functional groups,
The range of 30-80% is more preferable. If it is 20% or less, the effect on the surface active function and curability when introduced is small. If it is 80% or more, the viscosity tends to increase during the synthetic reaction. As the blocking agent, curing reaction, from the viewpoint of dissociation temperature, C ₄ or more aliphatic alcohols, aromatic alcohols, phenols are preferable, and the modifying effect of these half-blocked isocyanates is to improve the surface-active function and curability. It is noticeable in.

Modification of main chain terminal α, ω epoxy group and introduction of ethylenically unsaturated group: The epoxy group at the main chain terminal can be modified as necessary to introduce an ethylenically unsaturated group at the main chain terminal. As a method of introducing, (meth) acrylic acid is reacted with an epoxy group at the end of the main chain and directly introduced through an ester bond, or a hydroxyl group is first introduced to form an ester bond, a urethane bond, or an acyl urethane bond. There is a step-by-step method of introducing it. As a method of introducing the hydroxyl group, glycolic acid, lactic acid, hydroxypivalic acid, a monohydroxymonocarboxylic acid such as dimethylolpropionic acid, or a dihydroxymonocarboxylic acid to an epoxy group at the terminal of the main chain is reacted to form an epoxy group with a carboxyl group. Examples thereof include a method of ring-opening, or a method of reacting with a monohydroxyamino group or dihydroxyamino acid to open the epoxy group with an amino group to introduce the epoxy group.

By introducing an ethylenically unsaturated group into the main chain as described above, the ethylenically unsaturated group in the side chain can be appropriately combined, and necessary curability and physical properties can be controlled.

Main chain and side chain functional groups: A hydroxyl group contained in the main chain in the above process of synthesizing the resin according to the present invention or an active hydrogen-containing group carried at the side chain end in the first step of introducing a side chain, For example, some hydroxyl groups, amino groups, etc. may be modified by the first step or the second step for introducing the side chain, respectively, but it is possible to leave some of them, if necessary, and, if desired, It is also possible to modify at least a part of the active hydrogen-containing group end to carry a blocked isocyanate group on the side chain end, and also the main chain epoxy group, if necessary, remains at least partially unmodified. It can be done. Thus, according to the present invention, the resin may contain various functional groups in the main chain and side chains depending on the embodiment, but these functional groups are optionally combined with other curing agents to contribute to the composite curing of the entire resin. be able to.

Curing with active energy rays When the active energy ray-curable resin of the present invention is cured with active energy rays, a photopolymerizable monomer, or a low molecular weight oligomer, a photopolymerization initiator (or a sensitizer),
A thermal polymerization inhibitor (or stabilizer) or the like may be added, and if necessary, a thermal polymerization inhibitor (or stabilizer), a sensitization aid, a colorant,
A surfactant, an ultraviolet absorber, a matting agent, a thixotropic agent, and the like are further mixed with various thermoplastic resins, thermosetting resins, curing agents, etc. to prepare an active energy ray curing composition for use. . When the curable composition is cured with an electron beam, it is not always necessary to add a sensitizer.

Examples of the photopolymerizable monomer or low molecular weight oligomer include unsaturated polyester resins, urethane acrylate resins, epoxy acrylate resins, polyester acrylate resins, spirane acrylate resins, polyether acrylate resins, and other low molecular weight oligomers, styrene, Vinyltoluene, divinylbenzene, vinyl acetate, acrylonitrile, methacrylonitrile, acrylic acid ester (for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, ethylene glycol diacrylate, trimethylolpropane) Triacrylate), methacrylic acid ester (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethyl methacrylate). Sill, glycidyl methacrylate,
Ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate), diethyl itaconate, dibutyl itaconate, diethyl fumarate, diethyl maleate and the like are known.

Examples of the sensitizer include benzoin, benzoin methyl ether, benzoin propyl ether, benzoin butyl ether, benzophenone, diacetyl, benzyl, dibutyl disulfide and dibenzyl disulfide.

Further, as the thermal polymerization inhibitor, hydroquinone, t-
Butylhydroquinone, p-methoxyphenol, catechol, benzoquinone and the like can be mentioned.

The active energy ray in the present invention is an ultraviolet ray, an electron beam,
X-rays and radiation, producing free radicals upon irradiation,
All active energy rays that induce the addition polymerization of vinyl bonds are included.

