JP7285486B2 - Photoreactive composition - Google Patents

Description

The present invention relates to a photoreactive composition that cures upon irradiation with light.

Conventionally, a photoreactive composition is known which can be cured in a short time by light irradiation and which can be patterned by using a photomask, a laser irradiation device, or the like. Photoreactive compositions are widely used, for example, as hard coats for films and molded articles, resist materials, and the like.

Frontal photoreaction and domino free radical photopolymerization (DFRP) are known as methods for curing photoreactive compositions.

In the frontal photoreaction, the radicals generated from the photoradical generator by light irradiation cause the polymerization reaction of the monomer, and the heat of the reaction activates the thermal radical generator, thereby curing deep parts that cannot be photoexcited. It is said to be possible. However, since the frontal photoreaction is a system that cures by heat generation, the temperature of the reaction system rises, and for example, when manufacturing a molded article in contact with a non-heat-resistant adherend, the adherend may be deformed. There is a problem of letting

On the other hand, in the DFRP system, for example, as described in Non-Patent Document 1, upon irradiation with light, a base is generated from the photobase generator, and the base is used as a catalyst to react with the base multiplier, resulting in a base component. concentration increases. The reducing properties of the base component cause the thermal radical generator to decompose at low temperatures, resulting in free radical polymerization of the vinyl monomer. Non-Patent Document 1 shows that a DFRP system with a base multiplier shortens the induction time and improves the reaction rate compared to a system using a photobase generator and a thermal radical generator as catalysts. It is The DFRP system is not a system that cures by heat generation, so even if a heat rise cannot be expected, curing progresses in deep areas where photoexcitation is impossible, and it is said that a high conversion rate can be obtained. .

Minghui He, et al., Journal of Polymer Science, PART A: POLYMER CHEMISTRY 2014, 52, 1560-1569

However, even with the DFRP system, there is a problem that only the surface is hardened and it is difficult to harden the deep part when producing a molded object that is difficult to transmit light, a molded object with a thick film, a molded object with a complicated shape, etc. .

An object of the present invention is to provide a photoreactive composition that can be efficiently cured to deep portions even when producing a molded article that is difficult to transmit light.

The photoreactive composition according to the present invention contains a vinyl monomer and a filler, and is placed in a test tube having a diameter of 0.6 cm and a height of 5 cm. The test tube was injected to a height of 3 cm from the bottom of the tube, and light was irradiated from above the test tube for 360 seconds at a light intensity of 30 mW/cm ² using an LED lamp having a central wavelength of 365 nm, and allowed to stand at 25 ° C. for 24 hours. The polymerization rate of the vinyl monomer at a position 1 cm from the bottom of the test tube is 90% or more.

A specific aspect of the photoreactive composition according to the present invention further includes a photobase generator and a thermal radical generator having a 10-hour half-life temperature of 60° C. or higher.

In another specific aspect of the photoreactive composition according to the present invention, the photobase generator is an oxime ester-based compound, an ammonium-based compound, a benzoin-based compound, a dimethoxybenzylurethane-based compound, and an ortho-nitrobenzylurethane-based compound. At least one selected from the group consisting of

In still another specific aspect of the photoreactive composition according to the present invention, the vinyl monomer is a nitrogen atom-containing vinyl monomer. Preferably, the vinyl monomer containing a nitrogen atom is (meth)acryloylmorpholine, N-vinyl-2-pyrrolidone, vinylpyridine, N-vinylcarbazole, (meth)acrylamide, N,N-dimethylacrylamide, N, At least one selected from the group consisting of N-diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, and dimethylaminopropylamide. More preferably, the vinyl monomer containing a nitrogen atom is the (meth)acryloylmorpholine.

In still another specific aspect of the photoreactive composition according to the present invention, the thermal radical generator is an organic peroxide or polysulfide.

Yet another particular aspect of the photoreactive composition according to the present invention further comprises a vinyl monomer containing no nitrogen atoms.

In still another specific aspect of the photoreactive composition according to the present invention, the content of the filler is in the range of 10 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the photoreactive composition. It is in.

In still another specific aspect of the photoreactive composition according to the present invention, the content of the base amplifier is less than 2 mol% relative to 100 mol% of the vinyl monomer.

According to the present invention, it is possible to provide a photoreactive composition that can be efficiently cured to deep portions even when producing a molded article that is difficult to transmit light.

