JP3474640B2 - Photopolymerization method and photopolymerization apparatus used for this reaction - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a (meth) acrylic acid ester of an alkyl alcohol used as a raw material for an ultraviolet curable resin or a coating liquid, which is applied to a support such as a plastic film, paper, a release film and a metal foil. The present invention relates to a photopolymerization device for obtaining prepolymers and oligomers containing as a main component.

[0002]

2. Description of the Related Art For example, various double-sided adhesive tapes are used in various industrial fields. Many of them are coated with acrylic adhesive. As the acrylic pressure-sensitive adhesive, a solution-type or water-dispersion type emulsion in which a compound copolymerizable with a (meth) acrylic acid ester of alkyl alcohol is polymerized by solution polymerization or emulsion polymerization is used.

In recent years, ultraviolet ray and electron beam curable solventless adhesives containing acrylic monomers and oligomers as main components have been attracting attention from the viewpoint of environmental pollution countermeasures. UV-curable adhesives are mainly composed of a composition consisting of (meth) acrylic acid ester and a compound capable of copolymerization, but have low viscosity. Therefore, add a thickener to adjust the viscosity so that it can be applied. It is necessary to prepolymerize the curable pressure-sensitive adhesive to have an appropriate viscosity.

As the thickener, a polymer, an oligomer or an inorganic filler is generally used. Polymers and oligomers used as thickeners are difficult to select because few of them are compatible with UV-curable adhesives. On the other hand, the inorganic filler requires a special mixer to disperse it in the UV-curable pressure-sensitive adhesive, and the UV-curable pressure-sensitive adhesive after dispersion causes precipitation of the inorganic filler, resulting in poor solution stability.

It is a good method to prepolymerize the UV-curable pressure-sensitive adhesive composition to increase the viscosity so that it can be applied.
When the composition contains a component which easily reacts or gels, it is difficult to obtain a uniform coating solution having a desired viscosity range and a small amount of partial gel. For prepolymerization, the following batch type polymerization apparatus, that is, a heating polymerization vessel having heating and cooling functions and capable of controlling the internal temperature is widely used. Alternatively, a photopolymerization kettle in which a tubular lamp protected by a light-transmitting tube such as a quartz tube is placed in the kettle, or a photopolymerization kettle made of quartz glass so that light can be irradiated from the outside of the kettle is used. It

[0006]

When a composition comprising a (meth) acrylic acid ester of an alkyl alcohol and a copolymerizable compound and a thermal polymerization initiator is polymerized in a heating polymerization kettle, a peroxide or an azo compound is formed. Once the decomposition occurs, it is difficult to stop it because the reaction proceeds in a chain. Even if the internal temperature is cooled, it is difficult to control the polymerization reaction. Therefore, it is difficult to produce a prepolymer having a desired viscosity range. Further, there is a risk of explosion if the heat generated by the polymerization reaction is not controlled.

The composition obtained by changing the thermal polymerization initiator of the above composition into a photopolymerization initiator is placed in a quartz polymerization kettle and irradiated with ultraviolet rays from a high pressure mercury lamp or a medium pressure mercury lamp to polymerize the composition. Even when the lamp cannot be turned on instantly, it takes several minutes until the light intensity stabilizes, so it is difficult to control the polymerization, and the polymer adheres to the wall of the container or partially gels. There are drawbacks such as. Even with the UV irradiation method, it is difficult to obtain a prepolymer having a desired viscosity unless the UV irradiation method is devised.

The present invention photopolymerizes the above-mentioned prepolymer of the UV-curable pressure-sensitive adhesive to produce a prepolymer having a desired viscosity without partial gel, which is difficult in the prior art, by a safe and inexpensive method. It is an object of the present invention to provide a photopolymerization device that can be used.

[0009]

The present inventors have found that when a photopolymerizable composition containing a (meth) acrylic acid ester of alkyl alcohol and a copolymerizable compound as a main component is irradiated with ultraviolet rays in a nitrogen gas atmosphere, However, it was found that the polymerization reaction was stopped within a few seconds when the irradiation was stopped. From this, the photopolymerization apparatus of the present invention capable of controlling the photopolymerization reaction was completed. This photopolymerization apparatus can be used in a method of producing a uniform liquid prepolymer (hereinafter referred to as a prepolymer) having a desired viscosity range of a photopolymerizable composition and having a small amount of partial gel.

