JPS6143367B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a curable resin that is flexible and tough with excellent adhesion. In recent years, radiation-curable resins have been attracting attention as materials using curing systems using radiation such as electron beams and ultraviolet rays in response to the progress of environmental pollution, increases in energy costs, and restrictions on energy use. As such photosensitive compositions, resin compositions having a backbone of polyester resin, polyurethane resin, epoxy resin, etc. and having double bonds that can be polymerized by radiation are often used, but they generally do not contain volatile organic solvents. It is very desirable from the point of view of environmental conservation, as it contains no or only a small amount of paint. It has been put to practical use in a wide range of fields, including printing inks, adhesives, flexible circuit overlays and other coating materials, solder resists for printed circuit boards, etching resists, plating resists, and inks for printed circuits. However, such curing reactions caused by irradiation with electron beams or ultraviolet rays cause radical polymerization of ethylenic double bonds rapidly within a short period of time, resulting in shrinkage or residual strain during curing. As a result, compared to conventionally used thermosetting and solvent-volatile resins, it lacks adhesion to surrounding resins or metals, which often limits its use in the various applications listed above. Ta. On the other hand, although there are radiation-curable resins that have excellent adhesion, they often have problems with their original characteristic of rapid curing. For example, epoxy resin and α, β-
Radiation-curable resins whose main component is adducts of unsaturated acids cure rapidly when exposed to radiation and have high hardness, but they have poor toughness and shrinkage during curing, resulting in poor adhesion. It had drawbacks. Radiation-curable resins containing liquid polybutadiene or liquid polyisoprene and acrylic acid ester as main components exhibit excellent adhesion when irradiated with radiation, but require a relatively long time for complete curing. In view of these points, we are improving materials, improving composition,
Furthermore, although thermoplastic resins and thermosetting resins that are not directly involved in the radiation curing reaction have been added, it is often not possible to achieve the intended purpose. The purpose of the present invention is to impart flexibility and toughness to the resulting cured product by selecting specific compounds as unsaturated polyurethane resins and cross-base agents, and to significantly improve adhesion to various adherents. The object of the present invention is to provide a curable resin that has been cured. The present invention is a curable resin composition containing an ethylenically unsaturated compound and an unsaturated polyurethane resin having two or more end groups having a polymerizable ethylenically double bond and having a molecular weight of 1,300 to 20,000. The unsaturated polyurethane resin is a cationic unsaturated polyurethane resin, and the ethylenically unsaturated compound has the following general formula: (In the formula, A represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms) as a main component. The cationic unsaturated polyurethane resin of the present invention includes, for example, polyol (A), organic polyisocyanate (B)
and ethylenically unsaturated compounds with active hydrogen
(C) and a cationic compound (D) can be obtained by various methods. As the polyol (A), various polyester polyols, polyether polyols, and other polyols can be used. Examples of polyester polyols include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as adipic acid, suberic acid, sebacic acid, and brassylic acid, terephthalic acid, and isophthalic acid as acid components, and ethylene glycol, propylene glycol, neopentyl glycol, Polyester polyols whose polyol components include aliphatic diols having 1 to 6 carbon atoms such as hesamethylene glycol, ether glycols such as diethylene glycol and dipropylene glycol, spiroglycols, and N-alkyl dialkanolamines such as N-methyldiethanolamine; Polycaprolactone polyol etc. can be used, and specific examples include polyethylene adipate polyol, polybutylene adipate polyol,
