JP2003267951A - Active energy ray curing compound and polymer for optical material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray curing compound affording a sufficient polymerization rate even when the amount of a polymerization initiator used for a monomer is ≤1 mass% and providing an active energy ray curing composition affording a resin having a high refractive index and excellent heat resistance by polymerization thereof and further a polymer for optical materials obtained by curing the active energy ray curing composition and having the high refractive index. <P>SOLUTION: The active energy ray curing compound contains ≥2 maleimidocarboxylic acid ester structures and at least sulfur atom in one molecule. The active energy ray curing composition comprises the compound. The polymer for the optical materials is obtained by curing the active energy ray curing composition and has ≥1.53 refractive index. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an active energy ray-curable compound and an active energy ray curable compound in which a polymerization initiator is not added at all or only a very small amount may be added, and the resulting polymer has a high refractive index. The present invention relates to a curable composition and a polymer for an optical material having a high refractive index with little odor during bleed-out and curing.

[0002]

2. Description of the Related Art Plastic materials having a high refractive index are widely used for optical materials, especially for spectacle lenses. Compared to conventional glass lenses, plastic lenses are lighter in weight and easier to mold, and have superior impact resistance, but they are prone to yellowing, difficult to obtain a high refractive index, and poor in abrasion resistance. There is also. It has long been known that resins containing halogen atoms other than sulfur and fluorine have a high refractive index. This is because Fumio Ide "Optoelectronics and Polymer Materials" Kyoritsu Shuppan Co., Ltd. (1
995) on pages 8-12.

Acrylic resins are often used as resins for plastic lenses and the like. In most cases, a polymerization initiator is used to polymerize the acrylic monomer, but the unreacted polymerization initiator remaining in the obtained resin or the decomposition product of the polymerization initiator is the surface of the plastic lens. It often causes bleed-out and yellowing, and has problems such as being heated during curing and generating an odor. JP-A-5-249301 discloses that a monomer component 100 is used when a plastic spectacle lens molding resin is produced by polymerizing an acrylic monomer.
It is described that 0.005 to 5 parts by mass of the polymerization initiator is used with respect to parts by mass, but when the addition amount of the polymerization initiator is 1% by mass or less with respect to the monomer component, it is practical. There is a problem in that a proper polymerization rate cannot be obtained.

[0004]

The problem to be solved by the present invention is that the total amount of the polymerizable compounds contained in the active energy ray-curable composition is not used even if a polymerization initiator is used at all. On the other hand, there is provided an active energy ray-curable compound capable of obtaining a sufficient polymerization rate even if it is 1% by mass or less, and polymerizing to give a resin having a high refractive index and excellent heat resistance. Provide an active energy ray-curable composition containing an active energy ray-curable compound,
Furthermore, there is little odor when bleeding out and curing,
It is intended to provide a polymer for an optical material having excellent heat resistance and a high refractive index.

[0005]

Means for Solving the Problems The present inventors have focused on the fact that a maleimide carboxylic acid ester is polymerized without a polymerization initiator to give a polymer having excellent heat resistance, and is represented by the following general formula 1. If a polymerizable compound according to the present invention is blended in an active energy ray-curable composition, the bismaleimide compound itself becomes
It has been found that a polymer which acts as a polymerization initiator or a curing agent for resins and has a high refractive index and excellent heat resistance can be obtained without using a polymerization initiator.