FIG. 1 is a schematic front view showing a test tube used for measuring the degree of polymerization of vinyl monomers in the deep part.

The details of the present invention are described below.

The photoreactive composition of the invention comprises a vinyl monomer and a filler.

In the present invention, when the photoreactive composition is irradiated with light using the test tube shown in FIG. be. Although the upper limit of the polymerization rate of the vinyl monomer in the deep part of the test tube is not particularly limited, it can be, for example, 100% or less.

When measuring the polymerization rate of the vinyl monomer in the deep part of the test tube, first, a test tube 1 having a diameter D of 0.6 cm and a height L0 of 5 cm was exposed to a photoreaction up to a height L1 of 3 cm from the bottom 2 of the test tube 1. Inject sexual composition 3. Next, an LED lamp having a central wavelength of 365 nm is used to irradiate the test tube 1 from above with light intensity of 30 mW/cm ² for 360 seconds. After light irradiation, it is allowed to stand at 25° C. for 24 hours. The operations up to this point are assumed to be performed with the test tube 1 standing upright as shown in FIG. Subsequently, the polymerization rate of the vinyl monomer is measured at a position 1 cm from the bottom 2 of the test tube 1 after standing (L2 in FIG. 1 is 1 cm).

The light irradiation time varies depending on the composition of the photoreactive composition, but it is preferable that the polymerization rate of the vinyl monomer in the depth of the test tube becomes 90% or more in 60 seconds, and the vinyl monomer in the depth of the test tube reaches 90% in 30 seconds. is more preferably 90% or more, and most preferably the polymerization rate of the vinyl monomer at the depth of the test tube is 90% or more in 5 seconds.

The polymerization rate of the vinyl monomer was measured by measuring the FT-IR spectrum before and after light irradiation at a position 1 cm from the bottom 2 of the test tube 1, and before and after light irradiation near 1637 cm ^-1 attributed to the C=C stretching vibration of the vinyl group. It is calculated from the peak intensity change in (peak after light irradiation/peak before light irradiation). The peak before light irradiation refers to the peak measured after injection of the photoreactive composition 3 and before light irradiation. Moreover, the peak after light irradiation refers to the peak measured after standing at 25° C. for 24 hours after the light irradiation. As a measuring device, FT/IR6600 (manufactured by JASCO Corporation) or its ^equivalent can be used.

In the present invention, the polymerization rate of the vinyl monomer at the depth of the test tube measured by the above method is preferably 90% or more, more preferably 95% or more. When the polymerization rate of the vinyl monomer is equal to or higher than the above lower limit, even the deep part of the molded article obtained by light irradiation can be cured more efficiently.

In the present invention, the photoreactive composition may further contain a photobase generator and a thermal radical generator having a 10-hour half-life temperature of 60° C. or higher. In this case, when the photoreactive composition of the present invention is irradiated with light, a base is generated from the photobase generator. The thermal radical generator decomposes at a low temperature due to the reducing property of the base component generated from the photobase generator, and free radical polymerization of the vinyl monomer occurs. This makes it easier to adjust the rate of polymerization of the vinyl monomer in the deep portion of the test tube.

Also, the vinyl monomer is preferably a vinyl monomer containing a nitrogen atom. In this case, the free radical polymerization of the vinyl monomer can be progressed more efficiently by the thermal radical generator decomposed by the reducing properties of a small amount of the base component generated from the photobase generator without adding a base multiplier. can. This makes it easier to adjust the rate of polymerization of the vinyl monomer in the deep portion of the test tube.

In the present invention, the content of the base multiplier in the photoreactive composition is preferably less than 2 mol % with respect to the total 100 mol % of the vinyl monomers. Alternatively, it is preferred that no base amplifier is included in the photoreactive composition. In this case, heat generation is suppressed, and free radical polymerization can proceed at 40° C. or less.

The photoreactive composition of the present invention contains a vinyl monomer and a filler, and the polymerization rate of the vinyl monomer at the depth of the test tube measured by the above method is within the above range. Therefore, even in the case where the filler is included and the light does not reach the deep part, the deep part can be cured at a low temperature by irradiating the surface portion with the light. As described above, the photoreactive composition of the present invention can be efficiently cured to deep portions even in the case of producing a molded article that hardly transmits light.