Adipate polyols such as polyethylene propylene adipate polyol, terephthalic acid polyols (e.g., Toyobo Co., Ltd., product name Vylon)
RUX, Vylon RV-200L), polycaprolacne polyol (eg, Daicel Chemical, trade name Plaxel 212, Plaxel 220), and the like. Specific examples of polyether polyols include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, and the like. In addition, other polyols include epoxy group-containing polyols (e.g., Siel Kagaku, trade name Epicote 828, 834, 1001, 1002, 1003, 1004), polycarbonate polyols (e.g., West Germany, Bayer AG, trade name Desmofene 2020E), polybutadiene Polyol (e.g. Nippon Soda, product name G-
1000, G-2000, G-3000, Idemitsu Petrochemical Co., Ltd. (trade name: Poly bd R-45 HT), polypentadiene polyol, castor oil polyol, and the like. These polyols can be used alone or in combination of two or more. Organic polyisocyanate (B) used in the present invention
Examples include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), tolidine diisocyanate (TODI), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), isophorone diisocyanate ( IPDI),
These include diisocyanates such as hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), and lysine diisocyanate (LDI), and polyisocyanates such as triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate (PAPI), and carbodiimide-modified MDI. can be used alone or in combination of two or more. In the present invention, various types of ethylenically unsaturated (C) having an active cedar element can be used, but representative examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-propanediol,
-Butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol,
Mono(meth)acrylates of dihydric alcohols such as polyethylene glycol and polypropylene glycol; mono- and di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin; Examples include di- and tri(meth)acrylates, and these may be used alone or in combination of two or more. The cationic compound (D) can be obtained by using a polyol compound containing a tertiary amino group such as N-methyldiethanolamine and quaternizing it with a quaternizing agent such as dimethyl sulfuric acid. In the synthesis of the unsaturated polyurethane resin of the present invention, it is optional to use a chain extender (E) in addition to the above-mentioned components, and such chain extenders include, for example, 2- to 6-functional chain extenders with a molecular weight of 500 or less. Examples include polyols having a molecular weight of 500 or less and diamines having a primary or secondary terminal amino group. Suitable chain extenders include (a) ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol,
Polyols such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, xylylene glycol (b) Hydrazine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,
Diamines such as 4-cyclohexanediamine (c) Alkanolamines such as ethanolamine, diethanolamine, and triethanolamine (d) Hydroquinone, pyrogallol, 4,4'-isopropylidene diphenol, aniline, and the above polyols and diamines and polyols with a molecular weight of 500 or less obtained by adding propylene oxide and/or ethylene oxide to alkanolamines in any order. When synthesizing the cationic unsaturated polyurethane resin of the present invention, the ratio of each component can be appropriately determined from a wide range depending on the intended use of the curable resin, but usually polyol (A), ethylenic resin having active hydrogen, The chemical equivalent ratio of the active hydrogen groups contained in the unsaturated compound (C) and the chain extender (E) used as necessary to the NCO group of the organic polyisocyanate (B) is 0.9 to
1.4, preferably 0.95 to 1.2, and the reaction is usually carried out at 30 to 130°C, preferably
It is best to do it at 40-120℃. In the present invention, the cationic unsaturated polyurethane resin can be synthesized without a solvent, in the presence of an organic solvent, or in the presence of an ethylenically unsaturated compound used as a crosslinking agent described later. Examples of organic solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl propionate, ethers such as dioxane and cellosolve acetate, and dimethylformamide and dimethyl sulfoxide. In the present invention, an ethylenically unsaturated compound represented by the following general formula (1) is used as a crosslinking agent. (In the formula, A represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms). Specific examples include ethylene glycol, propylene glycol, 1,3-