[0006]

[Chemical 3] (1)

(In the formula, X is -S-, -SS-, -SO.
_{2 -, - SO 2 -O -} , - SO-, or carbon atoms 1-2
0 represents a polymethylene group or an alkylene group. R ₁ ~
R ₈ is independently a hydrogen atom, a halogen atom other than fluorine, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom other than fluorine,
_{SH, -S-R 11 (R} 11 is an alkyl group having 1 to 10 carbon _{atoms), - SO-R 12 (} R 12 is an alkyl group having 1 to 10 carbon _{atoms), - SO 2 -R 13 (} R 13 is 1 to 1 carbon atoms
0 alkyl group), -S-φ (φ represents an aryl group), -SO-φ (φ represents an aryl group), or-
Represents SO ₂ -φ (φ represents an aryl group). Either X or R _{1 to} R ₈ has at least one sulfur atom. R ₉ and R ₁₀ are each independently a hydrogen atom,
Alternatively, it represents an alkyl group having 1 to 5 carbon atoms. m and n are integers of 1 or more that may be the same or different, and are numbers satisfying m + n <9. Y and Z each independently represent a polymethylene group having 1 to 10 carbon atoms or an alkylene group. )

That is, the present invention provides an active energy ray-curable compound represented by the above general formula 1 and having a sulfur atom in the molecule, and an active energy ray-curable composition containing the active energy ray-curable compound. The above problem was solved by providing a polymer for an optical material, which is obtained by polymerizing the active energy ray-curable composition and has a refractive index of 1.53 or more.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The active energy ray-curable compound represented by the general formula (1) of the present invention (hereinafter, the active energy ray-curable compound is simply referred to as "active energy ray-curable compound (A)". ) Has at least two benzene rings and two 5-membered rings derived from a maleimide group in the molecule, the polymer obtained by polymerizing
High hardness and excellent heat resistance. Further, since it has a sulfur atom in the molecule, it has a high refractive index. When the ring structure of the active energy ray-curable compound (A) increases, the solubility in a solvent tends to decrease, but the tendency is relieved by having a (poly) ether bond between the benzene ring and the bond. ing. When the number of repeating ether bonds m and n increases, the flexibility of the obtained polymer also improves. In order for the polymer to have appropriate flexibility, m + n is preferably 4 or more, and more preferably 6 or more. However, when m + n exceeds 8, the refractive index tends to decrease.

In the general formula (1), when R _{1 to} R ₈ are a halogen atom other than fluorine or an alkyl group containing a halogen atom other than fluorine, the refractive index of the resulting polymer is high. R ₉ and R ₁₀ preferably have a small number of carbon atoms in order to keep the solution viscosity of the polymer finally obtained low, and the most preferable case is a hydrogen atom.

The active energy ray-curable compound (A) is
It is a maleimide carboxylic acid ester of a dihydric alcohol. Specific examples of the dihydric alcohol include bis (4-
Hydroxyethoxyphenyl) sulfone, 2- (2-
An alkylene oxide adduct of bisphenol S such as (4- (4- (2- (2-hydroxy-ethoxy) -ethoxy) -benzenesulfonyl) -phenoxy) -ethoxy) -ethanol, bis (3-methyl-4- ( Examples thereof include sulfides such as 2-hydroxyethoxy) phenyl) sulfide. When X in the general formula (1) is -SS-, the wavelength dependence of the refractive index is the smallest, and then
-S -, - SO -, - SO 2 -, - increase in _SO 2 -O- order.

On the other hand, examples of the maleimidocarboxylic acid include maleimidoacetic acid, maleimidopropionic acid, maleimidobutyric acid, maleimidocaproic acid, and maleimidoundecanoic acid. As the chain length of the connecting chain represented by X in the general formula (1) is longer, the number of maleimide groups per unit mass of the active energy ray-curable compound (A) is smaller, and the crosslinking density of the polymer finally obtained is In the present invention, the active energy ray-curable compound (A) having a maleimidoacetic acid residue having the shortest connecting chain is most preferable because it lowers.

Among the active energy ray-curable compounds (A), in particular, the active energy ray-curable compound represented by the general formula (2) (hereinafter, the active energy ray-curable compound is simply referred to as "active energy ray-curable compound"). The polymer obtained from the curable compound (B) ") has high heat resistance and a high refractive index.

