JP5821661B2 - Novel bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds, optical information recording material and optical information recording medium - Google Patents

Description

  The present invention relates to novel bis- or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds exhibiting a non-linear light absorption effect, a production method thereof, an optical information recording material containing the same, The present invention relates to a formed optical recording medium.

  In recent years, a high-intensity pulsed laser beam having a wavelength of less than 600 nm (for example, a wavelength of 400 to 410 nm, an output of 1 to 100 W, a pulse width of 1 to 10 psec, a recording layer of an optical information recording medium such as an optical disk such as a so-called Blu-ray disc, A technique has been proposed in which a region near the focal point is made an optically heterogeneous region (region functioning as a recording mark) with respect to the surrounding region by focusing and irradiating a frequency of 0.1 to 10 GHz (Patent Document 1). ). In such a technique, in order to cope with the increase in recording capacity required for the optical information recording medium in recent years, it is required to shorten the recording mark formation time, that is, to shorten the information writing time to the optical information recording medium. In the technique of Patent Document 1, the writing speed is increased by blending a photoacid generator in the recording layer.

JP 2010-15632 A

  However, in the case of the optical information recording medium proposed in Patent Document 1, since the photoacid generator is highly photothermally sensitive, it can be stored in a high temperature environment (about 40 to 60 ° C.) that can occur in a general house or warehouse in the summer. Occasionally, unintended acid is generated from the photoacid generator contained in the recording layer, so that the optical information recording medium gradually discolors, and there is a concern that the recording mark may disappear in the span of several decades. ing.

  For this reason, it is stable in a high-temperature environment that can occur in ordinary houses and warehouses instead of materials that have problems with long-term storage such as photoacid generators, but two-photons when irradiated with high-intensity pulsed laser light. There has been a demand for a compound that exhibits a preferable non-linear light absorption effect that causes an absorption phenomenon and that can shorten the writing time.

  An object of the present invention is to solve the above-described conventional problems, and when writing a recording mark on a recording layer of an optical information recording medium with a high-intensity pulsed laser beam having a wavelength of less than 600 nm, particularly 400 to 410 nm. Another object of the present invention is to provide a novel compound exhibiting a non-linear light absorption effect to be added to the recording layer in order to shorten the writing time.

  The present inventors have found that the above object can be achieved by a novel compound in which a specific aryl compound is disubstituted or trisubstituted at the ethynyl group end of 1,1-diphenyl-2-propyn-1-ol, The invention has been completed.

  That is, the present invention is a bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compound represented by the formula (1).

  In formula (1), Ar is a substituted or unsubstituted divalent or trivalent aryl group, and n is 2 or 3.

  The present invention also provides a process for producing bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of formula (1), wherein 1-hydroxy-1, By reacting 1-diphenyl-2-propyne with di- or trihalogenated aryl of formula (3) under Sonogashira coupling reaction conditions, bis or tris (3-hydroxy-3,3 of formula (1) A process for producing -diphenyl-1-propynyl) aryl compounds is provided.

  In the formulas (2) and (3), Ar and n are as described in the formula (1).

  The present invention also relates to a thermosetting optical information recording material for forming the recording layer of an optical information recording medium on which recording is performed by forming a recording mark by condensing a pulsed laser beam on the recording layer. An optical information recording material containing a bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compound of the above formula (1) in addition to an epoxy compound and an epoxy curing agent I will provide a.

  The present invention also has a recording layer formed from a cured product of the above-described thermosetting optical information recording material of the present invention, and forms recording marks by condensing pulsed laser light on the recording layer. An optical information recording medium on which recording is performed is provided.

  The novel bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of the present invention have two or three 3-hydroxy-3,3-diphenyl- Since the 1-propynyl groups are directly bonded to each other, they exhibit a nonlinear light absorption effect that causes a two-photon absorption phenomenon with respect to high-intensity pulsed laser light having a wavelength of 600 nm or less, particularly 400 to 410 nm. Therefore, when a recording mark is written on the recording layer of the optical information recording medium with a high-intensity pulsed laser beam, the bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compound of the present invention is recorded on the recording layer. In the case of blending, the writing time can be greatly shortened.

