JPH04175315A - Photocurable composition - Google Patents

Abstract

PURPOSE:To obtain a photocurable composition which can give a cured product excellent in internal homogeneity, accuracy of surface transfer, an ability to cut ultraviolet rays, transparency and hue by adding a specified photopolymeriza tion initiator and an ultraviolet absorber to a specified sulfur-containing mono mer. CONSTITUTION:A photocurable composition comprising 100 pts.wt. monomer based on a sulfur-containing monomer (A) of the formula, 0.02-0.3 pt.wt. at least one photopolymerization initiator (B) selected among those based on benzophenone and acetophenone and 0.01-0.2 pt.wt. at least one ultraviolet absorber (C) selected among those based on benzophenone and benzotriazole. In the formula, R<1> is H or methyl; R<2> is 1-6 C alkylene; Ar is 6-30 C arylene or the like; X is -O- or the like; Y is -S- or the like; m and n are each 1-5; and p is 0-10.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photocurable composition that is cured by irradiation with active energy rays such as ultraviolet rays. The present invention relates to a photocurable composition for cast polymerization suitable for manufacturing parts.

(Prior Art) A method has been proposed for manufacturing plastic lenses by irradiating a photocurable resin with ultraviolet rays from a mercury lamp or the like as an active energy source (Japanese Patent Laid-Open No. 1983-1944).
No. 01, No. 63-207632, etc.).

This method has the advantage of being able to be cured in a short time by UV irradiation, but internal homogeneity and surface transfer precision are not sufficient, and this type of resin lens that is generally obtained by UV curing is made of polymethyl methacrylate, polycarbonate, etc. , because its transparency and hue are inferior to that of diethylene glycol bisallyl carbonate polymers, etc.
There was a practical problem.

(Problems to be Solved by the Invention) The present invention can provide a cured product that has good internal homogeneity and transfer accuracy, has UV blocking properties, and has excellent transparency and hue, and is suitable for use in optical components. The present invention aims to provide a photocurable composition suitable for mass production, particularly a photocurable composition for casting.

(Means for Solving the Problems) The present invention provides a photocurable composition in which a specific photopolymerizable monomer contains a specific photopolymerization initiator and a specific ultraviolet absorber in a specific composition ratio. It was possible to achieve that purpose.

That is, the photocurable composition of the present invention has the following formula: (A) Represents a ren group, an aralkylene group, or a halogen atom-substituted group other than fluorine, each having 6 to 30 carbon atoms, X represents 10- or -8-, and Y represents X is 10-
When it shows -8- or -5O2-, X is -3
-s-, -5O2-.

-CO-, or a group selected from an alkylene group, an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylenethioether group, and an aralkylenethioether group each having 1 to 12 carbon atoms, and m and n are Each represents an integer of 1 to 5, and p represents a number of O to 10. 100 parts by weight of a monomer mainly composed of a sulfur-containing vehicle represented by (B) at least one photopolymerization initiator selected from benzophenone photopolymerization initiators and acetophenone photopolymerization initiators. (C) 0.02 to 0.3 parts by weight of at least one UV absorber selected from benzophenone UV absorbers and benzotriazole UV absorbers.
The composition contains 1 to 0.2 parts by weight.

The monomer (A) in the photopolymerizable composition of the present invention is a monomer whose main component is the sulfur-containing monomer represented by (I) above.

