JPS6071624A - Curing resin - Google Patents

Abstract

PURPOSE:A curable resin that is obtained by adding an ethylenically unsaturated compound mainly composed of a specific compound to a specific unsaturated polyurethane resin, thus giving a cured product by irradiation with electron beams, being suitable for coating, ink, etc., because of its high adhesion, flexibility and toughness. CONSTITUTION:The objective curable resin is obtained by adding (A) an ethylenically unsaturated compound, preferably more than 60wt% of an ethylenically unsaturated compound of the formula [A is 2-4C (holo)alkyl] as a crosslinking agent to (B) an unsaturated polyurethane of 1,300-20,000 average molecular weight having 2 or more terminal groups of polymerizable ethylene double bonds, preferably at a weight A/B of 50/50-20/80.

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. Such a photosensitive composition has a backbone of polyester resin, polyurethane resin, epoxy resin, etc., and contains two polymers that can be polymerized by radiation.
Resin compositions having multiple bonds are often used, but they generally do not contain volatile organic solvents or contain only a small amount of volatile organic solvents, which is very preferable from the point of view of environmental protection, and also helps in saving energy and curing. It is also superior in terms of overall economic efficiency, taking into account various factors such as time savings, so paints, printing inks, adhesives, flexible circuit overlays and other coating materials, solder resists for printed circuit boards, etching resists, etc. It has been put into practical use in a wide range of fields, including inks for metsuki resists and 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 or solvent-volatile resins, they lack adhesion to surrounding resins or metals, so their use in the various applications mentioned above is often limited. . On the other hand, there are some radiation-curable resins that have excellent adhesion141, but in those cases, problems often arise in the rapid curing property that is their original characteristic1.
Radiation-curable resins whose main ingredients are additives cure rapidly when irradiated with radiation M and have high hardness, but they have the disadvantage of poor toughness and poor adhesion due to large shrinkage during curing. Was. 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 this, efforts have been made to modify materials, improve compositions, and even add thermoplastic resins and thermosetting resins that are not directly involved in radiation curing reactions, but these efforts do not necessarily meet the intended purpose. Cases where this cannot be achieved: (1) The purpose of the present invention is to select a specific compound as a crosslinking agent to be used in combination with an unsaturated polyurethane resin, thereby imparting flexibility and strong blade properties to the resulting cured product. Another object of the present invention is to provide a curable resin that has significantly improved adhesion to various adherends. The present invention is a curable resin having two or more terminal groups having a polymerizable ethylenically double bond and containing an unsaturated polyurethane resin having an Mn of 1,300 to 20,000 and an ethylenically unsaturated %li+ compound, The ethylenically unsaturated compound is characterized by containing as a main component a compound represented by the following general formula % (1) (in the formula, the person represents an alkylene group having 2 to 4 carbon atoms or a 10 alkylene group). It relates to curable resins. The unsaturated polyurethane resin of the present invention is, for example, a polyol (
5) can be obtained by various methods using an organic polyisocyanate (B) and an ethylenically unsaturated compound 0 capable of absorbing active hydrogen. As the -1 Natsuki polyol (5), 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, superic acid, senoacic acid, and brassylic acid, terephthalic acid, and isophthalic acid as acid components, and ethylene glycol, propylene glycol, and neopentyl. Polyol components include aliphatic diols having 1 to 6 carbon atoms such as glycol and hexamethylene glycol, ether glycols such as diethylene glycol and dipropylene glycol, spiroglycols, and N-alkyl dialkanolamines such as N-methyljetanolamine. Specific examples include adipate polyols such as polyethylene adipate polyol, polybutylene adipate polyol, and polyethylene propylene adipate polyol, and terephthalic acid polyols (e.g., Toyobo Co., Ltd., commercial products). Name Byron 1.1. U
X, Vylon RV-20OL>, polycaprolactone 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. Other polyols include epoxy group-containing polyols (e.g. Shell Kagaku Co., Ltd., trade name Ko Picoat 828).
, 834 , +001 , 1002, 1003 , +
004), polycarbonate polyol (e.g., Bayer AG, West Germany, trade name Desmophen 2020E), polybutadiene polyol (e.g. Nippon Soda, trade name G-10)
00, G-2000, G-3000, Idemitsu Petrochemical Co., Ltd. (trade name: Poly bd R-45HT), polypentadiene polyol, castor oil polyol, etc. These polyols are 1 type or 2 + "■"
Both can be used simultaneously. Examples of the organic polyisocyanates used in the present invention preferably include monolayers, such as diphenylmethane diisocyanate (MDI), lylene diisocyanate (TDI), and toridine diisocyanate (TOI).
I), xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI), isoporone diisocyanate 1-(IPDI), hexamethylene diisocyanate (i(DI)), dicyclohexylmethane diisocyanate (1-I MDI), lysine diisocyanate (L Examples include diisocyanates such as I) I), triphenylmethane triisocyanate, polymethylene polyphenylisocyanate (1) API), and carposiimide-modified MJ) I':Q polyisocyanates, and these include IJffi or two or more types. can be used simultaneously. In the present invention, various types of ethylenically unsaturated compounds having active hydrogen can be used; representative examples include ethylene glycol, propylene glycol, 1,3-propanediol, and 1゜3-butanediol. , mono(meth)acrylates of dihydric alcohols such as 1,4-butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, mono- and di(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerin. 4 such as meth)acrylate, pentaerythritol, etc.
Examples include di- and tri(meth)acrylates of alcohols having higher valences, and these may be used alone or in combination of two or more. In the synthesis of the unsaturated polyurethane resin of the present invention,
It is also optional to use a chain extender (D) in addition to the compounding ingredients.
The following 2 to (i-functional polyol and molecular weight ゛500
The following diamines having a primary or secondary terminal amino group can be mentioned. Examples of suitable chain extenders include (a) ethylene glycol, diethylene glycol,
Polyols (b) such as propylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, 1,4-cyclohexanediol, 1,4-cyclohexane dimetatool, xylylene glycol, etc. Diamines (C) such as hydrazine, ethylenediamine, TeI-ramethylenediamine, hexamethylenediamine, l,4-cyclohexanediamine, etc. Alkanolamines such as ethanolamine, jetanolamine, and 1-liethanolamine (d) Hydroquinone, Pyrogallol, 4,4-isopropylene diphenol, aniline and the above polyols, diamines,
Examples include polyols having a molecular weight of 500 or less obtained by adding propylene oxide and/or ethylene oxide to alkanolamines in any order. When synthesizing the 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. The chemical equivalent ratio of the active hydrogen group contained in the compound (Q and the chain extender G used as necessary) and the NCO group of the organic polyisocyanate-1 to (g) is 09 to 14, preferably 0. It is best to react in the range of .95 to 12, and the reaction is usually 30 to 130°.
C1 is preferably carried out at 40 to 120°C. In the present invention, the 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, which will be 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. 113 (1) Cl-12=C-COO-A-OH (1) (in the formula, A represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms). Specific examples include monomethacrylates such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, I,4-butanediol, and 3-chloro-2-hydroxypropyl. Examples include methacrylate. The reason for employing the compound of general formula (1) in the present invention is: (1) When comparing acrylate and methacrylate,
In terms of physical properties and adhesion of the cured product, the use of methacrylate is significantly superior. (2) When comparing the presence or absence of OH groups among the same methacrylates, those having OJ-1 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) has significantly improved physical properties and adhesion of the cured product compared to a compound having the same OH group as a methacrylate with a larger molecular weight by connecting the alkyl group with an ether bond. It is excellent. In the present invention, unsaturated polyurethane resin and general formula (1)
The weight ratio of the ethylenically unsaturated compound containing the compound is preferably 30:0 to 95:5, and 50:50 to 80.
