JPH1081716A - Ultraviolet ray absorbing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject absorbing agent consisting of a polymer obtained by polymerizing a component containing a specific dibenzoylmethane, especially excellent in absorbing property of UV-A and useful as a cosmetic material. SOLUTION: This ultraviolet rays absorbing agent consists of a polymer obtained by polymerizing (A) 4-tert-butyl-4'-(2-methacroyloxyethoxy) dibenzoylmethane expressed by the formula with preferably (B) a monomer copolymerizable with the component (A), especially an alkyl (meth)acrylate having a 1-4C alkyl group, e.g. methyl (meth)acrylate. Further, e.g. the weight ratio of the components (A) to (B) is preferably made as >=0.01/99.99.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an ultraviolet absorber. More specifically, the present invention relates to an ultraviolet absorber excellent in ultraviolet absorption and useful as a raw material for cosmetics, fibers, films, inks, paints, contact lenses, lenses for eyeglasses, and the like.

[0002]

2. Description of the Related Art Ultraviolet rays are constantly falling on us in daily life. UV light has a wavelength of 320-400n
m long wavelength ultraviolet (hereinafter referred to as UV-A), wavelength 2
It can be divided into 90-320 nm middle wavelength ultraviolet (hereinafter, referred to as UV-B) and 180-290 nm short wavelength ultraviolet (hereinafter, referred to as UV-C).

[0003] The ultraviolet rays that have the greatest effect on human society are due to sunlight, but most of the UV-C is absorbed by the ozone layer, and UV-B and UV-B are absorbed.
A reaches the surface. The ultraviolet rays UV-B and UV-A
The consequences are for the human body and for all substances surrounding humans.

[0004] UV-B mainly acts on the surface of the skin, rapidly causing sunburn, causing spots, freckles, and drying of the skin. UV-A reaches the dermis of the skin. Not only promote skin aging, but also enhance the skin's degenerative action by UV-B.

[0005] As is apparent from the above, UV-
Protecting the skin from UV-A as well as B
UV-A absorbers have been developed and marketed in the field of cosmetics, which are important in preventing the promotion of skin aging and preventing the occurrence of spots, freckles and other adverse effects.

Therefore, in order to protect the skin from UV-A, attempts have been made to use inorganic powders such as titanium dioxide and zinc oxide in cosmetics.

However, since the inorganic powder has a low ultraviolet absorbing property, it needs to be used in a large amount in order to protect ultraviolet rays in the UV-A region. Has the disadvantage that it is impaired.

Also, for example, 4-tert-butyl-
4'-methoxydibenzoylmethane (Dibodan Co., Ltd.
It has also been attempted to incorporate a low molecular weight UV absorber such as Parasol A) into cosmetics.

[0009] However, the low molecular weight ultraviolet absorber has a disadvantage that its safety such as irritation to skin and absorption is poor.

On the other hand, in the field of polymer materials which are indispensable to human society, for example, fibers, films, inks,
There is an increasing demand for ultraviolet absorbers for preventing deterioration of polymer materials such as paints and contact lenses due to ultraviolet rays. Furthermore, as the development of functional polymer materials progresses,
Films that remove ultraviolet rays from transmitted light, such as ultraviolet ray cut films, have become commercially available.

However, generally, for example,
When a low molecular weight ultraviolet absorber such as tert-butyl-4'-methoxydibenzoylmethane is used in the field of polymer materials such as fibers, films, inks, paints, and contact lenses, the production or molding process is required. There is a problem that the low molecular weight ultraviolet absorber sometimes volatilizes and elutes, and furthermore, volatilizes from the surface of the obtained molded product, bleeds out and repels on the surface.

Therefore, in order to solve the above problem, development of a copolymer using a monomer having an ultraviolet absorbing structure as one polymerization component has been promoted.

For example, a polymerization component containing methyl methacrylate as a main component is mixed with a 2-hydroxy-5-acryloxyalkylphenyl-2H-benzotriazole as an ultraviolet-absorbing monomer, and the polymerization component is copolymerized. It has been proposed to use the obtained copolymer as a contact lens or a lens for spectacles (Japanese Patent Application Laid-Open No. 60-1985).
-38411).