FIG. 1 is a schematic cross-sectional view of an optical information recording medium. 2 is a ¹ H-NMR chart of the aryl compound of the formula (1a) in Example 1. FIG. 3 is a ¹ H-NMR chart of an aryl compound of the formula (1b) in Example 2. FIG. 4 is a ¹ H-NMR chart of an aryl compound of the formula (1c) in Example 3. FIG. 5 is a ¹ H-NMR chart of an aryl compound of the formula (1d) in Example 4. FIG. 6 is a ¹ H-NMR chart of an aryl compound of the formula (1e) in Example 5. FIG. 7 is a ¹ H-NMR chart of an aryl compound of the formula (1f) in Example 6. FIG.

  The novel compounds of the present invention are bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of formula (1) below.

  In formula (1), Ar is a substituted or unsubstituted divalent or trivalent aryl group, and n is 2 or 3. When n is 2, Ar is necessarily a divalent aryl group, and when n is 3, Ar is necessarily a trivalent aryl group.

  Here, as the divalent or trivalent aryl group, benzene-di or triyl, biphenyl-di or triyl, benzophenone-di or triyl, triphenylamine-di or triyl, naphthalene-di or triyl, phenanthrene-di or Triyl, anthracene-di or triyl, quinoline-di or triyl, isoquinoline-di or triyl, benzoxazole-di or triyl, benzoisoxazole-di or triyl, benzothiazole-di or triyl, benzofuran-di or triyl, benzothiophene -Di- or triyl, pyridine-di or triyl, etc. are mentioned. Among these, preferred divalent or trivalent aryl groups include benzene-di or triyl, biphenyl-di or triyl, benzophenone-di or triyl, triphenylamine-di or triyl. Among them, benzene-1,4-diyl, benzene-1,3-diyl, biphenyl-4,4'-diyl, benzophenone-4,4'-diyl, benzene-1,3,5-triyl, or triphenylamine Preferred is -4,4 ', 4 "-triyl.

  The divalent or trivalent aryl group described above preferably has no substituent, but within the range not impairing the effects of the invention, a halogen atom such as a fluorine atom or a chlorine atom; a nitro group; a hydroxy group Group: alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group and t-butyl group; alkoxy group such as methoxy group and ethoxy group; cyano group; hydroxyl group; It may be substituted with a substituent such as an amino group.

  Preferred specific embodiments of the bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of the formula (1) include the following formulas (1a) to (1f).

  Of these compounds represented by the formulas (1a) to (1f), the compounds of the formulas (1b), (1e) and (1f) are more preferable from the viewpoint of the writing speed onto the optical information recording medium.

  The bis- or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of formula (1) of the present invention described above can be used in the Sonogashira coupling reaction (for example, Tetrahedron Lett. 1975, 4467). J. Org. Chem. 2001, 66, 1910-1913) can be used according to the following reaction formula.

  Specifically, 1,1-diphenyl-2-propyn-1-ol, which is a terminal alkyne of formula (2), is di- or trihalogenated of formula (3) under known Sonogashira coupling reaction conditions. Bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of formula (1) can be prepared by reacting with aryl.

  In these formulas, Ar and n are as described for formula (1), and X is a halogen atom (preferably a bromine atom or an iodine atom).