The composition to be preliminarily polymerized was also a composition obtained by removing from the UV-curable pressure-sensitive adhesive composition a component that easily reacts or gels.

The photopolymerization device used in the present invention is a light comprising an ultraviolet ray generating means 1 comprising a high pressure mercury lamp 2, a condenser mirror-3 and a shutter device 4, and an optical fiber for propagating the ultraviolet ray generated from the ultraviolet ray generating means 1. It is composed of a propagation means 5 and a photopolymerization pot 6.

The ultraviolet rays generated from the spherical high-pressure mercury lamp 2 are collected at one point by the condenser mirror 3 and guided to an optical fiber which is a light propagating means. The optical fiber may be made of quartz or plastic.

A photopolymerizable composition 11 comprising a compound copolymerizable with an acrylic ester monomer of an alkyl alcohol having 2 to 14 carbon atoms and a photoinitiator is placed in a photopolymerization pot 6 and an ultraviolet ray generating means is provided. The photopolymerizable composition in the photopolymerization vessel is irradiated with the ultraviolet light generated in 1 through the light propagating means 5 for several seconds.
Polymerization is gradually advanced while irradiating in a cycle of stopping for several tens of seconds. This makes it easy to obtain prepolymers having the desired viscosity range and low partial gels. The photopolymerizable composition may be first irradiated with ultraviolet rays for several tens of seconds and then irradiated with ultraviolet rays in the above cycle.

The acrylic acid ester monomer of alkyl alcohol having 2 to 14 carbon atoms used in the present invention is an ester of alkyl alcohol having 2 to 14 carbon atoms and acrylic acid. , Ethyl acrylate, butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, isononyl acrylate, isooctyl acrylate, lauryl acrylate, decyl acrylate, etc. Can be used.

Further, in the present invention, a compound copolymerizable with the acrylic ester is used for improving and improving the adhesive property of the adhesive tape. Such a compound has a vinyl group and is selected from those which undergo photopolymerization. Among them, monomers having a functional group such as acrylic acid, methacrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, and glycidyl methacrylate are preferable.

Acrylic esters containing the following alkyl groups, for example, tetrafurfryl acrylate
It is possible to use bisphenol, isobonyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, phenyl acrylate, cyclohexyl acrylate and the like.

Further, oligoester acrylates such as nonylphenoxy polyethylene glycol acrylate and nonylphenoxy polypropylene glycol acrylate.
It can also be used. Also, these monomers
When the copolymer is copolymerized with an alkyl acrylate monomer of an alkyl alcohol having 2 to 14 carbon atoms, the glass transition point of the resulting copolymer is increased. Therefore, the amount of these monomers used is It is preferable that the glass transition point of (1) does not exceed -15 ° C. If the glass transition point of the copolymer is -15 ° C or higher, the tack at room temperature decreases, which is not preferable.

As the photopolymerization initiator, an acetophenone-based or benzophenone-based one is preferable because the polymerization rate is high and the polymerization rate is close to 100%. As such a photopolymerization initiator, a commercially available one can be used.

For example, 4-phenoxydicycloacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-
1-Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoylmethyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like, and mixtures thereof can be used.

The amount of the photopolymerization initiator used is such that the number of carbon atoms is 2 to 1.
0.005 to 0.05 parts by weight is added to 100 parts by weight of the total of 4 alkyl alcohol acrylic ester monomers and the acrylic ester monomers. In particular, 0.01 to 0.02 part by weight is preferable. When the amount is 0.005 parts by weight or less, the polymerization is difficult, and when the amount is 0.05 parts by weight or more, a rapid polymerization reaction occurs and the polymerization cannot be controlled.

In the present invention, a photopolymerization composition containing hollow microspheres (microballoons) for improving the adhesion to the uneven surface was also examined. Micro balloons used in the present invention are USP 3,615,972, US
It can be manufactured by the method disclosed in P4075, 138, USP 4,287, 308 and the like. A vinylidene chloride-acrylonitrile copolymer resin, a methacrylonitrile-acrylonitrile copolymer resin, or the like, which is used as a wall film of microcapsules containing low-boiling hydrocarbons, can be used. 0 using urethane prepolymer
It is also possible to use a microballoon whose wall film is made of urethane rubber from a / W emulsion system.