In addition, since the photoreactive composition of the present invention contains a filler, it is possible to enhance the mechanical strength, electrical conductivity, thermal conductivity, etc. of the resulting molded article. Alternatively, the resulting molded article can be colored or imparted with a light-shielding property.

In particular, the photoreactive composition of the present invention can be efficiently cured to the depths of a molded article by irradiation with light, and can improve electrical conductivity and thermal conductivity. It can be suitably used for

Further, in the present invention, even in the case of producing a thick-film molded body, it is possible to harden deep portions at a low temperature. For this reason, the photoreactive composition of the present invention can be used at a low temperature and in a deep region, even when a thick-film molded article is produced under conditions cooled by environmental conditions (for example, under outdoor conditions in winter). can be cured up to In addition, the photoreactive composition of the present invention suppresses deformation of the adherend and maintains a high conversion rate even when a thick-film molded article in contact with a non-heat-resistant adherend is produced. Molded bodies can be produced.

The temperature reached during the reaction of the photoreactive composition of the present invention is not particularly limited, but is preferably 100° C. or lower, more preferably 50° C. or lower. The temperature reached during the reaction of the photoreactive composition of the present invention can be measured by thermography.

In addition, the photoreactive composition of the present invention uses a mold having a complicated shape (for example, a mold having voids) having a portion that becomes a shadow of light, and the photoreactive composition is injected into the mold to react. It is possible to harden even shadow areas at a low temperature even in cast polymerization such that the resin is cured.

The details of each material will be described below.

(vinyl monomer)
Although the vinyl monomer is not particularly limited, it is preferably a vinyl monomer containing a nitrogen atom. Also, a plurality of types of vinyl monomers may be used, and a nitrogen atom-containing vinyl monomer and another vinyl monomer may be used in combination. When a vinyl monomer containing a nitrogen atom is used, the free radical polymerization of the vinyl monomer can proceed more efficiently without adding a base multiplier.

a vinyl monomer containing a nitrogen atom;
The vinyl monomer containing a nitrogen atom is not particularly limited, and examples include (meth)acryloylmorpholine, N-vinyl-2-pyrrolidone, vinylpyridine, N-vinylcarbazole, (meth)acrylamide, N,N-dimethyl acrylamide, N,N-diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, dimethylaminopropylamide, and the like. These vinyl monomers may be used individually by 1 type, and may use multiple types together. Among them, the vinyl monomer containing a nitrogen atom is preferably a vinyl monomer containing a nitrogen-containing ring, from the viewpoint of more efficiently curing the molded body obtained by light irradiation to the depth thereof, and (meth) Acryloylmorpholine is preferred. In addition, "(meth)acryloyl" means "acryloyl" or "methacryloyl".

other vinyl monomers;
Other vinyl monomers include, for example, vinyl monomers that do not contain nitrogen atoms.

Nitrogen-free vinyl monomers include, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) ) (meth)acrylic acids such as 2-hydroxyethyl acrylate and tetrahydrofurfuryl (meth)acrylate and esters thereof. As vinyl monomers containing no nitrogen atoms, vinyl monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, methyl vinyl ether, styrene and divinylbenzene, and compounds having unsaturated double bonds such as isoprene may be used. As the vinyl monomer containing no nitrogen atom, polyfunctional monomers such as pentaerythritol tri(meth)acrylate and trimethylolpropane tri(meth)acrylate may be used.

As other vinyl monomers, (meth)acrylamide, (meth)acrylamide derivatives such as isopropylacrylamide, and (meth)acrylonitrile may be used.

These other vinyl monomers may be used individually by 1 type, and may use multiple types together.

In this specification, "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid". In addition, "(meth)acrylate" means "acrylate" or "methacrylate".

When another vinyl monomer is included, the content of the other vinyl monomer is not particularly limited, but is preferably 10 mol% or more and preferably 250 mol% or less with respect to 100 mol% of the vinyl monomer containing a nitrogen atom. be. When the content of the other vinyl monomer is within the above range, the deep part of the molded article obtained by light irradiation can be cured more efficiently.

(filler)
The filler is not particularly limited, and may be an inorganic filler or an organic filler. Especially, it is preferable that it is an inorganic filler. In addition, an inorganic filler and an organic filler may be used together.