However, since the above-mentioned copolymer is poor in transparency, it is difficult to use the copolymer in products requiring optical transparency such as contact lenses and eyeglass lenses. Furthermore, in order to avoid yellowing of contact lenses and spectacle lenses, it is necessary to transmit light having a wavelength exceeding 400 nm. However, the copolymer has a disadvantage of absorbing light having a wavelength exceeding 400 nm. Have.

[0015]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has excellent ultraviolet absorbing properties, for example, for cosmetics, fibers, films, inks, paints, contact lenses, and lenses for glasses. Another object of the present invention is to provide an ultraviolet absorber which can impart optical transparency and is excellent in UV-A absorption.

[0016]

According to the present invention, there is provided a compound of formula (I):

[0017]

Embedded image

4-tert-butyl-4 '
The present invention relates to an ultraviolet absorber comprising a polymer obtained by polymerizing a polymerization component containing-(2-methacryloyloxyethoxy) dibenzoylmethane.

[0019]

DETAILED DESCRIPTION OF THE INVENTION As described above, the ultraviolet absorbent of the present invention has the formula (I):

[0020]

Embedded image

4-tert-butyl-4 'represented by the formula
It comprises a polymer obtained by polymerizing a polymerization component containing-(2-methacryloyloxyethoxy) dibenzoylmethane.

In the present invention, formula (I):

[0023]

Embedded image

4-tert-butyl-4 'represented by the formula
Since-(2-methacryloyloxyethoxy) dibenzoylmethane is used as a polymerization component, the resulting ultraviolet absorber has significantly improved ultraviolet absorption.

In the present invention, the total amount (100% by weight) of the polymerization component is 4-tert-butyl-
4 '-(2-methacryloyloxyethoxy) dibenzoylmethane, i.e., the polymer is 4-
A homopolymer of tert-butyl-4 '-(2-methacryloyloxyethoxy) dibenzoylmethane may be used.
A copolymerizable monomer copolymerizable with tert-butyl-4 '-(2-methacryloyloxyethoxy) dibenzoylmethane (hereinafter, referred to as a copolymerizable monomer) may be appropriately contained depending on the purpose.

Examples of the copolymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, Optionally substituted alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate; methyl vinyl ether, n- Propyl vinyl ether, i-butyl vinyl ether, n-butyl vinyl ether, styrene, α-methylstyrene, (meth) acrylonitrile,
Vinyl monomers such as vinyl acetate, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, ethylene, propylene, isoprene, chloroprene, and butadiene; carboxyl group-containing vinyl monomers such as (meth) acrylic acid and itaconic acid; β-hydroxy Hydroxyl-containing vinyl monomers such as ethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate and allyl alcohol; methylol-containing vinyl monomers such as N-methylol (meth) acrylamide; amino groups such as dimethylaminoethyl (meth) acrylate Vinyl monomer containing; acid amide group-containing vinyl monomer such as (meth) acrylamide; glycidyl group-containing vinyl monomer such as glycidyl (meth) acrylate and glycidyl allyl ether; γ- (meth) Methacryloyloxy trimethoxy silane, vinyl triacetoxy silane, such as hydrolyzable silyl group-containing vinyl monomers such as vinyltrimethoxysilane and the like, and these can be used alone or in admixture of two or more.

Among the copolymerizable monomers, an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms is preferable because it has a high glass transition temperature and can provide a polymer having excellent moldability. .

In this specification, "~ (meth) acryl ..." means ~ acryl ... and / or ~ methacryl ...
Means

When the above-mentioned copolymerizable monomer is contained in the polymerization component, the above-mentioned 4-tert-butyl-4'-
The ratio of (2-methacryloyloxyethoxy) dibenzoylmethane to the copolymerizable monomer [4-tert-butyl-4 '-(2-methacryloyloxyethoxy) dibenzoylmethane / copolymerizable monomer (weight ratio)] is as follows: In order to exhibit sufficient ultraviolet absorption, 0.01 / 9
It is desirably at least 9.99, preferably at least 0.02 / 99.98. Further, in order to effectively disperse the obtained ultraviolet absorber in, for example, a contact lens, a lens for eyeglasses, etc., and to exhibit sufficient ultraviolet absorption while maintaining excellent optical transparency, the above-mentioned ratio is required. (Weight ratio) is 10/90 or less, preferably 5/95
It is desirable to make the following.