:20 is more preferable. If 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 as long as the purpose is not impaired, and specific examples of these compounds include unsaturated polyester resins, saturated polyester resins, epoxy resins, and (meth)acrylic acid, etc. esters, polyurethane resins, realyl phthalate resins, ketone resins, alkyds (ffJ resins, phenolic resins, rosin-modified phenolic resins, rosin esters, maleic acid-modified rosin esters, urea resins, melamine resins, polyamide resins, styrene (meth) ) Acrylic acid copolymer or its ester, styrene-maleic anhydride resin or its ester, poly(meth)acrylate, 05-C9
petroleum resin, hydrogenated petroleum resin, polybutadiene, natural or synthetic rubber, polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, polyvinyl alcohol,
Examples include 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 unsaturated polyurethane resin of the present invention. In the present invention, other ethylenically unsaturated compounds may be used as crosslinking agents as necessary when curing the curable resin described in item 2. Various known compounds can be used as ethylenically unsaturated compounds, but representative examples include styrene, rene, and vinyl

[2ene, chlorostyrene, t-butylstyrene, α-methylstyrene, divinylbenzene, acrylic acid, methacrylic acid, methyl, ethyl, isopropyl acrylic acid or methacrylate, 1
]-butyl, t-butyl, α-ethylhexyl, ]]-
Nonyl, 1]-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, Nt-butylaminoethyl ester, etc., ethylene glycol monoacrylate,
Propylene glycol monoacrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, molecular weight (-hereinafter MW
)200-1000 polyethylene glycol mono(meth)acrylate, MW200-1000 polyethylene glycol monomethyl ether mono(meth)acrylate, (W200-1000 polypropylene glycol mono(meth)acrylate, MW200-1
000 polypropylene glycol monomethyl ether mono(meth)acrylate), MW200-1000 polyethylene glycol monoethyl ether mono(meth)acrylate, MW2.00-1000 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. -Hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, glycerin di(meth)acrylate
Acrylate, glycerin I/su(meth)acrylate, trimethylolethane (meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate-1-, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, ethylenebisacrylamide,
Examples include diallyl phthalate, triallyl isocyanurate, dibutyl fumarate, and vinyl acetate. However, if present during the urethanization reaction, 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, more preferably 10% by weight or more. Known thermal polymerization inhibitors can be added.For example, hydroquinone, mono-tert-butylhydroquinone, 2,5-;-tert-butylhydroquinone, hydroquinone monomethyl ether, catechol, 1
)-tert-butylcatechol, benzoquinone, 2,
Examples include 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 suppressing the photocuring reaction, and therefore, the addition 1 will increase the total amount of the unsaturated polyurethane resin and crosslinking agent. It is desirable that the amount is in the range of 0001 to 25% by weight, preferably 0005 to 1% by weight. Furthermore, in the present invention, if necessary, a dispersing agent, which is commonly used,
Additives such as lubricants, abrasives, antistatic agents, etc. can be added. Furthermore, in the present invention, additives such as colorants, flame retardants, and lubricants commonly used in applications such as paints, inks, and adhesives, and fillers such as glass, mica, and iron powder may be added. good. The curable resin of the present invention can be cured by a known method. For example, when curing with an electron beam, an electron beam irradiation device with an accelerating voltage of 20 to 2000 KeV is used in an inert gas atmosphere so that the total absorption line m is 0.5-505-5O,
A cured product can be obtained by irradiating preferably at 2-30 Mrad. In addition, in the present invention, other curing means such as those using thermal energy such as infrared rays, high frequency waves, or microwaves, that is, heating curing methods, curing methods using ultraviolet rays obtained from mercury lamps, xenon lamps, etc., or X-rays, γ-rays, etc. It can also be done using other radiation curing methods. 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, no polymerization initiator is particularly required. However, 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 te-butyl peroxide, and di-t6rt-butyl peroxide. oxide, dialkyl peroxides such as dicumyl peroxide, te
Peroxy esters such as rt-butyl peroxylaurate and tert-butyl peroxybenzoate,
Examples include azo compounds such as azobisisophthyronitrile. Further, polymerization accelerators such as metal soaps such as cobalt and manganese for the above-mentioned ketone peroxides, or reducing amines for the above-mentioned /'% idrobaroxides can also be used. As described above, the curable resin of the present invention contains a crosslinking agent containing an unsaturated polyurethane resin and a specific ethylenically unsaturated compound of general formula (1), It is strong and has excellent adhesion properties, making it useful for various uses such as coatings, inks, adhesives, etc. The following is a detailed explanation with synthesis examples and examples. ,
A simple part or % indicates a mold part or a mold part. Synthesis Example 1 TDI (1923f
) and warm it to 90°C, then add polyethylene adipate (
Molecular weight! 000) 552.1f was gradually added dropwise and reacted for about 3 hours, and then a mixed solution of 628g of 2-hydroxyethyl acrylate (ethylene glycol monoacrylate, hereinafter abbreviated as HE A) and hydroquinone 1672 was gradually added dropwise and reacted for about 3 hours. After reacting for 2.5 hours, diethylene glycol 2807 was gradually added dropwise to obtain an unsaturated polyurethane resin (1). Synthesis example 2 (a) 2.4-'I''D I 312.2f(+))
HIUA, 208.29 (C) Dibutyltin dilaurate 0.0521 Put component (a) into a reactor using a stirrer, heat to 50°C,
While maintaining this temperature, the mixture of components (b) and (C) was added dropwise over a period of 2 hours and 20 minutes, and then the mixture was added dropwise for about 1 hour until no OH absorption was detected in the infrared absorption spectrum (IR).
After stirring for 50 minutes, an intermediate (P+) was obtained. (d) 2.4- T DI 386.9 g(e)
PEG-10001123, 8g (f) Dibutyltin dilaurate 0157 In a reactor with a separate stirring device (d
) After adding the ingredients and heating to 70°, (e) and (f)
The mixture of components was gradually added and reacted for about 1 hour and 50 minutes until no OH absorption was detected at In, to form the intermediate (
P2) was obtained. Then (g) Intermediate (Pl) 54717g (11) Intermediate (P2) 13q44. q(1) N-methyljetanolamine 2340ii'(j) Dimethyl sulfate 208. Pl Add ingredients (g) and (11) to a reactor using a new stirring device, heat to 50°C, and then heat (i) while maintaining this temperature.
) was added and reacted for 2 hours and 3.0 minutes until the absorption of NCO was no longer detected in II (,), and then the (j) component, tetrahydrofurfuryl acrylate-1-5955!i' and hydroquinone 37 were reacted. The mixture was added gradually and reacted for an additional 30 minutes after the addition to form an unsaturated polyurethane resin (I[
) was obtained at a concentration of 80 times. In Examples 1 to 2, the unsaturated polyurethane resins (PU) obtained in the synthesis examples and the various crosslinking agents listed in Table 1 were mixed in the proportions listed in the table (P (-
The curable resin of the present invention was produced using the following method: T (17J, solid content exchanged). In the table, HEMA is hydroxyethyl methacrylate, HPMA is hydroxypropyl methacrylate, J (BMA is hydroxybutyl methacrylate, HPA is H)・' roxybrovir acrylate, DMA is ethyl methacrylate-1, 1) M A is provirun tacrylate. THF-A is tetrahydrofurfuryl acrylate, M-5E is HEMA with 5 moles of ethylene oxide added, and Mff8E is HEMA with 8 moles of ethylene oxide added. In order to investigate the properties of the resin, the resin was applied onto a glass plate using an applicator, and the resin was cured using a curtain beam type electron beam irradiation device. I S K (33
0] and JIS f (5400). In the table, the unit is 100Φ modulus (kQ/cn
D), tensile strength (A: (J/crJ), elongation at break (
%), and a load of 500 g was used in the DuPont impact.The results are also shown in Table 1. Comparative Examples 1 to 10 Curable resins were prepared in the same manner as in the examples using the formulations shown in Table 2, and all of their properties were measured. The results are also shown in the $2 table. Table 1 Table 2 (hereinafter referred to as ``1-1-'') Procedural amendment (voluntary) October 18, 1981 Commissioner of the Japan Patent Office Kazuo Wakasugi Hardening Resin 3, Relationship with the person making the amendment Case Patent applicant Toyo Gomu Kogyo Co., Ltd. 4, Agent 6, Contents of the amendment to increase the number of inventions due to the amendment 1, Page 24 of the specification, lines 2 to 5, "Glass plate" 2...
. . . harden," [To make a film, pour the above resin solution onto a Teflon-coated steel plate to a dry thickness of 0.3 m + n, level it, After drying in an oven at 60°C for a day and a night, it was heated to an acceleration voltage of 200 KeV using a curtain beam type electron beam irradiation device.
The film was cured by irradiation with a beam current of 12 to A and an irradiation dose of 12 Mrad. Regarding the preparation of the coating film, the above resin solution was applied to a 50μ thick steel plate whose surface had been degreased using an applicator to a dry thickness of 30μ, and then placed in an oven at 80°C for 5 minutes. After drying, using the apparatus described in 61j, the accelerating voltage was 150 KeV and the beam current was 7.4 mA for 10 years.
The coating film was cured by irradiating the film at an irradiation dose of d. ” I am corrected. 2. Add the value from 2 to [14L296.148] in the column for Formulation 4 in Table 1 on page 25 of the specification, in the blank column for film physical properties. (hereinafter “2”)

Claims (2)

[Claims] (1) A curable resin containing an unsaturated polyurethane resin and an ethylenically unsaturated compound having two or more end groups having a polymerizable ethylenically double bond and having an Mn of 1,300 to 20,000, A curable compound characterized in that the sexually unsaturated compound is a compound represented by the following general formula % (1) (in the formula, the human represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms) as a main component. resin. (2) The curable resin according to claim 1, wherein the ratio of the unsaturated polyurethane resin to the ethylenically unsaturated compound is in the range of 30 nia 0 to 95:5 by weight.