Examples of organic fillers include polyethylene fine particles, polypropylene fine particles, polyvinyl alcohol fine particles, polyvinyl butyral fine particles, polyvinyl chloride fine particles, polyvinylidene chloride fine particles, polyvinylidene fluoride fine particles, acrylonitrile fine particles, acrylic rubber fine particles, polystyrene fine particles, divinylbenzene fine particles, and polyethylene terephthalate. Microparticles, polyimide microparticles, polyamide microparticles, cellulose microparticles, and the like can be used. These may be used individually by 1 type, and may use 2 or more types together.

Examples of inorganic fillers that can be used include metal oxides, metal carbonates, natural minerals, metal hydroxides, carbon materials, metal materials, and hollow inorganic fillers. These may be used individually by 1 type, and may use 2 or more types together.

Examples of metal oxides include silica, aluminum oxide, titanium oxide, zirconium oxide, zinc oxide, lead oxide, and indium tin oxide.

Examples of metal carbonates include calcium carbonate, magnesium carbonate, barium carbonate, and the like.

Examples of natural minerals include talc, mica, clay, and the like.

Metal hydroxides include aerosil, magnesium hydroxide, aluminum hydroxide and the like.

Carbon materials include graphite, carbon black, carbon nanotubes, and the like.

Metal materials include copper, gold, silver, iron, aluminum, stainless steel, platinum, and palladium.

Examples of hollow inorganic fillers include glass balloons and shirasu balloons.

Moreover, the inorganic filler may be surface-treated with a surface treatment agent such as a silane coupling agent.

Silane coupling agents include, for example, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3 -glycidylpropylmethyldimethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-propylisocyanatemethyldimethoxysilane, 3-isocyanatepropyltrimethoxysilane, etc. mentioned. These may be used individually by 1 type, and may use 2 or more types together.

The content of the filler is not particularly limited, but is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, more preferably 80 parts by weight or less, and more preferably 100 parts by weight of the total amount of the photoreactive composition. is 70 parts by weight or less. When the content of the filler is at least the above lower limit, the mechanical strength, electrical conductivity, and thermal conductivity of the molded article to be produced can be further enhanced. Further, when the filler content is equal to or less than the above upper limit, the deep part of the molded article obtained by light irradiation can be cured more efficiently.

The photoreactive composition of the present invention contains a large amount of such fillers, and even if the light does not reach the deep part, it can be cured to the deep part at a low temperature by irradiating the surface part with light. can be done.

(Photobase generator)
The photoreactive composition of the present invention may further contain a photobase generator. A photobase generator is a substance that generates a base upon irradiation with light. Examples of light include infrared rays, visible rays, and ultraviolet rays.

The photobase generator is not particularly limited, and examples thereof include oxime ester compounds, ammonium compounds, benzoin compounds, dimethoxybenzylurethane compounds, and orthonitrobenzylurethane compounds.

More specifically, the photobase generator includes, for example, 1,5,7-triazabicyclo[4.4.0]dec-5-ene 2-(9-oxoxanthen-2-yl)propionate, 9 -anthrylmethyl N,N-diethylcarbamate, (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine, guanidinium 2-(3-benzoylphenyl)propionate, 1-(anthraquinone-2 -yl) ethylimidazole carboxylate, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1-(anthraquinon-2-yl)-ethyl N,N-dicyclohexylcarbamate, dicyclohexylammonium 2-(3-benzoyl phenyl)propionate, cyclohexylammonium 2-(3-benzoylphenyl)propionate, 9-anthrylmethyl N,N-dicyclohexylcarbamate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidinium 2-(3- benzoylphenyl)propionate, 1,6-hexamethylene-bis(4,5-dimethoxy-2-nitrobenzylcarbamate), and the like. These may be used individually by 1 type, and may use 2 or more types together.

The content of the photobase generator is not particularly limited, but is preferably 0.1 mol % or more and preferably 1.0 mol % or less with respect to the total of 100 mol % of the vinyl monomers. When the content of the photobase generator is equal to or higher than the above lower limit, a more sufficient amount of base is generated and the concentration of the base component is further increased. When the content of the photobase generator is equal to or less than the above upper limit, the deep part of the molded article obtained by light irradiation can be cured more efficiently.

(Thermal radical generator)
The photoreactive composition of the present invention may further contain a thermal radical generator. As the thermal radical generator, for example, a thermal radical generator having a 10-hour half-life temperature of 60° C. or higher can be suitably used. Organic peroxides or polysulfides, for example, can be used as such thermal radical generators.