The wall film of the microballoon is preferably one having solvent resistance and heat resistance. As for the particle size of the micro-balloon, a very fine particle size is not suitable from the viewpoint of compressibility and resilience. Those having an average particle size of 20 to 100 μm can be used.
NobelIn having a wall membrane of preferably 60 to 80 μm and a methacrylonitrile-acrylonitrile copolymer resin
Dustries (Sweden) Expansion
I 091DE and the like are preferred. Also, the amount used is
500gr / c, which is the optimum pressure force for bonding work
In order to be able to be compressed at m ² or less and to be easily restored after removing the pressure, it is preferable to occupy 10 to 50% by volume of the pressure-sensitive adhesive. More preferably, it is 20 to 40% by volume. If it is 10% by volume or less, sufficient compression cannot be achieved, and if it is 50% by volume or more, the mechanical strength of the pressure-sensitive adhesive decreases.

By adding a polyfunctional oligoacrylate having a molecular weight of 300 or more to the prepolymer of the present invention, a pressure-sensitive adhesive having further excellent pressure-sensitive adhesive properties can be obtained. The polyfunctional oligoacrylate having a molecular weight of 300 or more is preferably a compound of 2 or more acrylic acid and a polyol, and having 10 or more carbons between vinyl groups at both ends.
Such a polyfunctional oligoacrylate is used to increase the cohesive strength of the pressure-sensitive adhesive at high temperatures. It is difficult to use a polyfunctional oligoacrylate having a molecular weight of 300 or less, because the distance between the cross-linking molecules becomes short, and even a small amount of use greatly affects the cohesive force.

Examples of the polyfunctional oligoacrylate having a molecular weight of 300 or more include, for example, enene ethylene glycol diacrylate (NK ester A-400, manufactured by Shin Nakamura Chemical Co., Ltd.), tetradecaethylene glycol diacrylate (NK). -Ester A-600, Shin Nakamura Chemical Co., Ltd.
Manufactured by K.K.), ethylene oxide-modified bisphenol A diacrylate (BP-4EA, manufactured by Kyoei-Shisha Yushi-Seikagaku Kogyo Co., Ltd.), propylene oxide-modified bisphenol A diacrylate.
(BP-4PA, manufactured by Kyoeizasha Oil and Fat Chemical Co., Ltd.),
Ethylene oxide modified trimethylol propane triacrylate (TPM-6EO-3A, manufactured by Kyoei Sashisha Oil & Fat Chemical Co., Ltd.), hydroxypivalate neopentyl glycol diacrylate (KAYARAD MAND)
A, manufactured by Nippon Kayaku Kogyo Co., Ltd. and its derivatives (KAYA)
RAD HX-620, Nippon Kayaku Kogyo Co., Ltd. etc. can be used.

The polyfunctional oligoacrylate having a molecular weight of 300 or more is added to the UV-curable pressure-sensitive adhesive composition in such a manner that the acrylic acid ester of alkyl alcohol having 2 to 14 carbon atoms and the copolymerizable compound are used. It is preferably 0.0001 to 0.002 mol per 100 parts by weight in total. If it is less than 0.0001 mol, the heat-resistant holding power of the adhesive tape tends to decrease, and if it is more than 0.002 mol, the tack of the adhesive tape tends to decrease.

The ultraviolet-curable pressure-sensitive adhesive composition used in the present invention may contain a small amount of pigment or dye for coloring so long as it does not hinder the transmission of ultraviolet rays. When the prepolymer of the present invention is used as an ultraviolet-curable pressure-sensitive adhesive, 0.05 to 1.0 part by weight of a photopolymerization initiator is added to 100 parts by weight of the prepolymer.

In the present invention, an acrylic ester monomer is used.
To produce a prepolymer in which microballoons and polyolefin powders are dispersed by incorporating microballoons and polyolefin powders made of elastic rubber / or resin into a photopolymerizable composition containing You can

The pressure-sensitive adhesive containing the prepolymer as a main component thus produced has excellent heat-resistant cohesive strength, excellent peeling property under static load, and further has a prepolymer in which micro-balloon and polyolefin powder are dispersed. From the above, it is possible to obtain an adhesive tape which is excellent in adhesiveness and compressibility on a rough surface having irregularities and has good workability.

