JPH04159307A - Photocurable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a photocurable composition that polymerizes and cures by irradiation with active energy rays such as ultraviolet rays. The present invention relates to a cast polymerization composition 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 active energy rays (Japanese Unexamined Patent Application Publication No. 61-194).
No. 401, Japanese Unexamined Patent Publication No. 63-207632, etc.). These methods have the advantage of short-time curing by UV irradiation, but at present, internal homogeneity and surface transfer accuracy are insufficient, and the transparency and hue of lenses obtained by UV curing are generally poor. , polymethyl methacrylate, polycarbonate, and diethylene glycol bisallyl carbonate polymers.

Therefore, lenses obtained by conventional methods using such ultraviolet rays have many practical problems.

[Problems to be Solved by the Invention] The present invention has been made to improve the drawbacks of the conventional method described above. The purpose of the present invention is to provide a cast polymerization composition suitable for manufacturing optical parts having high properties and excellent transparency and hue.

[Means for Solving the Problems] That is, the present invention provides: (A) 100 parts by weight of a diethylenically unsaturated monomer represented by the following formula [1], -(ii
CH・CH2'H+: (Here, A is -5-÷R'+R"-S→r, -5+R3-0→, R'-5-1 or -S+R"
-0-R5-0→, R'-5-, R1-R5 is
Each represents an alkylene group having 1 to 8 carbon atoms, l, m,
n each represents O or an integer of 1 to 4. ) (B) 0.01 to 0.3 parts by weight of a compound represented by the following formula [n] as a photopolymerization initiator (where, X represents a methyl group, a methoxy group, or a chlorine atom, and n represents 2 or 3, and Rh represents a phenyl group or a methoxy group.) (C) 0.01 to 0.2 weight of an ultraviolet absorber consisting of at least one selected from benzophenone ultraviolet absorbers and benzotriazole ultraviolet absorbers. The object of the present invention is to provide a photocurable composition comprising:

The photopolymerizable monomer used in the present invention is a diethylenically unsaturated monomer represented by cutting allowance [I], and specific examples thereof include the following.

Assuming that A is -5+R'-0→, R'-S-, CI(2=CH A is -S + R3-0-R5-0→, R'-S-
Assuming that CH2=CH C1(2=CH CH2=CH A is -S -(-RI -4-R2-S → ", where p is 4 or less excluding 0 is a number,
Indicates the degree of oligomerism. ) The photopolymerization initiator used in the present invention is a compound represented by cutting allowance [11], and specific examples thereof include the following.

2.6-cyphthylbenzoyldiphenylphosphine oxide, 2,4.6-dolylhenzoyldiphenylphosphine oxide, '2,4゜6-dolymethylbenzoylphenylphosphinic acid methyl ester, 2,6
Preferred photoinitiators include 2,4.6-cyclobenzoyldiphenylphosphine oxide, 2,6-cymethoxybenzoyldiphenylphosphine oxide,
Dolimethylbenzoyldiphenylphosphinoxide and trimethylhendiylphenylphosphinic acid methyl ester. These can be used alone or in combination of two or more, and diethylenically unsaturated monomers 1
0.01 to 0.3 parts by weight, preferably 0.02 to 0.2 parts by weight. If the amount of the photopolymerization initiator is too large, not only the internal homogeneity of the resulting polymer will be poor, but also the hue will deteriorate. On the other hand, if the amount of photopolymerization initiator is too small, a sufficient degree of curing cannot be obtained.

The ultraviolet absorbers used in the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxyhensiphenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2.2'-dihydroxy-4-methoxybenzophenone, 2.2'-dihydroxy-4,4'-dimethoxybenzophenone and other hensifhenone compounds;
2-(2'-hydroxy-5-methylphenyl)benzotriazole, i (2'-hydroxy-3', s'
-ditert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, etc., which may be used alone or in combination of two or more. can be used in combination, and 0.01 to 0
．． 2 parts by weight, preferably 0.03 to 0.1 parts by weight.

If the amount of ultraviolet absorber blended is too large, a sufficient degree of curing may not be obtained, or the internal homogeneity of the obtained cured product will be poor. On the other hand, if the amount of ultraviolet absorber is too small, desired ultraviolet blocking properties cannot be obtained.

In addition, the photocurable composition may optionally contain a polymerization accelerator,
Polymerization regulators, antifogging agents, mold release agents, and other additives can be added.

In order to polymerize and cure the photocurable composition of the present invention by irradiation with active energy rays, a wavelength of 200 to 600 nm is required.
Active energy rays are preferred, and the irradiation atmosphere may be either normal air or an inert gas atmosphere. Further, as a light source, a known chemical lamp, xenon lamp, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, etc. can be used.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

[Example 1] A specific example will be shown to explain the present invention in more detail. Note that parts in the examples indicate parts by weight. The various physical properties obtained in the Examples were measured by the following test methods.

(1) Light transmittance: using a test piece of Atsushi 20, 50
The light transmittance at 0 part m was measured.

(2) Refractive index and Atsube number: Measured at 25°C using an Atsube refractometer (manufactured by Atago Corporation).

(3) Optical distortion 2 Measured with a Toshiba distortion tester (manufactured by Toshiba Glass Co., Ltd.), and those with no optical distortion were marked as ○, and those with optical distortion were marked as ×.