The polymer used in the present invention is 4-t
tert-Butyl-4 '-(2-methacryloyloxyethoxy) dibenzoylmethane and, if necessary, a polymerizable component containing a copolymerizable monomer, for example, a polymerization initiator or the like is blended, and the polymerizable component is mixed by a usual polymerization method. Can be obtained by polymerizing

Examples of the polymerization initiator include di-t
organic peroxides such as tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, cumene peroxide; azobisisobutyronitrile, dimethyl-2,2'-azobis (2-methylpropionate), 2, Azo-based oil-soluble polymerization initiators such as 2'-azobis (2,4-dimethylvaleronitrile) are exemplified.

The amount of the polymerization initiator is not particularly limited, but is usually preferably about 0.01 to 5 parts based on 100 parts (parts by weight, hereinafter the same) of the total amount of the polymerization components.

The atmosphere in which a polymerization initiator is blended and the polymerization reaction is performed is preferably an inert gas atmosphere such as nitrogen gas or argon gas.

The polymerization method of the above-mentioned polymerization components is not particularly limited, and for example, a usual method such as emulsion polymerization, solution polymerization, or bulk polymerization can be employed.

For example, when the above-mentioned emulsion polymerization method is employed, for example, higher alcohol sulfate sodium salt, higher alcohol sulfate amine salt, alkyl sulfonate sodium salt, alkyl naphthalene sulfonate sodium salt, alkyl phosphate, dialkyl sulfosuccinate Surfactants such as rosin and rosin soap; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkylamine, polyoxyethylene alkyl amide, sorbitan alkyl ester, polyoxysorbitan alkyl Nonionic surfactants such as esters; trimethylaminoethylalkylamide halogenides, alkylpyridinium sulfates, alkyl A surfactant such as trimethyl ammonium halides, alone or in admixture of two or more kinds,
It is preferably used as an emulsifier.

The amount of the surfactant is not particularly limited, but is usually 0.1 to 100 parts by weight based on the total amount of the polymerization components.
It is preferable that the amount is about 1 part.

When the above-mentioned solution polymerization method is employed, for example, toluene, xylene, benzene,
Cyclohexane, n-hexane, heptane, ethyl acetate, methyl cellosolve, ethyl cellosolve, glyme,
Diglyme, methanol, ethanol, propanol,
Solvents such as butanol and dioxane, alone or
It is preferable to use a mixture of two or more species.

The polymerization temperature and the polymerization time when the polymerization components are polymerized are not particularly limited. For example, the type of copolymerizable monomer used if necessary, such as 4-tert-butyl-4 '-(2-methacryloyloxyethoxy) ) It may be appropriately adjusted according to the ratio of dibenzoylmethane to the copolymerizable monomer.

The polymer thus obtained is, for example, in the case of latex, after coagulating the latex,
Dehydration and drying may be performed to obtain a powder.For example, in the case of a dispersion, particles in the dispersion may be separated from a solvent by filtration, centrifugation, or the like, and dried to obtain a powder. .

The ultraviolet absorbent according to the present invention comprises 4-tert-
Butyl-4 '-(2-methacryloyloxyethoxy)
It is composed of a polymer obtained by polymerizing a polymerization component containing dibenzoylmethane and, if necessary, a copolymerizable monomer.In the present invention, as long as the purpose is not impaired, other polymers than the polymer are used. A resin or the like may be used, and a mixture of the polymer and the resin may be used as the ultraviolet absorber.