Specific examples of the monomer represented by (1) above include p-bis(β-acryloyloxyethylthio)xylylene, p-bis(β-methacryloyloxyethylthio)xylylene, and m-bis(β-methacryloyloxyethylthio)xylylene. (β-acryloyloxyethylthio)xylylene, m-bis(β-methacryloyloxyethylthio)xylylene, α, α′
-di(β-acryloyloxyethylthio)-2,3,
5゜6-tetrachloro-p-xylylene, α,α'-di(β-methacryloyloxyethylthio)-2゜3.5
．． 6-tetrachloro-p-xylylene, 4,4'-di(
β-acryloyloxyethoxy) di-phenyl sulfide, 4,4'-di(β-methacryloyloxyethoxy) diphenyl sulfide, 4,4'-di(β-acryloyloxyethoxyethoxy) diphenyl sulfone,
4,4'-di(β-methacryloyloxyethoxyethoxy)diphenyl sulfone, 4,4'-di(β-acryloyloxyethylthio)diphenyl sulfide, 4,
4'-di(β-methacryloyloxyethylthio)diphenyl sulfide, 4,4'-di(β-acryloyloxyethylthio)diphenylsulfone, 4,4'-cy(
β-methacryloyloxyethylthio) diphenyl sulfone, 4,4'-di(β-methacryloyloxyethylthio) diphenyl ketone, β, β'-di(p-acryloyloxyphenylthio) diethyl ether, β, β'
-di(p-methacryloyloxyphenylthio)diethyl ether, β.

Examples include β'-di(p-methacryloyloxyphenylthio)diethylthioether.

Furthermore, among the monomers represented by the above-mentioned (I), particularly preferable monomers are selected from the viewpoint of optical properties such as the refractive index of the polymer and ease of handling such as monomer viscosity. is -Shipage% formula% () (wherein, R1 represents a hydrogen atom or a methyl group, R3, R
' each represents a divalent hydrocarbon group having 1 to 4 carbon atoms,
Z represents a halogen atom excluding fluorine, l is O or 1-
Indicates an integer of 4. ) is a sulfur-containing monomer.

Specific examples of the monomer represented by (II) include p-bis[β-(meth)acryloyloxyisopropylthio]xylylene, m-his[β-(
meth)acryloyloxyethylthio]ethylphenylene, p-bis[β-(meth)acryloyloxybutylthiocotetrachloroxylylene, and even more preferred monomers are p-bis[β-(meth)acryloyloxy Ethylthiofoxylylene, and m-bis[β-(
meth)acryloyloxyethylthiophylylene.

The monomers represented by the general formula (I) detailed above [of course, the monomers represented by -Shinzo (I[)] may be used alone, or two or more types may be used. may be used in combination as appropriate. Furthermore, for the purpose of adjusting the optical properties of the resulting polymer or adjusting the monomer viscosity, a relatively small amount of the sulfur-containing monomer, preferably 100 parts by weight of the sulfur-containing monomer, is added. In contrast, 20 parts by weight or less of other radically polymerizable monomers can also be used in combination.

Other monomers that can be used in combination include (a) monofunctional acrylic acid and methacrylic acid esters such as methyl acrylate and methyl methacrylate, (b) ethylene glycol diacrylate, diethylene glycol dimethacrylate, α, α- '; Difunctional acrylic acid and methacrylic acid esters such as C4-(β-methacryloyloxyethoxyphenyl)propane, (c)
Examples include trifunctional acrylic acid and methacrylic esters such as trimethylolpropane trimellitate, and (d) aromatic vinyl compounds such as styrene and divinylbenzene.

Next, as the photopolymerization initiator (B) used in the present invention, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4-diphenoxy Dichloroacetophenone, jetoxyacetophenone, ■-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-
Examples include acetophenone compounds such as 1-one, benzophenone compounds such as benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, and 3,3'-dimethyl-4-methoxybenzophenone. Preferred of these photopolymerization initiators are 1-phenyl-2-hydroxy-2-methylpropan-1-one, l-hydroxycyclohexylphenyl ketone, hensifhenone, methyl hendylbenzoate, and diphenoxyhensiphenone. be.

The proportion of photopolymerization initiator (B) used is 100% of the total amount of monomers.
0.02 to 0.3 parts by weight, preferably 0
,05 to 0.2 parts by weight. If the proportion of the photopolymerization initiator is too high, the internal homogeneity of the cured product will be impaired or it will be colored, while if the proportion is too small, the cured product will not have sufficient hardness.