The active energy ray-curable resin of the present invention retains excellent physical properties peculiar to epoxy resin, has a good balance of flexibility and flexibility, and has further improved coating performance in terms of water resistance, durability and toughness. In addition, in the printing industry, as a plate material or a cured printing ink for letterpress, planographic printing, intaglio and screen printing plates, it is possible to color In the material industry, as a paint, packaging material or adhesive,
In the electronics industry, shadow masks, printed wiring ICs,
As a resist, dry film or encapsulant for electronic parts such as LSI, metal surface treatment industry, ceramics industry,
In the glass industry, precision machinery industry, building materials industry, automobile industry or shipbuilding industry, as a photoresist for plates and parts, in the textile industry as a surface treatment material, in the biomedical industry as an enzyme immobilizing agent and caries filler. It can be applied as a material obtained by a curing method using high energy rays.

Examples will be specifically described below, but "parts" and "%" in the examples are based on weight.

Example 1 A flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser was charged with 450 parts of an epoxy resin having an epoxy equivalent of 450 obtained by the reaction of bisphenol with epichlorohydrin and an epoxy resin having a number average molecular weight of 900, and methyl isobutyl ketone. 188 parts was added and dissolved, 300 parts of ε-caprolactone and 0.457 part of dibutyltin oxide were added under a nitrogen stream, and the reaction was carried out at 120 ° C. for 8 hours. Then the system temperature is raised to 30
111 parts of methacryloyl isocyanate while maintaining at ℃
And 0.4 parts of hydroquinone were added dropwise over 20 minutes. After completion of the dropping, the reaction between methacryloyl isocyanate and a hydroxyl group was checked by an infrared absorption spectroscopy, and the disappearance of the peak at 2250 cm ⁻¹ due to the —NCO group, —NH
It was confirmed that the peak at 3300 cm ^-1 due to the group and the peak at 1760 cm ^-1 shifted from the normal carbonyl group due to the acylcarbonyl group appeared. Furthermore, by nuclear magnetic resonance spectroscopy (NMR method), the appearance of a signal due to the proton of the —NH group and the chemical shift of the signal due to the vinyl proton to a high magnetic field of about 0.3 ppm were confirmed.

Next, by desolvating the system using a decompression device, the non-volatile content 99 having a side chain having an ethylenically unsaturated group in the main chain
% Active energy ray curable resin (A) was obtained.

Resin Curing Test 100 parts of the resin (A), 60 parts of trimethylolpropane triacrylate, 40 parts of N-vinylpyrrolidone and 4 parts of benzoin methyl ether were thoroughly mixed to obtain an ultraviolet curable composition. Cold rolled steel sheet degreased with this composition is 100μ
A coating film having a good adhesion was obtained with a pencil surface hardness of 2H and a coating film gloss of 89 by applying the above-mentioned coating and performing an ultraviolet treatment under the conditions described below.

UV treatment conditions Place the lamp length direction of the Japan battery high pressure mercury lamp HI-20N (80W / cm type, using concentrating type equipment) at a right angle to the traveling direction of the conveyor,
The height from the conveyor surface is 80 mm and the conveyor speed is 3 m / min.

Example 2 Using the same reactor as in Example 1, 450 parts of an epoxy resin having an epoxy equivalent of 450 obtained by the reaction of bisphenol and epichlorohydrin, 450 parts of an epoxy resin having a number average molecular weight of 900 and 188 parts of methylisobutylketone were charged. After dissolution, 900 parts of ε-caprolactone and 0.5 part of dibutyltin oxide were added under a nitrogen stream, and the reaction was carried out at 120 ° C for 8 hours. Then 104 parts of hydroxypivalic acid and benzyldimethylamine
0.4 part was added and the temperature was raised to 120 ° C. over 30 minutes, and the reaction was carried out until the epoxy value became 0 and the acid value became 1 or less, then 333 parts isophorone diisocyanate, 2-hydroxy acrylate 1
74 parts, 707 parts of a half-block isocyanate mixed solution obtained from 200 parts of methyl isobutyl ketone, and reacted until the absorption of the isocyanate group disappeared in the infrared absorption spectrum, and ethylenically unsaturated groups in the main chain and side chains The active energy ray-curable resin (B) was obtained.

100 parts of the obtained resin (B), 20 parts of trimethylolpropane triacrylate and 10 parts of N-vinylpyrrolidone were added to obtain an active energy ray-curable resin composition. Such a composition is applied to a degreased cold-rolled steel sheet so as to have a film thickness of 25μ, and after sufficiently volatilizing the solvent, electron energy 30
An electron beam of 0 KeV was irradiated under an electron current of 35 mA, and the dose was 3 Mra.
By giving d, a cured coating film having no surface tackiness was obtained. The coating film was transparent, had a pencil hardness of H, and had an adhesion of 100/100 in a cross-cut tape peeling test.