Examples of the resin which may be mixed with the polymer include polyethylene, polypropylene, polyisobutylene and polymethylbutene which may be crosslinked.
1, homopolymers of mono- or diolefins such as polymethylpentene-1, polyisoprene and polybutadiene, and mixtures of homopolymers such as polypropylene and polyethylene, polypropylene and polybutene-1, and polypropylene and polyisobutylene; ethylene- Propylene copolymer, propylene-butene-1 copolymer, propylene-isobutylene copolymer, ethylene-butene-1 copolymer, ethylene-propylene-hexadiene copolymer,
Copolymers using mono- or diolefins such as ethylene-propylene-dicyclopentadiene copolymer, ethylene-propylene-ethylidene norbornene copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer; Polystyrene, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-acrylate copolymer, styrene-acrylonitrile-methacrylate copolymer, styrene-acrylonitrile modified with acrylate polymer Copolymer, styrene-butadiene-styrene block copolymer, styrene-grafted styrene-polybutadiene graft copolymer, styrene-grafted acrylonitrile-butadiene-styrene copolymer And styrene-based polymers such as mixtures thereof; polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, rubber chloride, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinylidene chloride- Halogen-containing vinyl polymers such as vinyl acetate copolymers; polyacrylates, polymethacrylates, polyacrylamides,
A polymer comprising an α, β-unsaturated acid such as polyacrylonitrile or a derivative thereof; polyvinyl alcohol, polyvinyl acetate, polyvinyl polystearate, polyvinyl benzoate, polyvinyl polymaleate, polyvinyl butyral,
Unsaturated alcohols or amines such as polyallyl phthalate and polyallyl melamine, or polymers comprising acyl derivatives or acetal thereof, or unsaturated alcohols or amines such as ethylene-vinyl acetate copolymer or acyl derivatives thereof Or a copolymer of an acetal and another vinyl compound; a polymer of an epoxide such as a polymer using polyethylene oxide or bis-glycidyl ether; a polyoxymethylene; a polyoxymethylene using ethylene oxide as a comonomer; Polyacetals; polyalkylenes or polyarylene oxides such as polyoxyethylene, polypropylene oxide, polybutylene oxide and polyphenylene oxide; polyurethanes such as polyurethane and polyurea Down like; polycarbonates; polysulfones, polyamides 6, polyamide 6,6, polyamide 6,10, polyamide 11, polyamide 12, poly -m
Polyamides using diamines such as phenylene isophthalamide and dicarboxylic acids, aminocarboxylic acids, lactams thereof, etc .; dicarboxylic acids such as polyethylene glycol terephthalate and poly-1,4-dimethylolcyclohexane terephthalate and dialcohols, and hydroxycarboxylic acids Polyester using acid, its lactam, etc .; phenol-formaldehyde resin, urea-
A crosslinked resin comprising an aldehyde such as formaldehyde resin, melamine-formaldehyde resin and phenol, urea or melamine; a glycerin-phthalic acid resin or a mixture thereof with a melamine-formaldehyde resin; a saturated or unsaturated dicarboxylic acid; Polyesters comprising polyhydric alcohols, unsaturated polyester resins using vinyl compounds as crosslinking agents and halogen-containing modified products of the unsaturated polyester resins; cellulose, cellulose acetate, cellulose propionate, cellulose butyrate, methylcellulose, etc. Chemically modified homologous derivatives of cellulose such as cellulose ethers, natural polymers such as natural rubber, and the like, and these can be used alone or in combination of two or more.

When the above resin is mixed, in order for the obtained ultraviolet absorber to exhibit sufficient ultraviolet absorption, the ratio of the polymer and the resin in the ultraviolet absorber [polymer / resin ( Weight ratio)] is 1/99 or more, preferably 2/98 or more. In addition, in order to reduce the optical transparency of the material containing the ultraviolet absorber or eliminate the possibility of yellowing, the ratio (weight ratio) is 95/5 or less, preferably 90/10 or less. It is desirable to do.

The ultraviolet absorbent of the present invention includes the above-mentioned 4-te
rt-butyl-4 '-(2-methacryloyloxyethoxy) dibenzoylmethane (maximum absorption wavelength λmax: 3
57-359 nm, log εmax: about 4.6 in dichloromethane) is incorporated without a decrease in its ultraviolet absorptivity, so that the ultraviolet absorber has extremely excellent ultraviolet absorption, especially in the UV-A region. It has sex.

From the viewpoint of exhibiting a sufficient ultraviolet absorbing effect, the proportion of 4-tert-butyl-4 '-(2-methacryloyloxyethoxy) dibenzoylmethane in the total weight of the ultraviolet absorbing agent is 0.01%. % By weight, preferably 0.02% by weight, and from the viewpoint of lowering optical transparency and preventing yellowing, 10% by weight or less,
Preferably, the content is 5% by weight or less.

The ultraviolet absorbent of the present invention exhibits excellent ultraviolet absorption and optical transparency, and is particularly excellent in UV-A absorption. Therefore, the ultraviolet absorber is useful as a raw material for, for example, cosmetics, fibers, films, inks, paints, contact lenses, eyeglass lenses, and the like.