Organic peroxides are not particularly limited, and examples include benzoyl peroxide, diisopropyl peroxycarbonate, dioctyl peroxydicarbonate, t-butyl peroxylaurate, lauroyl peroxide, dioctanoyl peroxide, and hydrogen peroxide. , acetyl peroxide, cumyl peroxide, t-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, Potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, t-butyl pertriphenylacetate hydroperoxide, t-butyl performate, t-butyl peracetate, perbenzone t-butyl acid, t-butyl perphenylacetate, t-butyl permethoxyacetate, t-butyl per-N-(3-toluyl)carbamate, ammonium bisulfate, sodium bisulfate and the like.

Polysulfides are not particularly limited, and examples thereof include sulfur compounds such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and trimethylolpropane tris(3-mercaptopropionate).

These thermal radical generators may be used alone or in combination of two or more.

The content of the thermal radical generator is not particularly limited, but is preferably 0.1 mol% or more, more preferably 1 mol% or more, and preferably 5 mol% or less with respect to the total 100 mol% of the vinyl monomers. . If the content of the thermal radical generator is less than the above lower limit, the radical polymerization of the vinyl monomer may not proceed. When the content of the thermal radical generator exceeds the above upper limit, the so-called frontal photoreaction may occur in which the thermal radical generator is activated by the heat of the polymerization reaction of the monomer and the reaction progresses.

(Other additives)
In the present invention, the content of the base multiplier in the photoreactive composition is preferably less than 2 mol % with respect to the total 100 mol % of the vinyl monomers. Alternatively, it is preferred that no base amplifier is included in the photoreactive composition. When the content of the base multiplier is less than 2 mol %, the heat of reaction can be further suppressed.

The base multiplying agent is a substance that decomposes the base generated from the photobase generator as a catalyst to generate a new base. The generated base functions as a new catalyst, autocatalytically generates a large number of bases, and the concentration of the base component increases. The base multiplier may be a low-molecular-weight compound or a high-molecular-weight compound.

Examples of such a base amplifying agent include compounds represented by the following formula (1).

In formula (1), R ¹ and R ² are each hydrogen or hydrocarbon groups, or are linked to form a nitrogen-containing ring.

Examples of the hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 15 carbon atoms, and the like. . Specifically, the hydrocarbon group includes, for example, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, cyclooctyl group, phenyl group, tolyl group, naphthyl group, benzyl group, phenethyl group, or naphthylmethyl groups. Moreover, the hydrocarbon group may have a substituent such as an amino group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, or a hydroxyl group. When the above R1 and R2 are linked to form a nitrogen-containing ring, the nitrogen-containing ring may contain a plurality of heteroatoms (nitrogen, oxygen, sulfur, etc.) as constituent atoms.

An example of the base multiplier represented by formula (1) is 1-(9-fluorenylmethoxycarbonyl)piperidine.

As other additives, for example, phenol-based, phosphorus-based, amine-based or sulfur-based antioxidants, and benzotriazole-based or hydroxyphenyltriazine-based UV absorbers may be used. In addition, other additives include metal damage inhibitors, halogenated flame retardants such as hexabromobiphenyl ether and decabromodiphenyl ether, flame retardants such as ammonium polyphosphate and trimethyl phosphate, antistatic agents, stabilizers, pigments and dyes. You may use additives, such as. These additives may be used individually by 1 type, and may use multiple types together.

Next, the present invention will be clarified by giving specific examples and comparative examples of the present invention. In addition, the present invention is not limited to the following examples.

(Example 1)
As a photobase generator, 2-(9-oxoxanthen-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene (XT-tbd, Tokyo Chemical Industry Co., Ltd.) ) was used. Benzoyl peroxide (BPO, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a thermal radical generator. Acryloylmorpholine (ACMO, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as a vinyl monomer containing a nitrogen atom. Pentaerythritol triacrylate (PETA, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as another vinyl monomer. As a filler, silica surface-treated with 3-acryloxypropylmethyldimethoxysilane (manufactured by Azmax) was used. The silica surface treatment was carried out by adding 0.5 g of silica, 10 g of 3-acryloxypropylmethyldimethoxysilane and 2 drops of 5 mol % hydrochloric acid to 23 ml of toluene and refluxing the mixture at 110° C. for 8 hours. rice field.