Next, the same active energy ray-curable resin composition was applied to a 5 mm plastic plate so that the cured film thickness was 100 μ, and the anodic cathode was tungsten and the accelerating voltage was 50.
X-rays were irradiated with a dose of 1.2 million roents under a current of 40 mA at KV to obtain a cured coating film. This coating is transparent, has a pencil hardness of H and 100/100 in the crosscut tape peel test.
It had the adhesiveness of. Further, it was found that this coating film was a tough coating film without cracking or peeling even when it was extruded by 5 mm with an Erichsen extrusion tester.

Example 3 The same container as in Example 1 was charged with 450 parts of the same epoxy equivalent 450, an epoxy resin having a number average molecular weight of 900 and 188 parts of methyl isobutyl ketone and dissolved, and then 500 parts of ε-caprolactone and dibutyltin were added under a nitrogen stream. 0.5 part of oxide was added and the reaction was carried out at 180 ° C. for 8 hours. Then hydroquinone
Charge 0.5 parts, adjust the reaction temperature to 30 ° C while flowing air, and then add 20 parts of 100 parts of isocyanate ethyl methacrylate.
Dropwise over minutes. After completion of the dropping, check the completion of the reaction between isocyanate ethyl methacrylate and hydroxyl group by infrared absorption spectrum, then keep the reaction temperature at 85 ° C, and add 72 parts of acrylic acid and 1 part of triethylamine to 2 parts.
Dropped over time. After completion of the dropping, the reaction was further performed at 85 ° C. for 10 hours, and then the solvent was removed to obtain an active energy ray-curable resin (C) having a nonvolatile content of 99% and having an ethylenically unsaturated group in the main chain and side chain.

100 parts of the obtained resin (C), 50 parts of trimethylolpropane triacrylate, 30 parts of N-vinylpyrrolidone, 20 parts of butyl acrylate and 2 parts of benzoin methyl ether.
The parts were thoroughly mixed to obtain a photocurable resin composition. The composition was applied to a degreased cold-rolled steel sheet so as to have a film thickness of 50 μm, and an ultraviolet ray treatment was performed under the same conditions as in Example 1 to obtain a cured coating film. The resulting coating has a pencil surface hardness of 2
In the H and xylol rubbing tests, the substrate could not be seen even 50 times. Also, with an Erichsen extrusion tester, the coated plate is 5 m
Although it was extruded, the coating film did not crack or peel off. An abrasion test was conducted using a Taber abrasion tester, and the amount of abrasion loss per 1000 revolutions was 150 mg. Furthermore, this coating film was hard and had good adhesion, and was flexible and water resistant, even if it was immersed in warm water at 60 ° C for 5 hours, without any abnormalities such as whitening or glossiness. .

Comparative Example 1 The same container as in Example 1 was charged with 450 parts of the same epoxy equivalent 450, an epoxy resin having a number average molecular weight of 900 and 188 parts of methyl isobutyl ketone and dissolved, and then 500 parts of ε-caprolactone and dibutyltin were added under a nitrogen stream. 0.5 part of oxide was added and the reaction was carried out at 180 ° C. for 8 hours. Then hydroquinone
0.5 part was charged, the reaction temperature was kept at 85 ° C. while flowing air, and 72 parts of acrylic acid and 1 part of triethylamine were added dropwise over 2 hours. After completion of the dropping, the reaction was further performed at 85 ° C. for 10 hours, and then the solvent was removed to obtain an active energy ray-curable resin (E) having a nonvolatile content of 99% and having an ethylenically unsaturated group in the main chain and side chain.

A photocurable resin composition was prepared in the same manner as in Example 3 except that 100 parts of the obtained resin (E) was used to obtain a coating film.
The pencil hardness of the obtained coating film was 2H, and the base material was not visible even after 50 times in the xylol rubbing test, but cracking and peeling of the coating film were observed by the extrusion of 3 mm by the Erichsen extrusion tester. Also by Taber abrasion test
The amount of wear loss per 1000 revolutions was 250 mg.

The coating film obtained had sufficient hardness, but was in Example 3.
The adhesiveness and flexibility of the coating film were inferior to those of the resin composition described in 1.