Propanediol, 1,2-butanediol,
Examples include monomethacrylates such as 1,3-butanediol and 1,4-butanediol, and 3-chloro-2-hydroxypropyl methacrylate. The reason for employing the compound of general formula (1) in the present invention is that when acrylates and methacrylates are compared, the use of methacrylates is significantly superior in terms of physical properties and adhesion of the cured product. When comparing the presence or absence of OH groups among the same methacrylates, those with OH groups are significantly superior in the physical properties of the cured product, especially in terms of 100% modulus, tensile strength, and adhesion. Next, the compound of general formula (1) is significantly superior in the physical properties and adhesion of the cured product compared to a compound having the same OH group as a methacrylate, but in which the alkyl group is connected with an ether bond to increase the molecular weight. etc. In the present invention, the weight ratio of the cationic unsaturated polyurethane resin and the ethylenically unsaturated compound containing the compound of general formula (1) is preferably 30:70 to 95:5, more preferably 50:50 to 80:20. . When the ratio of both is within this range, the resulting cured product has excellent flexibility and exhibits sufficient strength and adhesion. In the present invention, other compounds can be mixed within a range that does not impair the purpose. Specific examples of these compounds include unsaturated polyester resins, saturated polyester resins, epoxy resins, and (meth)
Esters with acrylic acid, polyurethane resins, diallylphthanol resins, ketone resins, alkyd resins, phenolic resins, rosin-modified phenolic resins, rosin esters, maleic acid-modified rosin esters, urea resins, melamine resins, polyamide resins, styrene resins ( meth)acrylic acid copolymer or its ester, styrene-maleic anhydride resin or its ester, poly(meth)acrylate, _C5 - _C9 petroleum resin, hydrogenated petroleum resin,
Examples include polybutadiene, natural or synthetic rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, polyvinyl alcohol, and wax. Further, these known compounds can be added before or during the reaction as long as they do not interfere with the synthesis of the cationic unsaturated polyurethane resin of the present invention. In the present invention, other ethylenically unsaturated compounds can be used as crosslinking agents when necessary when curing the above-mentioned curable resin composition. Various known compounds can be used as the ethylenically unsaturated compound. Typical examples include styrene, vinyltoluene, chlorostyrene, t-butylstyrene, α-methylstyrene, divinylbenzene, acrylic acid, methacrylic acid, acrylic acid or methyl, ethyl, isopropyl, n- Butyl, t-butyl, α-ethylhexyl, n-nonyl, n-decyl, lauryl, stearyl ester, etc., n-butoxyethyl acrylic acid or methacrylic acid, cyclohexyl,
Phenoxyethyl, tetrahydrofurfuryl, glycidyl, allyl, benzyl, tribromophenyl, 2,3-dichloropropyl, N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N-t-butylaminoethyl ester, etc., ethylene Glycol monoacrylate, propylene glycol monoacrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate with molecular weight (hereinafter referred to as MW) 200-1000, MW200-1000
polyethylene glycol monomethyl ether mono(meth)acrylate with MW200~1000, polypropylene glycol monomethyl ether mono(meth)acrylate with MW200~1000,
Polyethylene glycol monoethyl ether mono(meth)acrylate with MW200~1000,
MW200-1000 polypropylene glycol monoethyl ether mono(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3
-propanediol di(meth)acrylate,
1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin Di(meth)acrylate, glicentri(meth)acrylate, trimethylolethane di(meth)acrylate, trimethylolethane tri(meth)acrylate,
Trimethylolpropane tri(meth)acrylate, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, ethylenebisacrylamide, diallyl phthalate,
Examples include triallylisocyanurate, dibutyl fumarate, vinyl acetate, and the like. However, if the compound is present during the urethanization reaction, the ethylenically unsaturated compounds having active hydrogen should be excluded from the above. In the present invention, the proportion of the compound of general formula (1) in the entire crosslinking agent is preferably 40% by weight or more, and more preferably 60% by weight or more.