Next, 1 mol% of the prepared XT-tbd (relative to 100 mol of PETA), 2 mol% of BPO (relative to 100 mol of PETA), 1.5 g of ACMO, 0.5 g of PETA, and the above was mixed with 0.01 g (0.5 parts by weight with respect to 100 parts by weight of the entire photoreactive composition) to prepare a photoreactive composition.

(Example 2)
A photoreactive composition was prepared in the same manner as in Example 1, except that silica surface-treated with 3-acryloxypropyltrimethoxysilane was used as the filler. The surface treatment in Example 2 was carried out by adding 0.5 g of silica and 10 g of 3-acryloxypropyltrimethoxysilane to 23 ml of toluene and refluxing the mixture at 110° C. for 8 hours.

(Example 3)
A photoreactive composition was prepared in the same manner as in Example 1, except that alumina surface-treated with 3-acryloxypropyltrimethoxysilane was used as the filler. Incidentally, the surface treatment in Example 2 was carried out by adding 1.0 g of alumina, 2.0 g of 3-acryloxypropyltrimethoxysilane and 4 drops of 5 mol % hydrochloric acid to 46 ml of toluene and refluxing the mixture at 110° C. for 8 hours. I went by.

(Example 4)
A photoreactive composition was prepared in the same manner as in Example 1, except that titanium oxide surface-treated with 3-acryloxypropyltrimethoxysilane was used as the filler. Incidentally, the surface treatment in Example 4 was carried out by adding 1.0 g of titanium oxide, 2.0 g of 3-acryloxypropyltrimethoxysilane, and 4 drops of 5 mol % hydrochloric acid to 46 ml of toluene, followed by refluxing at 110° C. for 8 hours. It was done by

(Examples 5-8)
A photoreactive composition was prepared in the same manner as in Example 1, except that the amount of filler added was changed to the ratio shown in Table 1.

(Example 9)
A photoreactive composition was prepared in the same manner as in Example 1, except that acryloylmorpholine (ACMO) as a nitrogen atom-containing vinyl monomer was changed to 1.5 g of hydroxyethylacrylamide.

(Example 10)
A photoreactive composition was prepared in the same manner as in Example 1, except that 1.5 g of tetrahydrofurfuryl acrylate was used instead of acryloylmorpholine (ACMO) as a vinyl monomer containing a nitrogen atom.

(Comparative example 1)
Example 1, except that acryloylmorpholine (ACMO) as a vinyl monomer containing a nitrogen atom was changed to 2-hydroxyethyl acrylate (1.5 g), and surface-treated silica was not used as a filler. A composition was prepared in the same manner.

(Comparative example 2)
A composition was prepared in the same manner as in Example 1, except that acryloylmorpholine (ACMO) as a vinyl monomer containing a nitrogen atom was changed to 1.5 g of 2-hydroxyethyl acrylate.

[evaluation]
(Reaction reaching temperature and gel fraction)
A test tube with a diameter of 0.6 cm and a height of 5 cm was filled with the photoreactive composition to a depth of 3 cm. An LED lamp having a central wavelength of 365 nm was used to irradiate light from above the test tube to carry out polymerization. At this time, the height of the LED lamp was adjusted so that the light intensity was 30 mW/cm ² and light irradiation was performed for 5 seconds.

The temperature reached during the reaction of the photoreactive composition was measured by thermography. Table 1 shows the results.

Moreover, the gel fraction of the photoreactive composition after polymerization was measured by the following method.

After standing at 25° C. for 24 hours after light irradiation, about 0.1 g of a sample is collected from a portion of about 1 cm from the bottom of the tester, and the obtained sample is immersed in 30 ml of THF at 25° C. for 12 hours and shaken. let me The immersed sample was filtered using a 200-mesh stainless steel wire mesh, and the stainless steel wire mesh was dried in an oven at 80° C. for 1 hour while leaving the filtration residue. The gel fraction (percentage) was then determined by dividing the weight of the dry residue by the weight of the sample taken.