Example 4 In a container similar to that of Example 1, 950 parts of an epoxy resin having the same epoxy equivalent of 950 and a number average molecular weight of 1900 and 500 parts of methyl isobutyl ketone were charged and dissolved, and then 126 parts of δ-valerolactone and dibutyl were introduced under a nitrogen stream. 0.5 part of tin oxide was added and the reaction was carried out at 180 ° C. for 8 hours. Then hydroquinone
0.5 part was charged, the reaction temperature was kept at 85 ° C. while flowing air, and 72 parts of acrylic acid and 1 part of triethylamine were added dropwise over 2 hours. After the completion of the dropping, the mixture was further reacted at 85 ° C. for 10 hours, then 222 parts of isophorone diisocyanate, 130 parts of hydroxypropyl acrylate, and 552 parts of a half-block isocyanate mixed solution obtained from 200 parts of methyl isobutyl ketone were added, and an isocyanate was detected by an infrared absorption spectrum. The reaction was carried out until there was no absorption of groups.

Then, the solvent was removed to obtain an active energy ray-curable resin (D) having a nonvolatile content of 90% and having an ethylenically unsaturated group in the main chain and side chain.

100 parts of the obtained resin (D), 10 parts of trimethylolpropane triacrylate, 20 parts of 1,6-hexanediol diacrylate and 2 parts of benzyl diethyl ketal were mixed to obtain an active energy ray-curable resin composition. The obtained composition is iron-coated with a die to a coating thickness of 350μ on an optical fiber with a diameter of 120μ containing silica glass as the main component coated with a primary coating material, and the secondary coating is performed by UV treatment. A glass fiber was obtained. Such optical glass fiber does not crack or peel even when bent, has sufficient tensile strength, and has a transmission loss after one month.
It was as small as 0.5 dB / km or less.

Example 5 In the same container as in Example 1, 450 parts of the same epoxy resin having an epoxy equivalent of 450 and a number average molecular weight of 900 and 188 parts of methyl isobutyl ketone were charged and dissolved, and then 115 parts of ε-caprolactone and dibutyltin were added under a nitrogen stream. 0.5 part of oxide was added and the reaction was carried out at 180 ° C. for 8 hours. Next, 63 parts of sodium N-methyltaurine and methyl cellosolve were added to this resin solution.
300 parts was added and reacted at 100 ° C. until the epoxy value became 0. Next, desolvation is performed, and then propylene oxide 1000
Part, 25 parts of potassium hydroxide and 150 parts of water were added and mixed thoroughly, and the suspension was placed in an autoclave, sealed, pressurized to 30 psi with nitrogen gas, and heated to 95 ° C over 30 minutes. Heated and then cooled to room temperature. The reaction was thoroughly stirred during heating and cooling.

The reaction product from which the solvent, potassium hydroxide and propylene oxide had been removed was dissolved again in 500 parts of methyl isobutyl ketone. Subsequently, 0.5 part of hydroquinone was charged, the reaction temperature was raised to 30 ° C. while flowing air, and 100 parts of isocyanate ethyl methacrylate was added dropwise over 20 minutes. After completion of the dropping, the completion of the reaction between isocyanate ethyl methacrylate and the hydroxyl group was checked by infrared spectrum to obtain an active energy ray-curable resin (F) having a nonvolatile content of 99% and having an ethylenically unsaturated group in its side chain.

100 parts of the obtained resin (F), 50 parts of trimethylolpropane triacrylate and benzoin methyl ether 2
The parts were thoroughly mixed to obtain a photocurable resin composition. The composition was applied onto art paper so as to have a thickness of 5 μm, and treated with ultraviolet rays in the same manner as in Example 1 to obtain a cured coating film. The obtained coating film had a pencil hardness of H and no peeling of the coating film was observed even after 30 times of rubbing with acetone.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirotoshi Umemoto 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Ryuzo Mizuguchi 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint (56) References JP 61-246265 (JP, A) JP 61-108618 (JP, A) JP 55-99910 (JP, A) JP 54-65790 (JP, A)

Claims (4)