More preferably it is % by weight or more. A known thermal polymerization inhibitor may be added for the purpose of stably storing the curable resin composition of the present invention. For example, hydroquinone, mono-tert
-Butylhydroquinone, 2,5-di-tert-butylhydroquinone, hydroquinone monomethyl ether, catechol, p-tert-butylcatechol, benzoquinone, 2,5-di-tert-butylbenzoquinone, 2,5-diphenyl-p-benzoquinone , 2,6-di-tert-butyl-p-cresol, and picric acid. It is desirable that these thermal polymerization inhibitors prevent only the thermal polymerization reaction (dark reaction) without inhibiting the photocuring reaction, so the amount added should be the total amount of the cationic unsaturated polyurethane resin and the crosslinking agent. against
A desirable range is 0.001 to 2.5% by weight, preferably 0.005 to 1% by weight. Furthermore, in the present invention, it is normally used as necessary. Additives such as dispersants, lubricants, abrasives, antistatic agents, etc. can be added. Furthermore, in the present invention, for example, paints, inks,
Colorants commonly used in applications such as adhesives,
Additives such as flame retardants and lubricants, fillers such as glass, mica, and iron powder may also be added. The curable resin composition of the present invention can be cured by a known method. For example, when curing with an electron beam, the total absorbed dose is A cured product can be obtained by irradiating at an amount of 0.5 to 50 Mrad, preferably 2 to 30 Mrad. In addition, in the present invention, other curing means such as infrared rays,
A method of curing using thermal energy such as high frequency or microwave, that is, a method of curing by heating, a method of curing with ultraviolet rays obtained from a mercury lamp, a xenon lamp, etc., or a method of curing by irradiation with other radiation such as X-rays or gamma rays is used. You can also do that. In the present invention, when using high-energy ionizing radiation such as electron beams, X-rays, and γ-rays, which have the effect of being absorbed by substances and emitting secondary electrons, it is not necessary to add a polymerization initiator. is also good, but
When curing by heating or ultraviolet rays, it is preferable to add a thermal polymerization initiator or a photopolymerization initiator. Examples of these thermal or photopolymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, hydroperoxides such as cumene hydroperoxide and tert-butyl peroxide, and di-tert-butyl peroxide. Examples include dialkyl peroxides such as oxide, dicumyl peroxide, peroxy esters such as tert-butyl peroxylaurate and tert-butyl peroxybenzoate, and azo compounds such as azobisisobutyronitrile. Further, polymerization accelerators such as metal soaps such as cobalt and manganese for the above-mentioned ketone peroxides, or cyclic amines for the above-mentioned hydroperoxides can also be used. As mentioned above, the curable resin of the present invention has a composition comprising a cationic unsaturated polyurethane resin and a general formula:
Contains a crosslinking agent containing the specific ethylenically unsaturated compound (1), and its cured product is flexible, tough, and has excellent adhesive properties, and is used for various purposes such as paints, inks, and adhesives. It is useful for A detailed explanation will be given below with reference to synthesis examples, examples, and examples. Note that "parts" or "%" simply means parts by weight or percent by weight. Synthesis example 1 (a) 2,4-TDI 312.2g (b) 2-hydroxyethyl acrylate (HEA) 208.2g (c) Dibutyltin dilaurate 0.052g Place component (a) in a reactor equipped with a stirring device and heat to 50°C. Then, while maintaining this temperature, the mixture of components (b) and (c) was added dropwise to (b) and (c) over 2 hours and 20 minutes, and then for about 1 hour until no OH absorption was detected in the infrared absorption spectrum (IR). The reaction was carried out for 50 minutes to obtain an intermediate (P ₁ ). (d) 2,4-TDI 386.9g (e) PEG-1000 1123.8g (f) Dibutyltin dilaurate 0.15g After placing component (d) in a reactor equipped with a separate stirring device and heating to 70℃, (e A mixture of components () and (f) was gradually added, and the mixture was allowed to react for about 2 hours and 40 minutes until no OH absorption was detected by IR to obtain an intermediate (P ₂ ). Then (g) Intermediate (P ₁ ) 544.7 g (h) Intermediate (P ₂ ) 1394.4 g (i) N-methyldiethanolamine 234.0 g (j) Dimethyl sulfuric acid 208.8 g Into a new reactor with stirring device (g) After adding component (h) and heating to 50℃, add component (i) while maintaining the temperature of and react for 2 hours and 30 minutes until no NCO absorption is detected by IR, then add component (j). A mixture of 595.5 g of tetrahydrofurfuryl acrylate and 3 g of hydroquinone was gradually added, and after the addition, the reaction was continued for another 30 minutes to obtain a solution containing 80% by weight of the cationic unsaturated polyurethane resin (I). Synthesis example 2 (k) 2,4-TDI 410.3g (l) PTMG1000 603.2g (m) PHA1000 586.7g (n) Dibutyltin dilaurate 0.17g Place component (k) in a reactor equipped with a stirring device and heat to 85°C. A mixture of components (l), (m), and (n) was gradually added dropwise into the solution, and the mixture was allowed to react for about 2 and a half hours until no OH absorption was detected by IR. Then, after lowering the liquid temperature to 80℃, (o) HEMA 153.1g (p) MEHQ 3.8g (q) Methyl ethyl ketone 473.7g (r) N-methyldiethanolamine 66.2g (s) Dimethyl sulfate 71.2g (o), ( A mixture of components p) and (p) is reacted dropwise, and after about an hour and a half, component (r) is reacted dropwise, and then component (s) is added while the liquid temperature is lowered to 60°C. After reacting for a while, a cationic unsaturated polyurethane resin solution () having a solid content of 80% by weight was obtained. Synthesis example 3 TDI (192.3g) was placed in a reactor equipped with a stirring device.