(Polymerization rate at the depth of test tube 1)
A test tube with a diameter of 0.6 cm and a height of 5 cm was filled with the photoreactive composition 3 up to a height of 3 cm from the bottom of the test tube. Next, the test tube was irradiated from above with light intensity of 30 mW/cm ² for 360 seconds using an LED lamp having a central wavelength of 365 nm. After the light irradiation, the test tube was left standing at 25° C. for 24 hours, and the polymerization rate of the vinyl monomer was measured at a position 1 cm from the bottom of the test tube. The polymerization rate of the vinyl monomer was measured by measuring the FT-IR spectrum before and after light irradiation at a position 1 cm from the bottom of the test tube, and before and after light irradiation at 1637 cm ^-1 attributed to the C=C stretching vibration of the vinyl group. It was calculated from the peak intensity ratio (after light irradiation/before light irradiation). In addition, "before light irradiation" refers to the state before polymerization, and "after light irradiation" refers to the state after standing at 25°C for 24 hours after light irradiation. The FTIR spectrum was measured using an apparatus "FT/IR6600" (manufactured by JASCO Corporation) at a measurement wavelength of 4000 to 400 cm ^-1 and 16 scans.

(Polymerization rate 2 at the depth of the test tube)
A test tube with a diameter of 0.6 cm and a height of 5 cm was filled with the photoreactive composition to a depth of 3 cm. An LED lamp having a central wavelength of 365 nm was used to irradiate light from above the test tube to carry out polymerization. At this time, the height of the LED lamp was adjusted so that the light intensity was 30 mW/cm ² and light irradiation was performed for 5 seconds.

After the light irradiation, the test tube was left standing at 25° C. for 24 hours, and the polymerization rate of the vinyl monomer was measured at a position 1 cm from the bottom of the test tube. The polymerization rate of the vinyl monomer was measured by measuring the FT-IR spectrum before and after light irradiation at a position 1 cm from the bottom of the test tube, and before and after light irradiation at 1637 cm ^-1 attributed to the C=C stretching vibration of the vinyl group. It was calculated from the peak intensity ratio (after light irradiation/before light irradiation). In addition, "before light irradiation" refers to the state before polymerization, and "after light irradiation" refers to the state after standing at 25°C for 24 hours after light irradiation. The FTIR spectrum was measured using an apparatus "FT/IR6600" (manufactured by JASCO Corporation) at a measurement wavelength of 4000 to 400 cm ^-1 and 16 scans.

The results are shown in Table 1 below.

1... Test tube 2... Bottom part 3... Photoreactive composition

Claims (9)

including a vinyl monomer, a photobase generator, and a filler;
The content of the photobase generator is 0.1 mol% or more and 1.0 mol% or less with respect to the total 100 mol% of the vinyl monomer,
The content of the filler is in the range of 10 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the photoreactive composition,
A test tube with a diameter of 0.6 cm and a height of 5 cm was filled with the photoreactive composition containing the vinyl monomer and the filler to a height of 3 cm from the bottom of the test tube, and an LED lamp having a central wavelength of 365 nm was used. Using a light intensity of 30 mW/cm ² for 360 seconds, the test tube was irradiated with light from above and allowed to stand at 25 ° C. for 24 hours. A photoreactive composition that is 90% or more. further comprising a thermal radical generator ;
2. The photoreactive composition according to claim 1, wherein the content of said thermal radical generator is 1 mol % or more and 5 mol % or less with respect to a total of 100 mol % of said vinyl monomers. The photoreactive composition according to claim 1, further comprising a thermal radical generator having a 10 -hour half-life temperature of 60°C or higher. The photobase generator is at least one selected from the group consisting of oxime ester-based compounds, ammonium-based compounds, benzoin-based compounds, dimethoxybenzylurethane-based compounds, and ortho-nitrobenzylurethane-based compounds. 4. The photoreactive composition according to any one of 3 . The photoreactive composition according to any one of claims 1 to 4 , wherein the vinyl monomer is a vinyl monomer containing a nitrogen atom. The vinyl monomer containing a nitrogen atom is (meth)acryloylmorpholine, N-vinyl-2-pyrrolidone, vinylpyridine, N-vinylcarbazole, (meth)acrylamide, N,N-dimethylacrylamide, N,N-diethyl 6. The photoreactive composition according to claim 5 , which is at least one selected from the group consisting of acrylamide, isopropylacrylamide, hydroxyethylacrylamide, and dimethylaminopropylamide. 7. The photoreactive composition according to claim 6 , wherein the vinyl monomer containing a nitrogen atom is the (meth)acryloylmorpholine. 3. The photoreactive composition according to claim 2 , wherein the thermal radical generator is an organic peroxide or polysulfide. A photoreactive composition according to any one of claims 5 to 8 , further comprising a vinyl monomer containing no nitrogen atoms.

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