In addition, examples of the ultraviolet absorber (C) used in the present invention include 2,4-dihydroxyhensiphenone, 2-
Hydroxy-4-methoxyhensiphenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2.2'-
Dihydroxydi4. Benzophenone compounds such as 4'-dimethoxybenzophenone, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2
'-Hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroquine-3').

5'-ditertiary-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tertiary+J-
Examples include henctriazole compounds such as phthyl-5'-methylphenyl)benzotriazole. These ultraviolet absorbers may be used alone or in combination of two or more.

The usage ratio of the ultraviolet absorber (C) is 100% of the total amount of monomers.
0.01 to 0.2 parts by weight, preferably 0
．． 03 to 0.1 part by weight. If the proportion of the ultraviolet absorber used is too high, the resulting polymer will not have sufficient hardness or the internal homogeneity of the polymer will be impaired. On the other hand, if the proportion of the ultraviolet absorber used is too small, sufficient ultraviolet blocking properties will not be obtained.

The photopolymerizable composition of the present invention may contain additives such as a polymerization accelerator, a polymerization regulator, an antifogging agent, a mold release agent, and the like, if necessary.

The photocurable composition of the present invention can be easily polymerized and cured by irradiation with active energy rays, preferably active energy rays with a wavelength of 200 to 600 nm. The atmosphere for irradiation may be normally the air, but may also be an inert gas atmosphere. As light sources for active energy rays, known chemical lamps, xenon lamps, low-pressure mercury lamps,
High-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, etc. are used.

Hereinafter, the present invention will be further explained in detail by giving Examples and Comparative Examples. "Parts" in these examples mean parts by weight.

Example 1 All sulfur monomers were p-bis(β-methacryloyloxyethylthio)xylylene represented by the structural formula % (this is referred to as "monomer 2"). )1
00 parts, 1-hydroxycyclohexyne-phenylketone (Ciba-Geigi's trade name Irgacure 184, referred to as "initiator ■") 0.1 part, 2-hydroxy-4
-Octoxybenzophenone (Kyodo Yakuhin Co., Ltd. trade name Biosorb 130, referred to as "absorbent ■") 0.05
and t-butylperoxy-2- as a polymerization regulator.
After adding 0.2 parts of ethylhexanoate and stirring and mixing uniformly, the resulting composition was degassed and placed into a 6-inch thick mold made of a mirror-finished glass plate and silicone rubber under an argon atmosphere. Cast below.

Next, from a distance of 40 cm above the glass surface, output 8
Ultraviolet rays were irradiated for 10 minutes (5 minutes each from both sides of the glass) using a 0 W/am high-pressure mercury lamp. After demolding the obtained cured product, it was heated in an air oven at 100° C. for 2 hours to obtain a colorless and transparent cured product with no optical distortion. This cured product was cut and polished to the dimensions of a measurement sample for measurement of physical properties, and the results of measurement of physical properties were as shown in Table 1.

Example 2 Monomer 09 was used instead of 100 parts of the monomer used in Example 1.
A colorless and transparent cured product without optical distortion was obtained in the same manner as in Example 1 except that 10 parts of triethylene glycol dimethacrylate (hereinafter referred to as "monomer (2)") were used. This cured product was processed in the same manner and its physical properties were measured.

The results were as shown in Table 1.

Example 3 Instead of 100 parts of monomer used in Example 1, 0 parts of monomer
90 parts and 2,2-bisC4-(2-methacryloyloxyethquin)phenyl]propane (this is referred to as "monomer ■")
That's what it means. ), except that a colorless and transparent cured product without optical distortion was obtained in the same manner as in Example 1.

This cured product was processed in the same manner and its physical properties were measured.

The results were as shown in Table 1.