  Among the dihalogenated aryls of formula (3), specific examples of dibromoaryl include 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene, 1,4-dibromo-2-nitrobenzene, 1,3-dibromotetrafluorobenzene, 1,4-dibromotetrafluorobenzene, 1,2-dibromo-4-fluorobenzene, 1,3-dibromo-5-fluorobenzene, 2,4-dibromotoluene, 3,5 -Dibromotoluene, 2,5-dibromotoluene, 2,2'-dibromobiphenyl, 4,4'-dibromobiphenyl, 3,3'-dibromo-4,4'-dimethoxybiphenyl, 4,4'-dibromooctafluoro Biphenyl, 2,5-dibromoxylene, 2,4-dibromoanisole, 3,5-dibromoanisole, 1 4-dibromo-naphthalene. 2,7-dibromonaphthalene, 1,5-dibromoanthracene, 2,6-dibromoanthracene, 9,10-dibromoanthracene, bis (4-bromophenyl) ether, N, N-bis (4-bromobenzyl) amine, 2,3-bis (4-bromophenyl) -2,7-butenedinitrile, 9,9-bis (4-bromophenyl) fluorene, 4,4'-dibromotriphenylamine, 4,4'-dibromobenzyl 2,8-dibromodibenzothiophene, 2,3-dibromo6,7-dicyanonaphthalene, 5,7-dibromo-2,3-dihydrobenzofuran, methyl 2,5-dibromobenzoate, 3,5-dibromo-4 -Methyl methylbenzoate, 3,5-dibromo-1-trimethylsilylbenzene, 1,4-dibromo-2,5-diethylbenzene 3,6-dibromo-9-phenylcarbazole, 3,6-dibromo-9-ethylcarbazole, 2,7-dibromocarbazole, 3,6-dibromocarbazole, 4,4'-dibromo-trans-stilbene, 2,6 -Dibromoanthraquinone, 4,4'-dibromo-4 "-cyclohexyltriphenylamine, 4,4'-dibromo-4" -phenyltriphenylamine, 1,3-dibromo-5- (trifluoromethoxy) benzene 4,4 "-dibromo-p-terphenyl, 1,3-dibromo-5-chlorobenzene, 2,4-dibromo-1-fluorobenzene, 2,7-dibromo-9-fluorenone, 2,7-dibromo Fluorene, 2,7-dibromo-9,9-dimethylfluorene, 2,7-dibromo-9,9-dihexylfluorene 2,7-dibromo-9,9-di-n-octylfluorene, 2,2-dibromo-9,9'-spirobi [9H-fluorene], 1,4-dibromo-2,5-dimethoxybenzene, 4, 4'-dibromobenzophenone and the like can be mentioned.

  Among the dihalogenated aryls of the formula (3), specific examples of diiodoaryl include 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,4-diiodo- 2,3,5,6-tetramethylbenzene, 4,4'-diiodobiphenyl, 2,2'-diiodobiphenyl, 4,4 "-diiodo-p-terphenyl, 9-acetyl-3,6 -Diiodocarbazole, bis (4-iodophenyl) amine, 4,4'-diiodo-3,3'-dimethylbiphenyl, 4,4'-diiodo-trans-stilbene and the like.

  Of the trihalogenated aryls of formula (3), specific examples of tribromoaryl include 1,2,4-tribromobenzene, 1,3,5-tribromobenzene. 2,4,6-tribromotoluene, tris (4-bromophenyl) amine, 1,3,5-tris (4-bromophenyl) benzene, 2,3 ′, 5-tribromobiphenyl, 2,4 ′, 5-tribromobiphenyl and the like can be mentioned.

  Of the trihalogenated aryls of formula (3), specific examples of triiodoaryl include 1,3,5-triiodobenzene, tris (4-iodophenyl) amine, 1,3,5-tris (4- And iodophenyl) benzene.

  The Sonogashira coupling reaction is a chemical reaction in which arylalkynes and aryl halides are cross-coupled by the action of a palladium catalyst, a copper catalyst, and a base to obtain an alkynylated aryl (aromatic acetylene). is there. The general operation of this reaction is as follows.