[Claims] 1. An epoxy resin containing at least one hydroxyl group and having an epoxy equivalent of 100 to 6000, wherein (Wherein R is hydrogen or a methyl group; n is an integer of 1 to 4) A line formed by a ring-opening polymer (average molecular weight 100 to 7000) of a lactone or a cyclic ether or ethylene oxide or propylene oxide represented by A linear oligomer is bonded as a side chain through an ester bond or an ether bond, and a segment having a terminal ethylenically unsaturated group having 16 or less carbon atoms has a urethane bond, an acyl urethane bond, a urea bond or an acyl bond at the end of the linear oligomer. Are bonded by a urea bond, optionally at least a part of the terminal epoxy group of the epoxy resin is converted to an ethylenically unsaturated group, a hydroxyl group or a zwitterionic group by modification, and the main chain portion and side chain portion Active energy ray curable resin having a molecular weight ratio of 0.1 to 10. 2. The epoxy resin is a bisphenol type epoxy resin, diglycidyl ether of glycols, diglycidyl ether of polyoxyalkylene glycols; diglycidyl ester of dicarboxylic acid; glycidyl ether and ester of hydroxycarboxylic acid; A reaction product of a functional active hydrogen-containing compound; from an epoxy resin having an ethylenically unsaturated group on at least a part of its terminals through an ester bond, a urethane bond, an acyl urethane bond, a urea bond, or an acyl urea bond The resin according to claim 1, which is selected from the group consisting of: 3. An epoxy resin having at least one hydroxyl group and having an epoxy equivalent of 100 to 6000, based on at least one hydroxyl group. (Wherein R is hydrogen or a methyl group; n is an integer of 1 to 4) ring-opening polymerization of a cyclic ether or lactam consisting of a lactone or ethylene oxide or propylene oxide, and having an active hydrogen-containing terminal group, and First to form linear oligomers with an average molecular weight of 100-7000
From the second step of introducing a segment having an ethylenically unsaturated group at the end of the linear oligomer by reacting the step and the vinyl isocyanate compound having an ethylenically unsaturated group and an isocyanate group with the product of the first step If desired, before or after the first step or after the second step, a step of modifying at least a part of the terminal epoxy groups of the epoxy resin into an ethylenically unsaturated group, a hydroxyl group or a zwitterionic group by modification. Containing at least one hydroxyl group and having an epoxy equivalent of 100
For the main chain of epoxy resin up to 6000, the formula (Wherein R is hydrogen or a methyl group; n is an integer of 1 to 4) A line composed of a ring-opening polymer (average molecular weight 100 to 7,000) of a lactone or ethylene oxide, a cyclic ether composed of propylene oxide, or a lactam. A linear oligomer is bound as a side chain by an ester bond or an ether bond, and a segment having a terminal ethylenically unsaturated group having 16 or less carbon atoms has a urethane bond, an acyl urethane bond, a urea bond or an acyl bond at the end of the linear oligomer. Urea bond, if desired, at least a part of the terminal epoxy group of the epoxy resin is modified to an ethylenically unsaturated group, a hydroxyl group or a zwitterionic group, the main chain portion and side chain portion A method for producing an active energy ray-curable resin having a molecular weight ratio of 0.1 to 10. 4. An epoxy resin containing at least one hydroxyl group and having an epoxy equivalent of 100 to 6000, based on at least one hydroxyl group. (Wherein R is hydrogen or a methyl group; n is an integer of 1 to 4) ring-opening polymerization of a cyclic ether or lactam consisting of a lactone or ethylene oxide or propylene oxide, and having an active hydrogen-containing terminal group, and First to form linear oligomers with an average molecular weight of 100-7000
In the step, the product of the first step is reacted with a diisocyanate compound, and then a compound having an ethylenically unsaturated group and an active hydrogen-containing end group is reacted to have an ethylenically unsaturated group at the end of the linear oligomer. A second step of introducing a segment, optionally before or after the first step, or after the second step, by modifying at least a portion of the terminal epoxy groups of the epoxy resin with an ethylenically unsaturated group, a hydroxyl group or A step of converting to a zwitterionic group, containing at least one hydroxyl group, and having an epoxy equivalent of 100.
For the main chain of epoxy resin up to 6000, the formula (Wherein R is hydrogen or a methyl group; n is an integer of 1 to 4) A line formed by a ring-opening polymer (average molecular weight 100 to 7000) of a lactone or a cyclic ether or ethylene oxide or propylene oxide represented by A linear oligomer is bonded as a side chain through an ester bond or an ether bond, and a segment having a terminal ethylenically unsaturated group having 16 or less carbon atoms has a urethane bond, an acyl urethane bond, a urea bond or an acyl bond at the end of the linear oligomer. Are bonded by a urea bond, optionally at least a part of the terminal epoxy group of the epoxy resin is converted to an ethylenically unsaturated group, a hydroxyl group or a zwitterionic group by modification, and the main chain portion and side chain portion A method for producing an active energy ray-curable resin having a molecular weight ratio of 0.1 to 10.