Example 4 Instead of 00.05 parts of the absorbent used in Example 1, 2-(
0.05 part of 2'-hydroquine-5'-methylphenyl) henztriazole (Kyodo Yakuhin Co., Ltd. product name Biosorb 520, referred to as "absorbent ■") was used, and the ultraviolet irradiation time was 10 to 12 minutes (glass 6 on each side
A colorless and transparent cured product with no optical distortion was obtained in the same manner as in Example 1, except that the temperature was changed to 1.5 minutes).

This cured product was processed in the same manner as in Example 1, and its physical properties were measured in the same manner. The results were as shown in Table 1.

Example 5 In place of 18,400.1 parts of Irgacure used in Example 1, 0.1 part of hensifenone ("initiator ■") was used, and the other conditions were the same as in Example 1 to produce a colorless product with no optical distortion. A transparent cured product was obtained.

This cured product was processed in the same manner as in Example 1, and its physical properties were measured in the same manner. The results were as shown in Table 1.

Example 6 In place of the monomer (2) used in Example 1, a monomer represented by the structural formula (%) (hereinafter referred to as "monomer (2)") was used. ), and the other procedures were the same as in Example 1 to obtain a colorless and transparent cured product with no optical distortion.

This cured product was processed in the same manner as in Example 1, and its physical properties were measured in the same manner. The results were as shown in Table 1.

Comparative Example 1 A cured product was obtained in place of 0.1 part of the initiator (1) used in Example 1.

This cured product was yellow in color. This cured product was processed in the same manner as in Example 1, and the physical properties were measured. The results are shown in Table 1.

Comparative Example 2 A cured product was obtained in the same manner as in Example 1 except that 0.1 part of the initiator (3) used in Example 1 was changed to 0.5 part.

This cured product was yellow and had optical distortion.

This cured product was processed in the same manner as in Example 1, and its physical properties were measured in the same manner. The results were as shown in Table 1.

Comparative Example 3 A composition was prepared in the same manner as in Example I except that 0.1 part of the initiator (3) used in Example 1 was changed to 0.005 part, and the composition was cured in the same manner. However, ultraviolet 20
Even after irradiation for 10 minutes on both sides of the glass (each side of the glass was irradiated for 10 minutes), a cured product that could be removed from the mold was not obtained.

Comparative Example 4 A composition was prepared in the same manner as in Example 1 except that 0.05 parts of the absorbent used in Example 1 was changed to 0.4 parts, and the composition was cured in the same manner.

However, even after irradiation with ultraviolet light for 20 minutes, a cured product that could be removed from the mold was not obtained.

The following is a cross mill (effects of the invention) The photocurable composition of the present invention can provide a cured product with excellent internal homogeneity, surface transfer accuracy, ultraviolet ray blocking properties, transparency, and hue, and can be used for the production of optical components. It can be used advantageously.

Claims (1)

[Claims] (1) (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 represents a hydrogen atom or a methyl group, and R^2
represents an alkylene group having 1 to 6 carbon atoms, Ar represents an arylene group or aralkylene group having 6 to 30 carbon atoms, or a group thereof substituted with a halogen atom excluding fluorine, and X represents -O - or -S-, Y indicates that X is -
When O- is indicated, -S- or -SO_2- is indicated, and X
indicates -S-, -S-, -SO_2-, -C
O-, or a group selected from an alkylene group, an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylenethioether group, and an aralkylenethioether group each having 1 to 12 carbon atoms, m and n
each represents an integer of 1 to 5, and p represents a number of 0 to 10. ) Monomer 1 whose main component is a sulfur-containing monomer represented by
00 parts by weight, (B) 0.02 to 0.3 parts by weight of at least one photopolymerization initiator selected from benzophenone photoinitiators and acetophenone photoinitiators, and (C) benzophenone ultraviolet absorption A photocurable composition comprising 0.01 to 0.2 parts by weight of at least one UV absorber selected from UV absorbers and benzotriazole UV absorbers.