[0029]

EXAMPLES The photopolymerization apparatus of the present invention will be specifically described below with reference to FIG. The photopolymerization apparatus 1 of the present invention comprises an ultraviolet ray generation means, a light propagation means 5 and a photopolymerization pot 6. In the ultraviolet ray generation means, the ultraviolet rays generated from the spherical high-pressure mercury lamp 2 are collected at one point by the condenser mirror 3, guided to the light propagation means 5 through the shutter 4, and introduced into the photopolymerization pot 6.

In the photopolymerization kettle 6, the photopolymerizable composition 11 stirred by the stirring blade 9 is irradiated with ultraviolet rays intermittently by the shutter 4 in a cycle of, for example, irradiation for several seconds to rest for several tens of seconds to gradually polymerize. Is preferred. A method may be adopted in which the viscosity sensor-8 and the shutter are interlocked with each other, and programming is performed so that the irradiation of ultraviolet rays is stopped when the viscosity of the photopolymerizable composition rises by a certain amount, and the polymerization is gradually advanced. On the other hand, since the photopolymerization composition 11 is controlled to have a constant temperature by the temperature control device 10, it prevents a rapid polymerization reaction or partial polymerization from occurring.

Example 1 Next, a method for producing a prepolymer using the photopolymerization apparatus of the present invention will be described. 2-ethylhexyl acrylate 9 kg,
Photopolymerization initiator 2-hydroxy 2-methyl-1-phenylpropane 1-on a mixed monomer consisting of 1 kg of acrylic acid
1.5 g of ON (Darocur 1173, manufactured by Merck & Co., Inc.) was weighed in a photopolymerization pot, and the photopolymerization initiator was dissolved in advance to obtain a photopolymerizable composition.

Next, nitrogen gas was blown into the photopolymerization kettle to replace oxygen with nitrogen gas. Subsequently, the photopolymerizable composition was heated to about 30 ° C. by the temperature controller 10 and irradiated with ultraviolet rays for 10 seconds while stirring, and then the shutter was operated to stop the irradiation. The temperature of the photopolymerizable composition immediately began to rise, but reached about 30.5 ° C. after about 30 seconds.

Thereafter, irradiation with ultraviolet rays for 5 seconds and stopping for 30 seconds were repeated, and the temperature rise was observed. The temperature of the photopolymerizable composition immediately increased after the irradiation, and became constant when the irradiation was stopped, and it was possible to safely irradiate the ultraviolet ray without a rapid temperature rise. After irradiation of 15 times, the viscosity of the photopolymerizable composition reached the target of about 1000 CPS, so the polymerization was stopped. The temperature at this time was 35.5 ° C. The viscosity of this prepolymer is 95 at 23 ° C.
It was 0 CPS.

(Preparation of Adhesive) 10 kg of the prepolymer prepared above was added to neopentyl diacrylate hydroxypivalate having a molecular weight of 312 [KAYARAD MAND].
A] and 20 g of a photopolymerization initiator (Darocur 117
3] was added to produce an ultraviolet-curable pressure-sensitive adhesive composition.

(Production of Adhesive Tape) A transparent PET film substrate having a thickness of 50 μm and a width of 300 mm, which is treated with a silicone release agent on both sides, has a thickness of approximately 0.4 mm from both ends of the substrate. The above-mentioned ultraviolet-curable pressure-sensitive adhesive composition was applied with a blank space of 5 mm each. On top of that, one side is
The release-treated surface of a transparent PET film having a thickness of 50 μm and a width of 300 mm, which had been treated with a release agent, was overlapped and then compressed between rolls to obtain a laminate having a coating layer thickness of about 0.4 mm.

Next, the above-mentioned laminate was arranged with six insect trap fluorescent lamps (main wavelength 352 nm, 0.44 mW / cm ² ) at 60 mm intervals in the width direction, parallel to the flow direction of the coating layer.
Approximately 2.00 mW from a height of 200 mm with respect to the irradiated object
Ultraviolet irradiation was carried out for 60 seconds through an irradiation furnace capable of performing ultraviolet irradiation of / cm ² . Immediately thereafter, with a high pressure mercury lamp (main wavelength 365 nm, output 80 W / cm),
Ultraviolet rays having an irradiation intensity of 35.5 mW / cm ² were irradiated for 30 seconds to sufficiently cure the ultraviolet ray curable pressure-sensitive adhesive composition. Then, while peeling off the PET film of 50 μm which had been subjected to the peeling on one side, the coated layer was wound inside to obtain an adhesive tape.