  That is, 1/10 mol of iodine is added to an approximately equimolar mixture of 1,1-diphenyl-2-propyn-1-ol, which is a terminal alkyne of formula (2), and di- or trihalogenated aryl of formula (3). Copper (I), palladium (II) dichlorobistriphenylphosphine and a basic solvent such as triethylamine are mixed, triphenylphosphine is added as necessary, and heated in a nitrogen atmosphere at room temperature or under reflux for 1 to 12 hours By doing so, novel bis- or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of the formula (1) can be obtained as products. If necessary, a high-purity bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compound of the formula (1) can be obtained by applying a known purification method.

  Here, 1,1-diphenyl-2-propyn-1-ol, which is the terminal alkyne of the formula (2), can use a commercially available product (Wako Pure Chemical Industries, Ltd.).

  The above-described bis- or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of the formula (1) according to the present invention record information by laser ablation with high-intensity pulsed laser light. It can be preferably blended as a sensitizer in the recording layer of the medium.

  As such a recording layer, a thermosetting epoxy compound having a high planar skeleton capable of realizing a high crosslinking density, and bis or tris (3-hydroxy-3,3-diphenyl-) of the formula (1) of the present invention. A cured resin layer obtained by curing a thermosetting optical information recording material containing 1-propynyl) aryl compounds and an epoxy curing agent can be preferably applied. This optical information recording material is also an embodiment of the present invention.

  If the content of the bis- or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of the formula (1) in the optical information recording material is too small, the effect of the invention is difficult to obtain and is too large. Since the optical disk characteristics such as recording density tend to decrease, the total amount of 100 parts by mass of the epoxy compound and epoxy curing agent described later is preferably 0.5 to 50 parts by mass, more preferably 10 to 20 parts by mass. Part by mass.

  As an epoxy compound constituting the optical information recording material, an epoxy compound widely used for forming a recording layer of an optical information recording medium can be applied. Among them, a high planar skeleton capable of realizing a high crosslinking density is used. Preferred examples include epoxy compounds having naphthalene residues, fluorene residues, anthracene residues, bisphenol A residues, biphenyl residues and the like. Two or more of these can be used in combination. In addition, these epoxy compounds are preferably bifunctional or more in order to realize a high crosslinking density.

Specific examples of the epoxy compound that can be preferably used in the present invention include a naphthalene type bifunctional epoxy compound (“HP4032” and “HP4032D”, both DIC Corporation), and a naphthalene type tetrafunctional epoxy compound (“HP4700”, both) DIC Corporation), naphthol type epoxy resin (ESN-475V, Nippon Kasei Manufacturing Co., Ltd.), fluorene type epoxy resin ("Oncoat 1020", "Oncoat 1040"), all of which are Nagase ChemteX Corporation "Ogsol EG", Osaka Gas Chemical Co., Ltd.), liquid bisphenol A type epoxy resin ("830CRP", DIC Corporation; "jER828EL", Mitsubishi Chemical Corporation), biphenyl type epoxy resin ("NC3000H", “NC3000L”, both Nippon Kayaku Co., Ltd .; “jER YX 4000 ", Mitsubishi Chemical Corporation), anthracene-like epoxy resin (" jER YX8800 ", Mitsubishi Chemical Corporation), and the like. Two or more of these epoxy compounds can be used in combination.

  As the curing agent for epoxy constituting the optical information recording material, a known curing agent for the epoxy compound can be used. For example, one or more amine compounds, sulfonates, iodonium salts, imidazoles, acid anhydrides, and the like can be used. Among these epoxy curing agents, an amine compound can be preferably used because the curing temperature can be lowered. Preferred examples of such amine compounds include tris (dimethylaminomethyl) phenol (DMP-30, Kanto Chemical Co., Inc.) and special amine compounds (U-Cat18X, San Apro Co., Ltd.).

  If the content of the curing agent for epoxy in the optical information recording material is too small, the epoxy compound cannot be sufficiently cured, and if it is too large, the cured product tends to be colored. It is 0.1-10 mass parts with respect to a part, More preferably, it is 0.5-1.5 mass part.

  The optical information recording material can contain a thermoplastic resin such as a phenoxy resin, an antioxidant, a colorant, and the like, if necessary.

  The optical information recording material of the present invention comprises an epoxy compound, an epoxy curing agent, a bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compound of formula (1), and optionally added It can be prepared by uniformly mixing the solvent and other additives to be further defoamed.

  Next, the optical information recording medium of the present invention having a recording layer formed using the optical information recording material of the present invention will be described.

  As shown in FIG. 1, the optical information recording medium 10 of the present invention changes the optical properties in the vicinity of the focal point F by condensing recording light hν such as high-intensity pulsed laser light inside the recording layer 1. It is for recording. Examples of such optical properties include refractive index and light reflectance. Usually, a cavity is formed as a recording mark. A pair of transparent substrates 2 such as a glass plate and a polycarbonate plate are disposed as a support or a protective member on one side, preferably both sides, of such a recording layer 1. A known optical film such as an antireflection film or a polarizing film may be laminated on the transparent substrate 2 as necessary.

  In the optical information recording medium 10 of the present invention, the above-described thermosetting optical information recording material of the present invention is applied on a transparent substrate on one side of a pair of transparent substrates 2 by a conventional method, and the other film is applied on the coating film. It can be produced by laminating a transparent substrate, heating the resulting laminate to a temperature of 80 to 120 ° C. to polymerize and cure the optical information recording material, and forming the coating film as the recording layer 1.

  As described above, the recording layer 1 of the optical information recording medium 10 of the present invention is formed from a cured product of the optical information recording material of the present invention. The epoxy compound constituting the optical information recording material has a high planar skeleton capable of realizing a high crosslinking density, and when a bifunctional or higher functional epoxy compound is used, steric hindrance is reduced and highly three-dimensionally crosslinked. . As a result, the crosslink density of the cured product increases, the molecular weight between crosslink points that decreases as the degree of crosslinkage increases, and the distance between recordable recording marks can be reduced.

  In the present invention, the preferred molecular weight between cross-linking points is 2000 or less, more preferably 500 or less. The molecular weight between crosslinking points can be calculated according to the following Flory equation.

Here, Mc is the molecular weight between cross-linking points, ρ is the density [g / cm ³ ] of the cured product, T is the temperature (° K), and E ′ is the high temperature region of storage elastic modulus (MPa) ( R is a gas constant.

Moreover, since the density of the hardened | cured material of an optical information recording material will become low crosslink density when too small, Preferably it is 1.210 g / cm < ³ > or more, More preferably, it is 1.240 g / cm < ³ > or more. In addition, since an upper limit has a limit as an organic substance, it is 1.5 g / cm < ³ > or less normally.

  Further, if the glass transition temperature of the cured product of the optical information recording material is too low, the durability of the optical information recording medium in a high temperature environment tends to decrease, and if it is too high, the writing speed tends to decrease. It is -140 degreeC, More preferably, it is 120-130 degreeC.

  In the optical information recording medium 10 of the present invention described above, a thermosetting optical information recording material is applied to one transparent substrate 2 by a conventional method, and the other transparent substrate 2 is stacked thereon, and then heated in an oven. It can be manufactured by curing.

  As described above, the optical information recording medium 10 of the present invention having such a recording layer 1 includes a semiconductor laser beam such as GaInN or a high-intensity pulsed laser beam such as a titanium sapphire laser (for example, Recording light hν having a peak power of 1 W or more and a pulse width of 1 nsec or less) is condensed and the vicinity of the focal point F is heated to a high temperature. As a result, the recording layer 1 in the vicinity of the focal point F can be altered so as to have optically different properties (existence of gaps, high and low refractive index, high and low reflectance, etc.) with respect to the other recording layer 1. And thereby recording can be performed. In addition, by adjusting the focal point F position and the size of the recording region by a known method, a plurality of recordings (in other words, a multilayered recording) can be performed in the thickness direction of the optical recording resin layer. Further, when reproducing light having a different output or the like is condensed in the optical recording resin layer from the same light source as the recording light hν, optical information such as light absorption and light reflection of the optically anisotropic portion is used as recording information. Can be acquired.