[0046]

EXAMPLES Next, the ultraviolet absorbent of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

Synthesis Example 1 (4-tert-butyl-4'-
(Synthesis of 2-hydroxyethoxy) dibenzoylmethane Oily sodium hydride (content of about 60) was placed in 560 ml of dry tetrahydrofuran charged in a 2 liter four-necked flask equipped with a stirrer, a thermometer and a condenser.
8% (2.00% by weight) was suspended at 27 ° C., and a solution of 168.18 g (1.00 mol) of 4 ′-(2-hydroxyethoxy) acetophenone in 300 ml of tetrahydrofuran was added at a reaction temperature of 45 ° C. While keeping below
The solution was dropped under a nitrogen gas stream.

Then, the mixture was stirred until the generation of hydrogen gas was eased, and then methyl 4-tert-butylbenzoate 2 was added.
35.5 g (1.20 mol) were added dropwise. After dropping,
The reaction temperature was gradually increased and stirring was continued under reflux for 12 hours. The disappearance of 4 '-(2-hydroxyethoxy) acetophenone was determined by TLC (silica gel plate, developing solution: n-hexane / ethyl acetate (volume ratio: 3/1) and HPLC).
[Column: ODS (silica gel chemically bonded with octadecyl group), 4.6 × 150 mm, developing solution: acetonitrile / 0.02 M phosphate buffer (pH 6.8) (volume ratio: 7/3)] Then, cool the reaction solution,
Neutralized and separated with a 12% aqueous hydrochloric acid solution. The organic layer was washed with a saturated saline solution, and the organic layer was concentrated. The crude crystals obtained were recrystallized from methanol to give white crystals 242.2.
g. The melting point of the obtained crystals was 95 to 95.5 ° C, and the yield was 67%.

Next, regarding the obtained crystal, ¹ H—N
MR (measured by GX-500, manufactured by JEOL Ltd.), ¹³
C-NMR (measured by GX-500, manufactured by JEOL Ltd.), infrared absorption spectrum (hereinafter referred to as IR)
(Measured by FTIR-4200, manufactured by Shimadzu Corporation), ultraviolet absorption spectrum (hereinafter referred to as UV)
(Measured by UV-240, manufactured by Shimadzu Corporation) and mass spectrum (GCMS QR, manufactured by Shimadzu Corporation)
(Measured at 5000), and elemental analysis was performed. These data are shown below.

(A) ¹ H-NMR (500 MHz, internal standard: TMS) (CDCl ₃ ) δ ppm: 1.36 (s, 9H, -C (C
_{H 3) 3), 4.01 (} br, 2H, -C H 2 -OH),
4.17 (t, 2H, J = 4.0Hz, -C H 2 -CH 2 -
OH), 6.78 (s, 1H, enol-based olefinic hydrogen), 7.00 (d, 2H, J = 9.0 Hz, aromatic nucleus hydrogen), 7.50 (d, 2H, J = 8.0 Hz, 7.91 (d, 2H, J = 9.0 Hz, aromatic hydrogen), 7.98 (d, 2H, J = 8.0 Hz, aromatic hydrogen), 17.01 (br, 1H) , Enol-based hydroxyl hydrogen) (b) ¹³ C-NMR (125 MHz, internal standard: CDC
l ₃ ) (CDCl ₃ ) δ ppm: 31.1, 35.0, 61.
3, 69.4, 92.1, 114.5, 125.6, 12
6.9, 128.7, 129.2, 132.7, 156.
0, 162.1, 184.3, 185.6 (c) IR (KBr) νcm ^-1 : 3389, 3117, 2953, 2344;
1605, 1506, 1453, 1312, 1267,
1231, 1178, 1127, 1087, 1046,
916, 851, 789, 627 (d) UV (dichloromethane) λmax: 359 nm (logεmax: 4.53) (e) Mass spectrum 340 (M ⁺ ) From these results, it was confirmed that the obtained white crystals were the desired 4-tert-butyl-4 '-(2-hydroxyethoxy) dibenzoylmethane.