(Evaluation of Adhesive Tape) Measurement of heat-resistant holding power It was carried out according to the measuring method of the holding power of JIS Z 0237. In this case, as the adherend, a 2 mm-thick stainless steel plate (width x length 3 mm x
150 mm) and an aluminum foil having a thickness of 0.05 mm (width × length 30 mm × 150 mm) were used. Adhesive (width 25 mm) is attached to aluminum foil (area is 25 mm x
50 mm), the PET film substrate was peeled off, and then the film was bonded to a stainless plate so that the bonding area was 25 × 25 mm. The adhesive piece was hung vertically and a load of 1 kg was applied from the stainless steel plate side to evaluate the heat resistance retention at 180 ° C.

The peeling resistance adhered material under static load was the same as in the case of measuring the heat resistant holding force, the adhesive tape was cut into a width of 20 mm and a length of 100 mm, and the stainless steel plate and the aluminum foil were bonded. . 50 ° C for the adhesive piece
In the atmosphere, the aluminum foil should be on the lower side, the stainless steel plate should be fixed horizontally, and the aluminum foil without adhesive should be bent at 90 degrees.
Keep vertical with a load of 00g. Then, after 24 hours, the peeled length of the aluminum foil was measured. As a result, the peeled length after 24 hours was 0.5 mm.

Example 2 Using the same photopolymerization apparatus as in Example 1, a prepolymer having the following composition was polymerized. 0.1 g of a photopolymerization initiator 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173, manufactured by Merck & Co., Inc.) was dissolved in a mixed monomer consisting of 9 kg of 2-ethylhexyl acrylate and 1 kg of acrylic acid. did.

Further, as a hollow microballoon, the wall film is a copolymer of methacrylonitrile and acrylonitrile, having an average particle size of 60 to 80 μm and a true density of 0.025.
g / cm ³ Expancel 091DE (Nob
100 g of El Industries) and 1 kg of Miperon XM-220 (manufactured by Mitsui Chemicals, Inc.) having a mean particle size of 30 μm and a density of 0.94 g / cm ³ as a polyolefin powder. Calculated from the densities, Expancel and Miperon XM-200 occupied 35% by volume and 9% by volume in the adhesive, respectively.

The above photopolymerizable composition was placed in the same photopolymerization apparatus as in Example 1, and nitrogen gas was blown thereinto to sufficiently replace oxygen with nitrogen gas. As in Example 1, the temperature of the monomer mixture liquid was set to 30 ° C., and the ultraviolet rays were irradiated for 10 seconds, the temperature immediately started to rise, but after about 30 seconds, it became 30.2 ° C. After that, the polymerization reaction is performed by repeating irradiation for 5 seconds and stopping for 30 seconds, and the viscosity sensor shows 900 cps.
The irradiation of ultraviolet rays was stopped at the point where was indicated. The viscosity of the obtained prepolymer at 23 ° C. was 850 cps.

Next, as in Example 1, prepolymer-1
Add 1.1 g of hydroxypivalic acid neopentyl diacrylate [KAYARAD MANDA] (20 g) and a photopolymerization initiator 2-hydroxy-2-methyl-1-phenylpropan-1-one [Darocur 1173] (15 g), and then add ultraviolet light. A curable pressure sensitive adhesive composition was prepared. Example 1
An adhesive tape was produced in exactly the same manner as in. The obtained pressure-sensitive adhesive tape had a thickness of 0.395 mm and was a compressible and reversible pressure-sensitive adhesive tape.

Tested in the same manner as in Example 1, the heat-resistant holding force had a deviation of 0.2 mm, and the peelability under static load was 0.5 mm for the peeled length. . Further, the following evaluation test was conducted.

(Compression and Restoration Test) The sinking distance when compressed at 500 g / cm ² and the adhesive tape after removing the load
The thickness of the cup was measured, and the restoration ratio to the original thickness was obtained.
The adhesive tape was attached to a flat plate with a thickness of 5 mm, a metal block of 500 gr in weight having a cylindrical portion with a cross-sectional area of 1 cm ² was placed, and the mixture was compressed at 23 ° C. and then sunk for about 30 seconds. Immediately after measuring the distance, the load was removed, and one hour later, the thickness of the restored adhesive tape was measured. As a result, the distance sunk by compression was 0.3 mm, and the thickness after 1 hour was 0.695 mm, which was restored to 97.9%.

(Adhesive Strength on Rough Surface with Roughness) A wall material was used as an adherend. This wall material is a sizing board spray-painted with acrylic paint, and the size of the protrusion is
The diameter was 1 to 7 mm and the height was 0.5 to 1 mm. This wall material was cut into a width of 30 mm and a length of 200 mm. Adhesive tape
The strip was cut into a width of 20 mm and a length of 100 mm and lightly stuck to the wall material. Next, an aluminum foil having a thickness of 50 μm cut into a width of 30 mm and a length of 200 mm was used as a backing material, and a roller having a load of about 2 kg was reciprocated once from above to bond the foil.

After adhering, after leaving at 23 ° C. for 48 hours, the peeling strength in the 90 ° direction was measured at a peeling speed of 300 mm / min. As a result, the pressure-sensitive adhesive was firmly adhered to the wall material, and the pressure-sensitive adhesive caused cohesive failure over the entire surface. This is because the pressure-sensitive adhesive tape compressed in the pressure-bonding work adheres well to the uneven surface of the adherend. Adhesive strength is 4kgf / cm
Met.

(Pullability) PET peeled on one side
A pressure-sensitive adhesive tape in which the film was replaced with a kraft release paper whose one surface was subjected to a peeling treatment was punched with a Viku mold. A circle having a diameter of 20 mm was punched continuously for 100 shots, but no adhesive adhered to the big blade.

[0048]

[Comparative Example 1] (Example of dissolution of various polymers) 2-ethylhexyl acrylate 9 kg, acrylic acid 1
Acrylic rubber 300 g (Toacron PS220, Toa Paint Co., Ltd.) in 10 kg of mixed monomer solution consisting of kg
Manufactured) was dissolved in a container equipped with a stirrer. The viscosity after complete dissolution was 750 CPS, and a uniform UV-curable pressure-sensitive adhesive composition was obtained. However, even if the acrylic rubber is cut into small pieces, it takes 48 hours to dissolve, and if the time for cutting the acrylic rubber into small pieces is also included, the production efficiency is significantly inferior to that of the present invention.

EFFECT OF THE INVENTION It is a safe photopolymerization apparatus in which the polymerization reaction is easily controlled and no explosion or the like occurs. Since the generated ultraviolet rays do not easily leak to the surroundings, it is not necessary to take measures against light leakage, so the equipment can be downsized. Since it can be used in a method of polymerizing a photopolymerizable composition containing an alkyl (meth) acrylic acid ester as a main component while controlling the amount of ultraviolet light so as not to cause a rapid polymerization reaction, a gel having a desired viscosity range can be used. A uniform prepolymer having a small amount can be easily manufactured.

[Brief description of drawings]

FIG. 1 is a schematic view showing a photopolymerization apparatus of the present invention.

[Explanation of symbols]

1 UV generation means 2 High pressure mercury lamp 3 Focusing mirror 4 Shutter device 5 Light propagation means 6 Photopolymerization equipment 7 Temperature measurement sensor 8 Viscosity measurement sensor 9 stirring wings 10 Temperature control device 11 Photopolymerizable composition

Claims (2)

(57) [Claims] 1. A photopolymerization apparatus comprising an ultraviolet ray generation means, a light propagation means for irradiating the photopolymerization composition with the ultraviolet rays generated by the ultraviolet ray generation means, and a polymerization vessel, wherein the ultraviolet ray generation means includes the A photopolymerization device, comprising a shutter device for controlling an input to the light propagating means, wherein the light propagating means comprises an optical fiber. 2. The photopolymerization device according to claim 1, wherein the shutter device works in conjunction with a viscosity sensor or a temperature sensor to adjust the input of ultraviolet rays to the light propagation means.