  Hereinafter, the present invention will be specifically described by way of examples.

<Example 1>
In a 100 mL three-neck flask purged with nitrogen, 1.47 g of 1,4-diiodobenzene, 1.86 g of 1,1-diphenyl-2-propyn-1-ol, 0.025 g of triphenylphosphine, bis (triphenylphosphine) 0.0125 g of palladium (II) dichloride, 0.0125 g of CuI (I) and 40 mL of triethylamine were added, and this mixture was heated to reflux for 4 hours, and stirred at room temperature for 16 hours to continue the reaction. After completion of the reaction, the reaction solution was neutralized with 5% aqueous hydrochloric acid solution, the organic phase was extracted with ethyl acetate, the resulting extract was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and the residue was ethanol. Was recrystallized to obtain 1.00 g (45% yield) of white crystals. The white crystals were identified by ¹ H-NMR (nuclear magnetic resonance measurement) (see FIG. 2) and MS (mass spectrometry measurement), and the purity was 99% or more (LC, Area%). From the above analysis results, the white crystals could be identified as the compound of formula (1a).

¹ H-NMR (CDCl ₃ ) [δ (ppm)]: 2.85 (s, 2H), 7.26-7.37 (m, 12H), 7.45 (s), 7.62-7. 66 (m, 8H)

MS (m / z): 473 (M-OH)

<Example 2>
Other than using 1,3-diiodobenzene instead of 1,4-diiodobenzene and changing the amount of 1,1-diphenyl-2-propyn-1-ol used from 1.86 g to 2.23 g Produced 1.70 g (yield 77%) of white crystals by repeating the same operation as in Example 1. The white crystals were identified by ¹ H-NMR (see FIG. 3) and MS, and the purity was 99% or more (LC, Area%). From the above analysis results, the white crystals could be identified as the compound of formula (1b).

¹ H-NMR (CDCl ₃ ) [δ (ppm)]: 2.86 (s, 2H), 7.26-7.37 (m, 13H), 7.45-7.48 (m, 2H), 7.62-7.66 (m, 9H)

MS (m / z): 473 (M-OH)

<Example 3>
The same operation as in Example 1 was repeated except that 1.81 g of 4,4′-diiodobiphenyl was used in place of 1,4-diiodobenzene to obtain 1.86 g of white crystals (64% yield). ) This white crystal was identified by ¹ H-NMR (see FIG. 4) and MS, and the purity was 99% or more (LC, Area%). From the above analysis results, the white crystals could be identified as the compound of formula (1c).

¹ H-NMR (CDCl ₃ ) [δ (ppm)]: 2.89 (s, 2H), 7.26 (m, 12H), 7.56-7.59 (m, 8H), 7.65- 7.69 (m, 8H)

MS (m / z): 549 (M-OH)

<Example 4>
2.08 g of white crystals (78% yield) was obtained by repeating the same operation as in Example 1 except that 1.52 g of 4,4′-dibromobenzophenone was used instead of 1,4-diiodobenzene. Got. The white crystals were identified by ¹ H-NMR (see FIG. 5) and MS, and the purity was 99% or more (LC, Area%). From the above analysis results, the white crystals could be identified as the compound of formula (1d).

