JPS60173009A - Curable composition - Google Patents

Abstract

PURPOSE:A light- or radiation-curable composition having excellent mechanical properties, containing a (meth)acrylate of a polyhydroxyhydrocarbon polymer. CONSTITUTION:A curable composition comprising a (meth)acrylate of a polyhydroxyhydrocarbon polymer of a number-average MW of 500-20,000 and, optionally, a photopolymerization initiator. A normally liquid or brittle waxy polymer having an average of at least 1.5, preferably 1.8-8.0, hydroxyl groups per molecule and having a main chain comprising a hydrocarbon is used. The preferred polyhydroxyhydrocarbon polymer is a hydrogenated polyhydroxydiene polymer. Examples of the photopolymerization initiators used include benzoin methyl ether and benzophenone. The amount of the initiator is 0.05-10wt% based on the total polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photo- or radiation-curable composition using a compound having a backbone of a polyhydroxy hydrocarbon polymer.

Conventionally, various photocurable compositions are known and used as coatings for paints and other coatings, but photocurable compositions with a backbone of a polyhydroxy hydrocarbon polymer having a specific molecular weight are unknown.

The present invention provides a new curable composition with excellent mechanical properties.

That is, in the present invention, the number average molecular weight is 500 to 2000.
The present invention relates to a photo- or radiation-curable composition comprising a (meth)acrylate of a polyhydroxy hydrocarbon polymer of No. 0 and, if necessary, a photopolymerization initiator. here (meta)
The word acrylate refers to both acrylate and methacrylate, but hereinafter it may also be simply referred to as acrylate.

To explain the present invention in more detail, the polyhydroxy hydrocarbon polymer (polyolefin polyol) used to produce the curable composition of the present invention has an average number of hydroxyl groups per molecule (hereinafter simply 1" hydroxyl group). A wax having a molecular weight of 1.5 or more, preferably 1.8 to 8.0, a number average molecular weight of 500 to 20,000, a main chain structure of hydrocarbon, and a liquid or brittle wax at room temperature. Those with the following shapes are used.

Various types of polyhydroxy hydrocarbon polymers can be mentioned. For example, hydrogenated or partially hydrogenated polyhydroxydiene polymers, oxidative decomposition and reduction products of isobutylene-diene monomer copolymers, α-olefin (e.g., ethylene, propylene, etc.)-nonconjugated diene (or Examples include oxidative decomposition and reduction products of conjugated diene) copolymers. Among these, hydrogenated products of polyhydroxydiene polymers are preferred.

Thus, the polyhydroxydiene polymer is produced using a conjugated diene or a conjugated diene and monomer as raw materials by a well-known method such as a radical polymerization method or an anionic polymerization method. In the case of radical polymerization, if the polymerization is carried out using hydrogen peroxide as a polymerization initiator, a conjugated diene polymer or copolymer having a hydroxyl group directly at the end can be obtained, but in the case of anionic polymerization, an alkali metal is first added to the end using an anionic polymerization catalyst. A pink polymer with a structure in which these are bonded is produced, and then a monoepoxy compound, formaldehyde, etc. are reacted. As the raw material conjugated diene, isoprene, chlorobrene, etc. can also be used, but butadiene-1,3 is preferred. Examples of copolymerization components include monomers such as styrene, acrylonitrile, methyl (meth)acrylate, and vinyl acetate. The amount of the copolymer component used is preferably 30% by weight or less of the amount of assembly material.

In addition, hydrogenation when producing hydrogenated products of polyhydroxydiene polymers is carried out by a conventional method using a catalyst such as nickel, cobalt, platinum, palladium, ruthenium, or rhodium alone or supported on a carrier. It may be carried out under hydrogen. Furthermore, a partially hydrogenated polyhydroxydiene polymer may also be used.

Other methods for producing hydrocarbon polymers having hydroxyl groups include a method in which a copolymer of an α-olefin and another heptamer is oxidatively decomposed and then reduced. For example, polyhydroxypolyisobutylene can be obtained by subjecting a butyl rubber-based polymer obtained by cationic polymerization of isobutylene and butadiene or 1,3-pentadiene to ozone decomposition treatment and then reducing it with lithium aluminum hydride.

In addition, in this invention, a part of polyhydroxy hydrocarbon type polymer can also be substituted with another polyol.

Examples of such polyols include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone polyol, castor oil, ethylene glycol, lower polyols such as trimethylolpropane, and trimethylolpropane. Examples include ethylene oxide adducts of lower polyols. Replaced (6
) is 0 to 4 of the polyhydroxy hydrocarbon polymer.
9% by weight is suitable. If it exceeds this range, the characteristics of polyhydroxy hydrocarbon polymers, such as excellent hydrolysis resistance, weather resistance, and heat resistance, will be lost.

There are no particular restrictions on the method of acrylating a polyhydroxy hydrocarbon polymer, but examples include transesterification of a polyhydroxy hydrocarbon polymer and an acrylic ester, or transesterification of a polyhydroxy hydrocarbon polymer and a polyisocyanate. Examples include a method in which a prepolymer containing an isocyanate group is once produced by reacting a prepolymer with an isocyanate group, and then reacted with an acrylate compound containing a functional group capable of reacting with the isocyanate group, preferably a hydroxyalkyl acrylate. Examples of acrylic esters used in the former method, that is, transesterification, include:
Examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and the like.

In the transesterification reaction, 0.1 to 30 equivalents of acrylic acid ester per equivalent of hydroxyl group are reacted at room temperature to 150°C in the presence of a catalyst such as para-toluenesulfonic acid if necessary.

The polyisocyanate used in the latter method may also be a conventionally known polyisocyanate, such as aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diinocyanate, tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenyl-4,4'-
Aromatic diisocyanates such as diisocyanate, 3-
Methyl isocyanate-3,5,ri-1-limethylcyclohexyl isocyanate, dicyclohexylmethane-
Examples include alicyclic diisocyanates such as 4,4'-diisocyanate.

The prepolymerization reaction is 0.5 to 1 per equivalent of water 1i1 group.
5 equivalents of isocyanate are reacted at room temperature to 200° C. for 0.1 to 20 hours, optionally in the presence of a catalyst. Ma IC%
Hydroxyacrylates may also be conventionally known ones, such as 2-human 0xyethyl (meth)acrylate, 2
-Hydroxypropyl (meth)acrylate-1~, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, pentaerythritol triacrylate, and the like. The acrylation reaction is 0.5 to 1 per equivalent of isocyanate group.
5 equivalents of hydroxyacrylate at room temperature to 200°C.
．． Allow to react for 1 to 20 hours.

In order to avoid gelation due to thermal polymerization during the production or storage of acrylate, 0.001 to 1% by weight of radical polymerization inhibitors such as hydroquinone and parabenzoquinone are added.
It is preferable to add it in advance.

In addition, when it is preferable to lower the viscosity of the reaction system during the acrylation reaction, organic solvents such as carbons, esters, ethers, and hydrocarbons may be added. Furthermore, a liquid ethylenically unsaturated compound capable of radical polymerization may be added, and this may be directly copolymerized as a component of the curable composition. Examples of the ethylenically unsaturated compound include styrene, aromatic hydrocarbon vinyl monomers such as vinyltoluene, (meth)acrylic acid esters, allyl esters, acrylonitrile, and the like. (meta)
Examples of acrylic esters include 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate-1
~, ethylene glycol di(meth)acrylate-1~, diethylene glycol di(meth)acrylate, 1.6-
Examples include hexanethiol di(meth)acrylate, neobentylglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and the like.

Although the photopolymerization initiator is not particularly limited,
Benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether,
Examples include benzophenone, and these can also be used together.

The amount of photopolymerization initiator used is 0.05 to 10 weight of the total polymer.
%, preferably 0.1 to 5%.

The active light for photocrosslinking has a wavelength of 200 nm.
A light beam of ~800 n+μ is used, and for example, light beams such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a sodium lamp, an ultraviolet fluorescent lamp, and sunlight can be used. Using these light sources, complete curing can usually be achieved by irradiation for 0.1 to 100 minutes. When the curing means is ionizing radiation such as electron beams or gamma rays, curing occurs quickly, so there is no need to use a polymerization initiator. Moreover, it can also be hardened by scanning with a beam of laser light.

In addition to the above-mentioned components, the curable composition of the present invention may contain a plasticizer, a colorant, a filler, or other auxiliary agents.