Heated to 90℃ and prepared polyethylene adipate (molecular weight
1000) 552.1 g was gradually added dropwise and reacted for about 3 hours, then a mixed solution of 62.8 g of HEA and 1.67 g of hydroquinone was gradually added dropwise and reacted for about 2.5 hours, and then 28.0 g of diethylene glycol was gradually added dropwise to form a nonionic solution. A polyurethane resin () was obtained. Examples 1 to 5 The cationic unsaturated polyurethane resin (PU) obtained in the synthesis example and the various crosslinking agents listed in Table 1 were used in the proportions listed (PU is calculated as solid content) to produce the products of the present invention. A curable resin composition was produced. In the table, HEMA stands for hydroxyethyl methacrylate,
HPMA is hydroxypropyl methacrylate,
HBMA is hydroxybutyl methacrylate,
HPA is hydroxypropyl acrylate, THF
-A is tetrahydrofurfuryl acrylate, M
-5E indicates HEMA with 5 moles of ethylene oxide added, and M-8E indicates HEMA with 8 moles of ethylene oxide added. For formulations using PU(), solvent drying was performed at 60°C for 24 hours before curing. In addition, in order to investigate the properties of the resin, to prepare a film, the above resin solution was placed on a Teflon-coated steel plate to a dry thickness of 0.3 mm.
After pouring and leveling it, and drying it in an oven at 60℃ for a day and night, use a curtain beam type electron beam irradiation device to obtain an irradiation dose of 12 Mrad at an acceleration voltage of 200 KeV and a beam current of 12 mA. The film was cured by irradiation. Regarding the preparation of the coating film, the above resin solution was applied to a 50μ thick steel plate with a degreased surface using an applicator so that the dry thickness was 30μ, and then dried in an oven at 80℃ for 5 minutes. After this, the coating film was cured by irradiation using the above-mentioned apparatus at an acceleration voltage of 150 KeV and a beam current of 7.4 mA to a dose of 10 Mrad. The physical properties of the obtained film and coating were determined according to JIS K6301 and JIS K5400, respectively.
Measured according to. In addition, the unit in the table is 100
% modulus (Kg/cm ² ), tensile strength (Kg/cm ² ), and elongation at break (%).
A load of 500g was used. The results are also shown in Table 1. Comparative Examples 1 to 7 Curable resin compositions were prepared in the same manner as in Examples using cationic or nonionic unsaturated polyurethane resins according to the formulations shown in Table 2, and their properties were measured. The results are also shown in Table 2.

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Claims (1)

[Scope of Claims] 1. A curable resin composition containing an unsaturated polyurethane resin having two or more terminal groups having a polymerizable ethylenically double bond and having n of 1,300 to 20,000 and an ethylenically unsaturated compound. wherein the unsaturated polyurethane resin is a cationic unsaturated polyurethane resin, and the ethylenically unsaturated compound has the following general formula: A curable resin composition characterized by containing as a main component a compound represented by the formula (wherein A represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms). 2 The weight ratio of cationic unsaturated polyurethane resin and ethylenically unsaturated compound is 30:70 to 95:
5. The curable resin composition according to claim 1, wherein the curable resin composition is in the range of 5.