[0014]

[Chemical 4] (2)

(In the formula, R ₉ and R ₁₀ each independently represent hydrogen or an alkyl group having 1 to 5 carbon atoms.
m and n are integers of 1 or more that may be the same or different, and are numbers satisfying m + n <9. )

The maleimidocarboxylic acid residue of the active energy ray-curable compound (B) is maleimidoacetic acid having the shortest connecting chain described above, and therefore the polymer using this is
The crosslink density is higher than that of the polymer using the active energy ray-curable compound (A) having a longer connecting chain.

The method for producing the active energy ray-curable compound (A) or the active energy ray-curable compound (B) is not particularly limited, and the condensation reaction of maleimide carboxylic acid and a dihydric alcohol, or maleimide carboxylic acid ester and 2 It can be produced by a known ester synthesis reaction such as a transesterification reaction with a polyhydric alcohol. In the ester synthesis reaction, acid catalysts, aliphatic or aromatic sulfonic acids, titanium alkoxides, silicon alkoxides, zirconium alkoxides, metal alkoxides other than alkaline catalysts, metal halides, metal oxides and the like, known conventional esterification catalysts, Alternatively, a transesterification catalyst can be used. In order to prevent the thermal polymerization of the maleimide group during the ester synthesis reaction, a known and commonly used polymerization inhibitor such as hydroquinone or 4-tert-butylcatechol may be used.

The active energy ray-curable composition of the present invention contains an active energy ray-curable compound (A) or an active energy ray-curable compound (B) as an essential component and, in addition, the active energy ray-curable composition. It may contain a monomer copolymerizable with the compound, a polymerization initiator, a solvent, and other various additives added as necessary. Examples of the monomer copolymerizable with the active energy ray-curable compound (A) or the active energy ray-curable compound (B) include (meth) acrylic acid, (meth) acrylic acid esters, styrene and the like, maleimide. Known monomers that can be copolymerized with the compound, or oligomers having a polymerizable functional group such as urethane (meth) acrylate can be mentioned.

Since the active energy ray-curable compound (A) or the active energy ray-curable compound (B) itself acts as a polymerization initiator, the active energy ray-curable composition of the present invention contains a polymerization initiator. Although it is not necessary to add an agent, when the concentration of the active energy ray-curable compound in the active energy ray-curable composition is extremely low or when a high polymerization rate is required, the usual thermal polymerization or activity As in the case of energy ray polymerization, a thermal polymerization initiator or a photopolymerization initiator can be used. However, when the obtained polymer is used as an optical material, the content is
A thermal polymerization initiator or a photopolymerization initiator within a range not exceeding 1% by mass based on the total amount of the active energy ray-curable compound contained in the active energy ray-curable composition and the monomer copolymerizable therewith. Is preferably added. When the addition rate exceeds 1% by mass, the unreacted polymerization initiator and its decomposition products remaining in the polymer are liable to give off an odor at the time of curing or reduce the light resistance.

There are no particular restrictions on the polymerization initiator that can be used in the active energy ray-curable composition of the present invention, and known and commonly used thermal polymerization initiators and photopolymerization initiators can be used.
Specifically, for example, thermal polymerization initiators such as benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, N, N′-azobisisobutyronitrile, and 1-hydroxy. Cyclohexyl phenyl ketone, benzoin butyl ether, benzyl dimethyl ketal, diethoxy acetophenone, acyloxime ester, 4-tert-butyl dichloroacetophenone, hydroxyacetophenone,
Examples thereof include photopolymerization initiators such as acylphosphine oxide, benzophenone, Michler's ketone, 2-ethylanthraquinone, and isobutylthioxanthone.

In order to improve storage stability, the active energy ray-curable composition of the present invention contains hydroquinone or 4
A known and commonly used polymerization inhibitor such as -tert-butylcatechol may be added. If necessary, a solvent such as acetone, toluene, ethyl acetate, chloroform, or dichloromethane can be added.

The active energy ray-curable composition of the present invention can be cured by irradiation with active energy rays such as ultraviolet rays and electron beams. As the active energy ray, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, a short arc lamp, a helium / cadmium laser, an argon laser, an excimer laser. It is preferable to use ultraviolet rays having a laser as a light source.

The active energy ray-curable composition of the present invention can also be cured by heat. In this case as well, curing can be carried out without an initiator, but if necessary, the above-mentioned known conventional polymerization initiator may be added.

When the polymer obtained by curing the active energy ray-curable composition of the present invention is used as a high refractive index optical material such as a coating agent or a lens for optical parts, the refractive index of the polymer is 1. It is preferably 0.53 or more. In order to obtain a polymer having such a high refractive index, sulfur in the molecule is used as a copolymerization monomer used together with the active energy ray-curable compound (A) or the active energy ray-curable compound (B). It is preferable to use a (meth) acrylic monomer having an atom, a halogen atom other than fluorine, and an aromatic ring.

[0025]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. Unless stated otherwise,
And "%" represent "parts by mass" and "% by mass", respectively.

Example 1 In a reaction vessel equipped with a cooling pipe and a decanter, 48 parts of maleimide acetic acid, 44 parts of bis (4-hydroxyethoxyphenyl) sulfone (“SE-2” manufactured by Meisei Chemical Industry Co., Ltd.), p- Toluenesulfonic acid monohydrate (5 parts), toluene (300 parts) and hydroquinone (0.2 parts) were charged, and while stirring, a mixed gas of oxygen and nitrogen having an oxygen content of 7% by volume was blown into the reaction mixture at a pressure of 65 kP.
Under the condition of a, the temperature is maintained at 70 ° C for 7 hours after being heated to 70 ° C
During this time, the produced water was removed from the reaction system through the decanter. Then, it was allowed to cool and left at room temperature for 24 hours. The precipitate was filtered off from the reaction mixture, the residual solvent was distilled off from the obtained precipitate, and silica gel was used as the filler, and a mixed solvent of chloroform and ethanol with a volume ratio of 98: 2 was used as the solvent. The reaction product was separated by column chromatography and the solvent was distilled off to obtain 24 parts of the active energy ray-curable compound (1) of bis (4-hydroxyethoxyphenyl) sulfone.

The active energy ray-curable compound (1) thus obtained was used to prepare an active energy ray-curable composition having the following composition. Active energy ray-curable compound (1) 100 parts Chloroform 200 parts

Example 2 100 parts of maleimidoacetic acid and bis (3-methyl-4- (2-hydroxyethoxy) phenyl) sulfide (manufactured by Meisei Chemical Co., Ltd., "HMPS") were placed in a reaction vessel equipped with a cooling pipe and a decanter. -20X ") 72
Parts, p-toluenesulfonic acid monohydrate 9 parts, toluene 6
00 parts and 0.4 parts of hydroquinone were charged, and while stirring, a mixed gas of oxygen and nitrogen having an oxygen content of 7% by volume was blown into the reaction mixture at a pressure of 65 kPa and a temperature of 70 ° C.
After the temperature was raised to 70 ° C., the temperature was maintained at 70 ° C. for 7 hours, during which the produced water was removed to the outside of the reaction system through a decanter. Then, it was allowed to cool and left at room temperature for 24 hours. The precipitate was separated from the reaction mixture by filtration, washed with methanol, and purified by recrystallization from acetone to obtain 27 parts of active energy ray-curable compound (2).

An active energy ray-curable composition was prepared in the same manner as in Example 1 except that the active energy ray-curable compound (2) was used in place of the active energy ray-curable compound (1). Prepared.

Example 3 In a reaction vessel equipped with a cooling pipe and a decanter, 75 parts of maleimide acetic acid, a mixture of an ethylene oxide adduct of bisphenol S represented by the general formula (3) and toluene (Meisei Chemical Industry Co., Ltd.). Made "Bisphe
NolS40X ") 82 parts, p-toluenesulfonic acid monohydrate 8 parts, toluene 520 parts, and hydroquinone 0.3 part are charged, and a mixed gas of oxygen and nitrogen having an oxygen content of 7% by volume is reacted under stirring. While blowing in, pressure 65
Under the condition of kPa, the temperature was raised to 70 ° C. and maintained at 70 ° C. for 14 hours, during which the produced water was removed from the reaction system via a decanter. After completion of the reaction, 0.3 part of hydroquinone was added, and the solvent was distilled off from the reaction mixture, followed by column chromatography using silica gel as a filler and a mixed solvent of chloroform and ethanol in a volume ratio of 98: 2 as a solvent. The reaction product was separated to obtain 80 parts of the active energy ray-curable compound (3).

[0031]

[Chemical 5] (3)

(In the formula, m = 1 to 3, n = 1 to 3, m + n
= 4. ) Active energy ray-curable compound (1) in Example 1
An active energy ray-curable composition was prepared in the same manner as in Example 1 except that the active energy ray-curable compound (3) was used instead of.

COMPARATIVE EXAMPLE 1 A reaction vessel equipped with a cooling tube and a decanter was placed in a mixture of 50 parts of acrylic acid, an ethylene oxide adduct of bisphenol S and toluene (“Bisphenol S40X” manufactured by Meisei Chemical Industry Co., Ltd.).
Parts, p-toluenesulfonic acid monohydrate 8 parts, toluene 5
60 parts and hydroquinone (0.3 parts) were charged, and while stirring, while blowing an oxygen / nitrogen mixed gas having an oxygen content of 7% by volume into the reaction mixture, the temperature was raised to 70 ° C. under the condition of a pressure of 65 kPa, and then 6 hours 70 The temperature was maintained at 0 ° C., and the generated water was removed to the outside of the reaction system through the decanter during this time. After cooling, 0.3 part of hydroquinone was added and the solvent was distilled off from the reaction mixture. Using silica gel as a filler and a mixed solvent of chloroform and ethanol in a volume ratio of 98: 2 as a solvent,
The reaction product was separated by column chromatography. The solvent is distilled off and the active energy ray-curable compound (H
1) 30 parts were obtained.

An active energy ray-curable composition was prepared in the same manner as in Example 1 except that the active energy ray-curable compound (H1) in Example 1 was used in place of the active energy ray-curable compound (1). Prepared.

Comparative Example 2 An active energy ray-curable compound (H1) was used in place of the active energy ray-curable compound (1) in Example 1, and a photopolymerization initiator “IRGA” manufactured by Ciba Specialty Chemicals was used. Cure 18
An active energy ray-curable composition was prepared in the same formulation as in Example 1 except that 5 parts of "4" was added. The active energy ray-curable compositions prepared in the above Examples and Comparative Examples were used to perform the following tests, and the results are shown in Table 1.

(Curability test of active energy ray-curable composition coating film) 10 parts of the active energy ray-curable compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were mixed with chloroform 1
After diluting with 0 part, after coating on a glass plate with a bar coater so that the coating film thickness after curing becomes 10 μm, chloroform is volatilized first at 50 ° C. and normal pressure and then at 50 ° C. and 133 Pa under reduced pressure. UV irradiation was performed using a UV irradiation device manufactured by Eye Graphics Co., Ltd. so that the irradiation amount was 3 kJ / m ² . With respect to the coating film after ultraviolet irradiation, the presence or absence of odor was examined by a sensory test, and the degree of curing was examined by a finger touch test. The case where a practical degree of curing was obtained was evaluated as ◯, and the case where a practical degree of curing was not obtained was evaluated as x.

(Measurement of Refractive Index) The active energy ray-curable compositions prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were coated on a glass plate having a thickness of 6 mm and a refractive index of 1.740 after curing. After coating with a bar coater to a film thickness of 100 to 200 μm, first at 50 ° C. and normal pressure, then at 50 ° C., 133
Chloroform is volatilized under a reduced pressure of Pa, and the irradiation amount is 50 kJ using a UV irradiation device manufactured by Eye Graphics Co.
Ultraviolet rays were radiated so as to be / m ² . Without peeling the cured coating film obtained by UV irradiation from the glass plate,
Using the Abbe refractometer "2T" manufactured by Atago Co., Ltd., 2
The D-line refractive index of the cured coating film at 5 ° C. was measured.
When the refractive index was 1.53 or more, it was evaluated that it could be used as a polymer for high refractive index optical materials.

(Weather resistance test)
Of the curable composition coating film).
Regarding the cured coating film of the energy ray curable composition,
・ Using a metal weather weather tester manufactured by Wintes
Under nitrogen atmosphere, light irradiation amount 180 J / cm ^Two・ In hr
4 hours, then leave for 4 hours without light irradiation
After 11 cycles of return, the bleeder is visually inspected.
I checked for the presence or absence of the horse. No bleedout observed
When the bleedout was observed, it was evaluated as ○, and when it was observed, it was evaluated as ×.
I paid.

[0039]

[Table 1]

[0040]

INDUSTRIAL APPLICABILITY The active energy ray-curable compound of the present invention has a maleimide group having high heat resistance as a polymerizable functional group, and has a sulfur atom and a benzene ring in the molecule. Therefore, a polymerization initiator is used. Even without it, the coating film can be irradiated with active energy rays to be cured, and a polymer having a high refractive index can be obtained. In the polymer obtained from the active energy ray-curable compound using a conventional polymerization initiator, unreacted polymerization initiator and low molecular weight decomposition products of the polymerization initiator remain as impurities, and odor is generated during the curing process. Or causing yellowing or bleeding out and impairing the weather resistance, while in the cured polymer using the active energy ray-curable compound of the present invention without adding a polymerization initiator, There are no such impurities. Therefore, when the active energy ray-curable compound is used, it does not emit an odor due to the polymerization initiator during the curing step, has weather resistance and heat resistance, and has a high refractive index. You can get coalesced.

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Claims (4)

[Claims] 1. An active energy ray-curable compound represented by the following general formula (1) and having a sulfur atom in the molecule. [Chemical 1] (1) (In the formula, X is —S—, —S—S—, —SO ₂ —,
-SO ₂ -O -, - SO-, or represents a polymethylene group or an alkylene group having 1 to 20 carbon atoms. R _{1 to} R
₈ are each independently a hydrogen atom, a halogen atom other than fluorine, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with a halogen atom other than fluorine, -S
_{H, -S-R 11 (R} 11 is an alkyl group having 1 to 10 carbon _{atoms), - SO-R 12 (} R 12 is an alkyl group having 1 to 10 carbon _{atoms), - SO 2 -R 13 (} R 13 is Carbon number 1-10
Alkyl group), -S-φ (φ represents an aryl group),
-SO-φ (φ represents an aryl group), or -SO ₂
Represents -φ (φ represents an aryl group). X or R ₁ ~
Any of R ₈ has at least one sulfur atom. R ₉ and R ₁₀ are each independently a hydrogen atom,
Alternatively, it represents an alkyl group having 1 to 5 carbon atoms. m and n are integers of 1 or more, which may be the same or different, and m
It is a number that satisfies + n <9. Y and Z each independently represent a polymethylene group having 1 to 10 carbon atoms or an alkylene group. ) 2. The active energy ray-curable compound according to claim 1, which is represented by the following general formula (2). [Chemical 2] (2) (In the formula, R ₉ and R ₁₀ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. M and n
Is an integer greater than or equal to 1, which may be the same or different,
It is a number that satisfies m + n <9. ) 3. An active energy ray curable composition comprising the active energy ray curable compound according to claim 1. 4. A polymer for optical materials, which is obtained by polymerizing the active energy ray-curable composition according to claim 3, and has a refractive index of 1.53 or more.