¹ H-NMR (CDCl ₃ ) [δ (ppm)]: 2.09 (s, 3H), 7.25-7.38 (m, 12H), 7.56-7.59 (m, 8H), 7.58-7.75 (m, 16H)

MS (m / z): 577 (M-OH)

<Example 5>
In a 100 mL three-necked flask purged with nitrogen, 0.94 g of 1,3,5-tribromobenzene, 2.23 g of 1,1-diphenyl-2-propyn-1-ol, 0.025 g of triphenylphosphine, bis (triphenyl) Phosphine) palladium (II) dichloride 0.0125 g, CuI (I) 0.0125 g, and triethylamine 40 mL were added, and this mixture was heated to reflux for 4 hours, and further stirred at room temperature for 16 hours for reaction. After completion of the reaction, the reaction solution was neutralized with 5% aqueous hydrochloric acid, the organic phase was extracted with ethyl acetate, the resulting extract was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and the residue was diluted with ethanol. By recrystallization, 1.1 g (yield 53%) of white crystals was obtained. The white crystals were identified by ¹ H-NMR (see FIG. 6) and MS, and the purity was 99% or more (LC, Area%). From the above analysis results, the white crystals could be identified as the compound of formula (1e).

¹ H-NMR (CDCl ₃ ) [δ (ppm)]: 2.87 (s, 3H), 7.25-7.37 (m, 18H), 7.59-7.64 (m, 15H)

MS (m / z): 679 (M-OH)

<Example 6>
A procedure similar to that of Example 5 was repeated except that 1.86 g of tris (4-iodophenyl) amine was used in place of 1,3,5-tribromobenzene. 63%) was obtained. The pale yellow crystal was identified by ¹ H-NMR (see FIG. 7) and MS, and the purity was 99% or more (LC, Area%). From the above analysis results, the pale yellow crystals could be identified as the compound of formula (1f).

¹ H-NMR (CDCl ₃ ) [δ (ppm)]: 2.85 (s, 3H), 6.98-7.02 (m, 6H), 7.25-7.41 (m, 24H), 7.63-7.67 (m, 12H)

MS (m / z): 846 (M-OH)

<Examples 7-11, Comparative Examples 1-3>
(Creation of optical information recording media)
1,6-Naphtodiol diglycidyl ether (HP-4032D, DIC Corporation) as an epoxy compound, and formulas (1a), (1b), (1d) to (1f) of Examples 1, 2, 4 to 7 And a sensitizer selected from diphenylacetylene (Comparative Example 2) and 1,4-diphenylbutadiyne (Comparative Example 3) in the blending amounts shown in Table 1, and tris as an epoxy curing agent. A liquid thermosetting optical information recording material was prepared by uniformly mixing 1 part by mass of (dimethylaminomethyl) phenol (DMP-30, Kanto Chemical Co., Ltd.) and defoaming. The optical information recording material was coated on a 0.15 mm thick cover glass substrate to a thickness of 0.30 mm, and a 0.75 mm thick glass substrate was placed thereon, and the oven was heated to 80 ° C. The recording medium was heated for 12 hours to cure the optical information recording material to form a recording layer, whereby an optical information recording medium having a recording layer having both surfaces sandwiched between glass substrates was obtained. In addition, the comparative example 1 is an example which does not mix | blend a sensitizer.

<Writing test evaluation>
(Evaluation of writing time reduction effect)
Laser light from a laser diode (wavelength: 405 nm, pulse width: 3 picoseconds, objective out-peak power: 19 W, repetition frequency: 1 GHz) is emitted using an objective lens (NA: 0.85). A recording mark was formed by focusing light at a depth of 50 μm in the recording layer of the information recording medium. At this time, writing was performed by forming a plurality of recording marks having different pulse laser light irradiation times (writing times). The adjustment of the writing time was controlled by a function generator (MP1800A, Anritsu Corporation).

  Next, the recording mark was read using the same laser diode. Specifically, the signal from the recording mark was branched from the deflecting beam splitter and the λ / 4 plate, and it was confirmed using a CCD (Charge Coupled Device) on the basis of whether or not the recording mark could be confirmed. The shortest irradiation time among the irradiation times of the pulse laser beam at the time of writing the record mark that was confirmed was set as the writing time of the optical information recording medium.