Example 1 Diethylenically unsaturated monomer of the following formula (1)C)12=CH
-@-CH2-3-CH2-◎-CHz-5-CHz+
CHoCHz...(1) (However, the bond to the aromatic nucleus at both ends is abbreviated as the secondary monomer (1) which is a mixture of p-position/m-position = 2) 100
0.1 part of 2.4.6-drimethylbenzoyldiphenylphosphine oxide (hereinafter abbreviated as TMDPO), 0.1 part of 2-hydroxy-4-octoxyhensiphenone ("
After adding 0.05 part of "Biosorb 130" (manufactured by Kyodo Yakuhin Co., Ltd.), stirring and mixing uniformly, defoaming, this liquid was placed in a 6 ml thick mold made of a mirror-finished glass plate and silicone rubber in an argon atmosphere. It was undercast. Then, ultraviolet rays were irradiated from a distance of 40 cm above the glass surface for 10 minutes (5 minutes on each side of the glass) using a high-pressure mercury lamp with an output of 80 W/cm. 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 product with no optical distortion. Thereafter, the sample was cut and polished to the dimensions of the measurement sample in order to measure its physical properties. The results of physical property measurements are as shown in Table-1.

Example 2 100 parts of monomer (1) in Example 1 was replaced with monomer (1)
The same procedure as in Example 1 was performed except that 80 parts of dipromostyrene and 20 parts of dipromostyrene were used to obtain a colorless and transparent cured product with no optical distortion. It was processed in the same manner as in Example 1 and its physical properties were measured. The measurement results were as shown in Table-1.

Example 3 100 parts of monomer (1) in Example 1 was replaced with monomer (1)
80815, p-bis(β-methacryloyloxyethylthio)xylylene was used in the same manner as in Example 1 to obtain a colorless and transparent cured product free of optical distortion. It was processed in the same manner as in Example 1 and its physical properties were measured. The measurement results are shown in the table.
It was as shown in 1.

Example 4 0.05 part of 2-hydroxy-4-octoxybenzophenone in Example 1 was converted into 2-(2'-hydroxy-5'
-Methylphenyl)benzotriazole ("Biosorb 520" manufactured by Kyodo Yakuhin Co., Ltd.) 0.05 part and the ultraviolet irradiation time was changed from 10 minutes to 12 minutes (6 minutes on each side of the glass). A colorless and transparent cured product with no optical distortion was obtained. It was processed in the same manner as in Example 1 and its physical properties were measured. The measurement results were as shown in Table-1.

Example 5 0.1 part of TMDP○ in Example 1 was added to 2. 4. 6-
The same procedure as in Example 1 was carried out except that 0.1 part of dolimethylbenzoylphenylphosphinic acid methyl ester (TMPME) was used to obtain a colorless and transparent cured product without optical distortion. It was processed in the same manner as in Example 1 and its physical properties were measured. The measurement results were as shown in Table-1.

Example 6 The same procedure as in Example 1 was carried out except that monomer (1) in Example 1 was replaced with monomer (2) below to obtain a colorless and transparent cured product with no optical distortion. It was processed in the same manner as in Example 1, and its physical properties were measured. The measurement results were as shown in Table-1.

CH2=CHi; CHz-5-CHzCHz-0-CH
zCHz-5-CHz (ToCH2CH.

(However, the bond to the aromatic nuclei at both ends is a mixture of p-position/m-position = %.) Example 7 Same as Example 1 except that the following monomer (3) was used as the monomer. A cured product was obtained in the same manner.

CH2=CHSCH2-5-CH2CH2-0-CH2
-0-CH2CH2-5-CH2=CH・C112 (However, the bond to the aromatic nucleus at both ends is a mixture of P-position/m-position = 2.) Comparative Example 1 TMDPOo in Example 1, 1 Example 1, except that 0.1 part of hensyl dimethyl ketal (BDK) was used for 0.1 part of hensyl dimethyl ketal (BDK).
A cured product was obtained in the same manner as above. However, it did not become colorless and transparent, but took on a yellow color. It was processed in the same manner as in Example 1 and its physical properties were measured. The measurement results were as shown in Table-1.

Comparative Example 2 A cured product was obtained in the same manner as in Example 1, except that 1 part of f7) TMDPOo in Example 1 was replaced with 0.5 part. However, it did not become colorless and transparent, but took on a yellow color.

Additionally, there was optical distortion. It was processed in the same manner as in Example 1 and its physical properties were measured. The measurement results were as shown in Table-1.

Comparative Example 3 The same procedure as in Example 1 was carried out except that 1 part of TMDPOo in Example 1 was replaced with 0.005 part. However, 20
Even when irradiated with ultraviolet rays for minutes (10 minutes on each side of the glass), a cured product that could be removed from the mold was not obtained.

Comparative Example 4 Example 1 except that 0.05 part of 2-hydroxy-4-octoxybenzophenone in Example 1 was replaced with 0.4 part.
operated in the same way. However, even after irradiating the glass with ultraviolet rays for 20 minutes (10 minutes on each side of the glass), no cured product that could be removed from the mold was obtained.

Claims (1)

[Claims] (1), (A) 100 parts by weight of diethylenically unsaturated monomer represented by the following formula [I] ▲ Numerical formula, chemical formula, table, etc. ▼ [I] (Here, A is ▲ Numerical formula, chemical formula, There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R^1 to R^5 are alkylene groups with 1 to 8 carbon atoms, respectively. and l, m, and n each represent 0 or an integer of 1 to 4.) (B) As a photopolymerization initiator, 0.01 to 0.3 parts by weight of a compound represented by the following formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (Here, X represents a methyl group, a methoxy group, or a chlorine atom, n represents 2 or 3, and R^6 represents a phenyl group or a methoxy group. ) (C) A photocurable composition comprising 0.01 to 0.2 parts by weight of an ultraviolet absorber consisting of at least one selected from benzophenone ultraviolet absorbers and benzotriazole ultraviolet absorbers in the above proportions.