The curable composition of the present invention has excellent mechanical properties, heat resistance,
It has weather resistance, hydrolysis resistance, and electrical insulation properties, and is suitable for coating metal products, ink for printed circuit boards, printing ink, vinyl flooring, and anti-vibration, waterproof, and moisture-proof coatings for electrical and electronic industrial surfaces. It can be used as such, and is extremely important industrially.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 Synthesis of acrylic polyolefin polyol Hydroxyl group 1
1 to 0.788n+eq/u, number average molecule ff130
00 polyolefin polyol (Polytail ■1”),
Mitsubishi Chemical Industries, Ltd.! ! 1) Mix 1000Q and 600g of methyl acrylate, then add hydroquinone O,ig
, para-toluenesulfonic acid as a transesterification catalyst5.
After adding 0g, the temperature was raised to 80℃ and nitrogen was added to 150℃.
The transesterification reaction was carried out while flowing at a rate of 0 d/min and discharging the generated methanol together with methyl acrylate.

After 8 hours, the presence of methanol was no longer recognized in the distillate, and the reaction was stopped when the amount of distillate m became extremely small. When the infrared absorption spectrum of the product was measured, it was found that the absorption of hydroxyl groups present in the raw material polyolefin polyol had almost disappeared.

The obtained product was dissolved in toluene, and the dissolved product was poured into aretone to remove para-toluenesulfonic acid contained in the product.

Hydroquinone was newly added to the purified product, and the mixture was dried under reduced pressure at 50° C. for 1 hour in a reduced-pressure dryer to obtain an acrylate-modified polyolefin polyol.

Production of curable composition The above acrylate-modified polyolefin polyol 100
g, lauryl, dodecyl (mixed) acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) 25 (], benzophenone 1.25 (])
, mixed with 2.5 g of benzoin isopropyl ether,
Melt it uniformly at 80℃, coat it on a glass plate, and make a 75μ
A layer of thickness was formed.

This coated product was exposed and cured for 10 seconds using a Ushio Electric's I U V H2000 mercury lamp at an irradiation intensity of 80 W/cm to obtain a cured film. The tensile strength of the obtained cured film was 150 Kg/a+'.

The elongation was 200%.

Example 2 Synthesis of acrylic modified polyolefin polyol Hydroxyl group: 893TIIOQ/+1, number average molecular weight: 2
After mixing 1'000 g of polyolefin polyol (Polytail IA manufactured by Mitsubishi Chemical Industries, Ltd.) and 199 g of isophorone diisocyanate at air temperature, the mixture was heated to 115°C.
The temperature was raised by immersing it in an A-il bath. When both were uniformly mixed, 1.2 g of dibutyltin dilaurate was added as a urethanization catalyst, and the mixture was reacted at 115° C. for 6 hours to produce a prepolymer. The infrared absorption spectrum of the product was measured, and it was confirmed that the hydroxyl groups in the raw material polyolefin polyol had almost disappeared.

Next, 0.0% of hydroquinone was added to all m of the above prepolymer.
After adding 65a, 108 g of 2-hydroxyethyl acrylate was added and reacted at 80° C. for 71 hours to synthesize an acrylate-modified polyolefin polyol.

Production of monocurable composition The above acrylate-modified polyolefin polyol 100
g to trimethylolpropane trimethacrylate-1-25
+7, add 2.5g of benzoin butyl ether, 80
A photocurable composition was synthesized by uniformly dissolving the mixture at ℃.

The obtained photocurable composition was coated on a glass plate, and 75
A layer with a thickness of μ is formed.

This coated product was exposed to light for 10 seconds at an irradiation intensity of 80 W/Cm using a UV)-12000 mercury lamp manufactured by Ushi A Denki Co., Ltd., and cured to obtain a cured film. The resulting cured film had a tensile strength of 52K (1/cm') and an elongation of 70%.

Applicant: Mitsubishi Chemical Industries, Ltd. Represented Patent Attorney Hase - (1 other person)

Claims (1)

[Claims] (1) A photo- or radiation-curable composition comprising (meth)acrylate of a polyhydroxy hydrocarbon polymer having a number average molecular weight of 500 to 20,000 and optionally a photopolymerization initiator.