<Discussion of results in Table 1>
The optical information recording medium of Comparative Example 1 was a medium having a recording layer containing no sensitizer, and the writing time was relatively long as 500 ns. The optical information recording media of Comparative Examples 2 and 3 have a recording layer containing a typical known sensitizer, but the writing time is improved as compared with the case of Comparative Example 1. Still had a write time of over 400 ns.

  On the other hand, among the optical information recording media of the examples containing the novel bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds in the recording layer, Example 9 having the longest writing time In the case of this optical information recording medium, it can be seen that the writing time of the optical information recording medium of Comparative Example 1 containing no sensitizer is shortened by 26%. Further, it was found that the writing time was shortened by 7.5% compared with the optical information recording medium of Comparative Example 2 having the shortest writing time among the comparative examples.

  The optical information recording medium of Example 11 containing trisubstituted tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds in the recording layer is disubstituted 3- (3-hydroxy-3). , 3-diphenyl-1-propynyl) aryl compounds are found to be greatly reduced in writing speed as compared with the optical information recording media of Examples 7 to 9 containing the recording layer.

  The novel bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of the present invention exhibit a non-linear light absorption effect with high intensity pulsed laser light having a wavelength of less than 600 nm. Therefore, when a recording mark is written on the recording layer of the optical information recording medium with a high-intensity pulsed laser beam having such a wavelength, the bis or tris (3-hydroxy-3,3-diphenyl-1) of the present invention is applied to the recording layer. When -propynyl) aryl compounds are blended, the writing time can be greatly shortened. Therefore, it is useful as a sensitizer for blending into the recording layer of the optical information recording medium.

DESCRIPTION OF SYMBOLS 1 Recording layer 2 Transparent substrate 10 Optical information recording medium F Focus hν Recording light

Claims (9)

Formula (1)

(In the formula (1), Ar is benzophenone-4,4′-diyl, benzene-1,3,5-triyl, or triphenylamine-4,4 ′, 4 ″ -triyl , and n is Ar Is 2 when is benzophenone-4,4'-diyl, or 3 when Ar is benzene-1,3,5-triyl or triphenylamine-4,4 ', 4 "-triyl. .)
Bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds represented by The compound of the formula (1) is represented by the following formula (1d)

The bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds according to claim 1, represented by: The compound of the formula (1) is represented by the following formula (1e)

The bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds according to claim 1, represented by: The compound of the formula (1) is represented by the following formula (1f)

The bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds according to claim 1, represented by: A process for the preparation of bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of formula (1) according to claim 1,
Reaction of 1,1-diphenyl-2-propyn-1-ol of formula (2) with a di- or trihalogenated aryl of formula (3) under Sonogashira coupling reaction conditions. A process for forming bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds.

(In these formulas, Ar is benzophenone-4,4′-diyl, benzene-1,3,5-triyl, or triphenylamine-4,4 ′, 4 ″ -triyl , and n is Ar 2 if benzophenone-4,4'-diyl, or 3 if Ar is benzene-1,3,5-triyl or triphenylamine-4,4 ', 4 "-triyl. X is halogen. ) A thermosetting optical information recording material for forming the recording layer of an optical information recording medium on which recording is performed by forming a recording mark by condensing pulsed laser light on the recording layer, the epoxy compound and Light containing bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of formula (1) according to any of claims 1 to 4 in addition to an epoxy curing agent Information recording material. The total content of the bis or tris (3-hydroxy-3,3-diphenyl-1-propynyl) aryl compounds of formula (1) in the optical information recording material is 100 parts by mass of the epoxy compound and the epoxy curing agent. The optical information recording material according to claim 6 , wherein the content is 0.5 to 50 parts by mass. A recording layer formed from a cured product of the thermosetting optical information recording material according to claim 6 or 7, and recording is performed by forming a recording mark by condensing a pulse laser beam on the recording layer. Optical information recording medium. The optical information recording medium according to claim 8, wherein the recording layer has a structure sandwiched between a pair of transparent substrates.

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