Synthesis Example 2 (4-tert-butyl-4'-
(Synthesis of (2-methacryloyloxyethoxy) dibenzoylmethane) 260 ml of cyclohexane charged in a 1-liter four-necked flask equipped with a stirrer, a thermometer, and a condenser
In the above, 4-tert-butyl-4 'obtained in Synthesis Example 1
-(2-hydroxyethoxy) dibenzoylmethane 10
0.0g (0.294 mole) and methacrylic acid
5 g (0.320 mol) are suspended at 27 ° C., 5.0 g of 4-toluenesulfonic acid monohydrate and o-methyl-4
After adding 0.1 g of hydroquinone, the reaction temperature was gradually raised while blowing air into the reaction solution, and stirring was continued for 15 hours under reflux dehydration. 4-tert-butyl-4 '
After confirming the disappearance of-(2-hydroxyethoxy) dibenzoylmethane by TLC and HPLC in the same manner as in Synthesis Example 1, the reaction solution was concentrated, and the obtained reaction mixture was dissolved in 240 ml of ethyl acetate at 50 ° C. After neutralization with a sodium hydroxide aqueous solution, liquid separation was performed. The organic layer was separated, washed with water, and concentrated crude crystals were recrystallized from toluene-methanol to obtain white crystals.
9.2 g were obtained. The obtained crystals have a melting point of 110-112.
° C and the yield was 66%.

Next, about the obtained crystal, Synthesis Example 1
¹ H-NMR, ¹³ C-NMR, IR, U
V and mass spectra were examined and elemental analysis was performed.
These data are shown below.

(A) ¹ H-NMR (270 MHz, internal standard: TMS) (CDCl ₃ ) δ ppm: 1.18 (s, 9H, -C (C
_{H 3) 3), 1.93 (} s, 3H, -CH 3) 4.15 (t, 2H, J = 4.0Hz, -O-CH 2 -), 4.27 (t, 2H, J = 4.0 Hz, —O—CH ₂ —), 5.61 (m, 1 H, vinylidene hydrogen), 6.15 (m,
1H, vinylidene hydrogen), 6.78 (s, 1H, enol olefin hydrogen), 7.00 (d, 2H, J = 8.0 Hz,
7.50 (d, 2H, J = 9.0 Hz, aromatic hydrogen), 7.91 (d, 2H, J = 8.0 Hz, aromatic hydrogen), 7.97 (d, 2H) , J = 9.0 Hz, aromatic nucleus hydrogen),
17.01 (br, 1H, enol-based hydroxyl hydrogen) (b) ¹³ C-NMR (125 MHz, internal standard: CDC
l ₃ ) (CDCl ₃ ) δ ppm: 18.3, 31.1, 35.0,
62.8, 66.1, 92.1, 114.5, 125.6,
126.9, 128.7, 129.2, 132.7, 13
5.9, 154.1, 156.0, 167.2, 184.
3, 185.6 (c) IR (KBr) νcm ^-1 : 3115, 2963, 2616, 2359,
1929, 1717, 1660-1440, 1414,
1312, 1267, 1237, 1184, 1167,
1049, 947, 851, 795, 629 (d) UV (dichloromethane) λmax: 358 nm (log εmax: 4.55) (e) Mass spectrum 408 (M ⁺ ) From these results, it was confirmed that the obtained white crystals were the desired 4-tert-butyl-4 '-(2-methacryloyloxyethoxy) dibenzoylmethane.

The obtained 4-tert-butyl-
The absorbance at a wavelength of 200 to 500 nm of a solution of 0.05 mmol of 4 '-(2-methacryloyloxyethoxy) dibenzoylmethane dissolved in 1 liter of dichloromethane was measured. The result is shown in FIG.

Example 1 The 4-tert-butyl-4 '-(2
-Methacryloyloxyethoxy) dibenzoylmethane (hereinafter, referred to as BMABM) 0.01 g, ethyl acrylate (hereinafter, referred to as EA) 2.0 g, methyl methacrylate (hereinafter, referred to as MMA) 17.99 g, and lauryl mercaptan (hereinafter, referred to as a reaction modifier) , LM) 9
0 μl, stearic acid as solvent (hereinafter referred to as SA)
0.12 g and 0.02 g of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) were put in a heat-resistant glass tube.

Next, the inside of the heat-resistant glass tube was flushed with nitrogen gas and sealed, and the content was polymerized at 70 ° C. for 6 hours to obtain a colorless and transparent polymer. The ratio of BMABM in the total weight of the polymer was 0.05% by weight.

The above polymer was heated at 150 ° C. and 180 kg / m ²
To form a film having a thickness of 1 mm.

Wavelength of the obtained film 190-700n
m-UV-visible Rec
ordering Spectrophotometer
(UV-240, manufactured by Shimadzu Corporation).
The result is shown by A in FIG.

From the results shown in FIG.
Has a light transmittance of about 75% and a light transmittance of 0% at a wavelength of 390 nm, and the obtained film has a reduced UV-A area, and is particularly excellent in absorbing ultraviolet rays up to a wavelength of about 390 nm. I understand.

Example 2 In Example 1, the amount of BMABM was changed from 0.01 g to 0.02 g, and the amount of MMA was changed from 17.99 g to 17.9.
A colorless and transparent polymer was obtained in the same manner as in Example 1 except that the amount was changed to 8 g. The ratio of BMABM in the total weight of the polymer was 0.1% by weight.

Next, a film having a thickness of 1 mm was prepared from the polymer in the same manner as in Example 1, and the light transmittance of the film was measured. The result is shown by B in FIG.

From the results shown in FIG.
Has a light transmittance of about 35% and a light transmittance of 0% at a wavelength of 390 nm is 0%, and the obtained film has an excellent UV-A absorption property, and in particular, has excellent absorption of ultraviolet rays up to a wavelength of about 390 nm. I understand.

Comparative Example 1 A colorless and transparent polymer was obtained in the same manner as in Example 1, except that BMABM was not used and the amount of MMA was changed from 17.99 g to 18 g.

Next, a film having a thickness of 1 mm was prepared from the polymer in the same manner as in Example 1, and the light transmittance of the film was measured. The result is shown by C in FIG.

From the results shown in FIG.
Has a light transmittance of about 93% and a light transmittance of about 390 nm at a wavelength of about 93%, which indicates that the obtained film is inferior in UV-A absorption at the UV-A level.

Example 3 0.2 g of BMABM, 39.8 g of MMA and 0.1 g of AIBM.
04 g and 60 g of toluene were placed in a reaction vessel, and after flushing the inside of the reaction vessel with nitrogen gas, the contents were polymerized at about 80 ° C. for 6 hours with stirring to obtain a colorless and transparent polymer. The ratio of BMABM in the total weight of the polymer was 0.5% by weight.

Next, a 40% by weight toluene solution of the polymer was prepared, and the solution was applied to a prepared glass with a bar coater, dried and peeled to produce a film having a thickness of 0.2 mm.

The light transmittance of the obtained film was measured in Example 1.
The measurement was performed in the same manner as described above. As a result, the light transmittance at a wavelength of 400 nm is about 45%, and the light transmittance at a wavelength of 390 nm is 0%.
%, And the obtained film was extremely excellent in absorbing UV rays in the UV-A region, particularly in the vicinity of a wavelength of 390 nm.

[0069]

The ultraviolet absorbent of the present invention exhibits excellent ultraviolet absorption and optical transparency, and is particularly excellent in UV-A absorption.

Accordingly, the ultraviolet absorbent of the present invention is useful as a raw material for, for example, cosmetics, fibers, films, inks, paints, contact lenses, lenses for spectacles, and the like.

[Brief description of the drawings]

FIG. 1 shows 4-tert-butyl- obtained in Synthesis Example 2.
Wavelength of 4 '-(2-methacryloyloxyethoxy) dibenzoylmethane in dichloromethane solution 200 to 500
It is a graph which shows the light absorbency in nm.

FIG. 2 is a graph showing light transmittance at wavelengths of 190 to 700 nm of the films obtained in Examples 1 and 2 and Comparative Example 1.

Continuation of front page (72) Inventor Yasuhiro Morita 18-8 Katayamacho, Kashiwara-shi, Osaka Inside Osaka Organic Chemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A compound of formula (I): An ultraviolet absorber comprising a polymer obtained by polymerizing a polymerization component containing 4-tert-butyl-4 '-(2-methacryloyloxyethoxy) dibenzoylmethane represented by the following formula: 2. The polymerizable component is 4-tert-butyl-4 '.
The ultraviolet absorber according to claim 1, which contains a copolymerizable monomer copolymerizable with-(2-methacryloyloxyethoxy) dibenzoylmethane. 3. The ultraviolet absorbent according to claim 2, wherein the copolymerizable monomer is an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms.