JP2002088007A - O-substituted calix arenes and technique associated therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide O-substituted calix arenes capable of providing a photocurable composition having good preservation stability before photocuring, and capable of providing a cured product having excellent heat resistance, adhesion to other materials, etc., after curing by allowing the calix arenes to be included in the photocurable composition. SOLUTION: This O-substituted calix arene or a derivative thereof has two or more kinds of phenol units having polymerizable functional groups introduced to the phenolic hydroxy groups of a part or the whole of phenol groups in the plural phenol units constituting the calix arene or the derivative thereof. The polymerizable oligomer for the photocurable resin contains the compound as an active ingredient, and the photocurable composition contains the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an O-substituted calixarene or a derivative thereof, a polymerizable oligomer for a photocurable resin containing the compound as an active ingredient, and a photocurable composition containing the compound.

[0002]

2. Description of the Related Art Calixarenes are cyclic oligomers in which a benzene ring having a phenolic hydroxyl group is connected at the ortho-position by a methylene chain. Calixarenes are obtained. Such calixarene and its derivatives are:
In recent years, researches on the use as various functional materials such as a curable resin composition, an optical recording material, a wiring material, and a film forming material have been actively conducted.

Japanese Patent Application Laid-Open No. 9-263560 discloses a photocurable composition comprising a calixarene compound in which only one kind of phenol unit constituting calixarene is O-alkenylated or O-alkynylated. Which are used by being contained in the same. When only a general unsaturated group-containing oligomer is used as the unsaturated group-containing oligomer used in the photocurable resin composition (for example, Comparative Example 3 in this specification), the heat resistance of the cured product obtained by photocuring Is to solve the problem that is low.

However, this photocurable composition has been improved in that the heat resistance of the cured product obtained by photocuring is low, but other physical properties of the cured product, particularly the storage stability of the composition before photocuring. It was found that the properties and the curing rate were low, and the properties of the cured product (for example, the adhesion to other products) had to be further improved.

[0005] The present invention has been made in view of the above-mentioned problems in the prior art, and an object of the present invention is to include a photocurable composition by adding it to a photocurable composition. The storage stability of the product is good and the product can be cured at a high curing rate, and the cured product after photocuring also has excellent heat resistance and adhesion to other products. An object of the present invention is to provide a novel O-substituted calixarene or a derivative thereof, a polymerizable oligomer for a photocurable resin containing the compound as an active ingredient, and a photocurable composition containing the compound.

[0006]

The O-substituted calixarene or a derivative thereof according to the present invention comprises a calixarene or a derivative thereof in which a plurality of phenol units are composed of two or more phenol units. A polymerizable functional group is introduced into a phenolic hydroxyl group in some or all of the phenol units.

The two or more phenol units are defined based on the presence or absence of a substituent (substituent for hydrogen of a phenolic hydroxyl group in the phenol unit or a substituent other than a methylene chain for bonding to an adjacent phenol unit). Or two or more phenol units having different structures depending on the substituents and / or their positions.

Since the O-substituted calixarene or its derivative of the present invention has high solubility in a photopolymerizable monomer, a photocurable composition having good uniformity can be obtained by dissolving it in the photopolymerizable monomer. Can be. Also,
Due to such a high solubility, the mixing ratio (O- according to the present invention) capable of obtaining a photocurable composition having good uniformity is obtained.
(Mixing ratio of substituted calixarene or a derivative thereof to a photopolymerizable monomer). This photocurable composition can be cured at a high curing rate, and the cured product after photocuring is
Excellent heat resistance and adhesion to other objects.

The O-substituted calixarene or a derivative thereof according to the present invention comprises the A constituent unit (a) and the B constituent unit (b) in the calixarene or a derivative thereof represented by the following formula (1). Phenolic units [ie
Phenol or a derivative thereof in the structural unit (a) and the structural unit (b)] (that is, a part of the structural unit (a), a part of the structural unit (b), or a part of both) or Includes those in which a polymerizable functional group has been introduced into the phenolic hydroxyl groups of all phenol units.

[0010]

Embedded image ... (1)

In the formula (1), A structural units (a) and B structural units (b) are combined, and one or two or more of A and B are combined. It means two or more kinds of cyclic compounds. In each cyclic compound, A and B are each an integer of 0 or more, and the sum of A and B is any of 3 to 8, and the structural unit (a) and the structural unit ( The order of connection in b) is arbitrary.

In the formula (1), R ¹ and R ² represent different substituents, and R ¹ and R ² are each a hydrogen atom,
Optionally branched alkyl group, optionally branched alkenyl group, optionally substituted phenyl group, optionally substituted aralkyl group, alicyclic group, halogen, nitro group, Represents an acyl group, an alkoxy group, a trifluoromethyl group, or a trimethylsilyl group. ]

Next, the polymerizable oligomer for a photocurable resin of the present invention comprises the above-mentioned O-substituted calixarene of the present invention or a derivative thereof as an active ingredient.

The photo-curable composition of the present invention comprises the O-substituted calixarene of the present invention or a derivative thereof.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The O-substituted calixarene or a derivative thereof according to the present invention is, for example, a calixarene or a derivative thereof, wherein a plurality of phenol units constituting the calixarene or a derivative thereof are two or more phenol units. Can be obtained by introducing a polymerizable functional group into a part or all of phenolic hydroxyl groups.

A calixarene or a derivative thereof in which a plurality of phenol units are composed of two or more phenol units can be obtained, for example, by reacting a mixture of a plurality of phenols having different substituents and / or different positions with aldehydes. In addition, it can be obtained by introducing various substituents after the synthesis of calixarene, or by a desubstituent reaction of calixarene.

A method for introducing a polymerizable functional group into a calixarene or a derivative thereof composed of a combination of two or more phenol units is as follows.
For example, the following can be mentioned.

In a nonpolar solvent such as toluene or xylene, sodium hydride (which may be in a solid or oil-dispersed state), potassium hydroxide (which may be in a solid or aqueous solution), potassium carbonate (in a solid state) Or an aqueous solution) and epichlorohydrin (an example of a compound for introducing a polymerizable functional group when a glycidyl group is introduced) and two or more phenol units in the presence of an alkali and a phase transfer catalyst. A method of substituting hydrogen of a phenolic hydroxyl group of calixarene constituted by a combination of the above.

As a reaction solvent, an aprotic polar solvent (for example, dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, pyridine, THF, or the like), a ketone-based solvent, or a glycol diether-based solvent (for example, diglyme, triglyme, Using tetraglyme, pentaglyme, or the like, an alkali (eg, sodium hydride [which may be in a solid or oil-dispersed state]), potassium hydroxide [which may be a solid or an aqueous solution], or potassium carbonate [Either solid or aqueous solution] etc. Solid or aqueous solution) and phase transfer catalyst (quaternary ammonium salt, quaternary phosphonium salt, polyoxyalkylene glycol, polyoxyalkylene glycol mono) A Epichlorohydrin (for introducing a polymerizable functional group in the case of introducing a glycidyl group) in the presence of tere, polyoxyalkylene glycol diether, crown ether, etc. (or in the presence of the alkali, without a phase transfer catalyst) A method in which hydrogen of a phenolic hydroxyl group of calixarene composed of a combination of a compound of the present invention) and two or more phenol units is substituted.

In both cases, the reaction is preferably carried out under a nitrogen stream, and the reaction temperature can be a temperature between room temperature and the reflux temperature of the reaction solvent. Also, HP
It is preferable to complete the reaction while tracking by LC, TLC or the like.

The O-substituted calixarene or a derivative thereof according to the present invention is a calixarene or a derivative thereof composed of a combination of two or more phenol units, wherein the phenolic hydroxyl group in some or all of the phenol units is O. —Substituted (polymerizable functional group). The O-substituted calixarene or derivative thereof according to the present invention comprises two or more kinds of O-substituted calixarenes or derivatives thereof having different numbers of phenol units or different substituents and / or positions in corresponding phenol units. May be used.

Examples of the combination of two or more phenol units include a phenolic hydroxyl group or a substituted phenolic hydroxyl group or a phenolic unit having a substituent at a position other than the methylene chain for bonding to an adjacent phenolic unit. It may be a calixarene composed of a combination of phenol units having no group, and having a substituent at a position other than the methylene chain for bonding to a phenolic hydroxyl group or a polymerizable functionalized phenolic hydroxyl group or an adjacent phenol unit. A calixarene comprising a combination of phenol units having different substituents and / or different positions may be used.

The O-substituted calixarene or a derivative thereof of the present invention comprises a calixarene or a derivative thereof represented by the following formula (1) in A structural units (a) and B structural units (b): A polymerizable functional group is introduced into a phenolic hydroxyl group of a part or all of the phenol units among the phenol units.

[0024]

Embedded image ... (1)

[Formula (1) is obtained by combining A structural units (a) and B structural units (b), and one or more of A and B are combined. It means two or more cyclic compounds, and in each cyclic compound, A and B are each an integer of 0 or more, and the sum of A and B is any of 3 to 8 (accordingly, as a combination of A and B, one is 8 The other is 0, one is 7 and the other is 0 or 1, one is 6 and the other is 0 to 2, one is 5 and the other is 0 to 3, one is 4 and the other is 0
To 4, one is 3 and the other is 0 to 3, one is 2 and the other is 1 or 2. ), And the combination order of the structural unit (a) and the structural unit (b) is arbitrary.

In the formula (1), R ¹ and R ² represent different substituents, and R ¹ and R ² may each be a hydrogen atom (H) or may have a branch (that is, have a branch). Or no) alkyl group (e.g., methyl group,
Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group or the like having 1 to 18 carbon atoms, alkenyl group which may be branched (for example, allyl group,
Those having 1 to 8 carbon atoms, such as propenyl group and butenyl),
Substituents (for example, an alkyl group [for example, having 1 to 8 carbon atoms], an alkoxy group [for example, having 1 to 4 carbon atoms],
A phenyl group which may have a halogen (e.g., a nuclear substituent such as F, Cl, Br, etc.) or a nitro group (i.e., unsubstituted or substituted); Aralkyl groups (for example, benzyl group, cumyl group, toluyl group, etc.) and alicyclic groups (for example, cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.) ), Halogen (eg, F, Cl, Br, etc.), nitro group, acyl group (eg, acetyl, propionyl, butyryl, valeryl, benzoyl, toluoyl, etc.), alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyl) C1 to C8 such as oxy), a trifluoromethyl group or a trimethylsilyl group. ]

Table 1 shows examples of the calixarene represented by the formula (1) or a derivative thereof. However, of course, the present invention is not limited to these.

[0028]

[Table 1]

The structures of CA1, CA2 and CA3 in Table 1 are as follows.

[0030]

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[0031]

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[0032]

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CA1 to CA4 and CA shown in Table 1
9 to CA11 mean a mixture in which A + B is a constant number in the table, and CA5 to CA8 mean a mixture in which the sum of A and B is any of 3 to 8.

In addition, typical examples of the O-substituted calixarene or its derivative of the present invention corresponding to the O-substituted calixarene of the above formula (1) or its derivative are shown below. However, of course, the present invention is not limited to these.

In these, the substituent means a polymerizable functional group, PH represents a benzene ring constituting a phenol unit cyclically bonded by a methylene chain, and R and R 'are each a substituent of PH ( R and R 'represent different substituents), m, p, q, and s each represent an integer of 0 or more (provided that m + p + q + s = A + B, and m and p are not 0 at the same time; q and s do not become 0 at the same time.)

The indication of the methylene chain is omitted. (Substituent -O-PH-R)_m, (Substituent -O-PH-R)_p, (Substituent -O-PH
-R ')_q, (Substituent -O-PH-R ')_S  (Substituent -O-PH-R)_m, (Substituent -O-PH-R)_p, (Substituent -O-PH
-R ')_q, (H-O-PH-R ')_S  (Substituent -O-PH-R)_m, (H-O-PH-R)_p, (Substituent -O-PH-R ')
_q, (H-O-PH-R ')_S  (Substituent -O-PH-R)_m, (Substituent -O-PH-R)_p, (H-O-PH-R ')
_q, (H-O-PH-R ')_S  (Substituent -O-PH-R)_m, (H-O-PH-R)_p, (H-O-PH-R ')_q, (H-
O-PH-R ')_S  (Substituent -O-PH)_m, (Substituent -O-PH)_p, (Substituent -O-PH-R ')
_q, (Substituent -O-PH-R ')_S  (Substituent -O-PH)_m, (Substituent -O-PH)_p, (Substituent -O-PH-R ')
_q, (H-O-PH-R ')_S  (Substituent -O-PH)_m, (H-O-PH)_p, (Substituent -O-PH-R ')_q, (H
-O-PH-R ')_S

In the O-substituted calixarenes or derivatives thereof of the present invention, the rate of polymerizable functionalization (for example, O-alkenylation or O-alkynylation) is from 10% to 100%.
%. The ratio of the polymerizable functional group in the O-polymerizable functionalized calixarene or a derivative thereof is represented by [the number of substituted hydroxyl groups / (the number of substituted hydroxyl groups + the number of unsubstituted hydroxyl groups)].
× 100 (%). The rate of the O-polymerizable functional group can be determined, for example, by quantifying the unreacted OH group by an acetylation method, or can be estimated from the reduction rate of the OH group in IR, NMR, or the like.

The polymerizable functional group in the O-substituted (polymerizable functionalized) calixarene or a derivative thereof of the present invention is a group having a double bond or a triple bond in the carbon chain, for example, an alkenyl group or an alkynyl group (preferably Is carbon number 3
To 8 alkenyl groups or alkynyl groups). Examples of the polymerizable functional group include an acryloyl group, a vinyl group, a propargyl group, an ethyl vinyl ether group, an isopropenyl group, a 2-propenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, and a sec-butenyl group. Group, t-butenyl group and the like.

Preferred examples of the polymerizable functional group include a group represented by the following formula (2).

[0040]

Embedded image .... (2)

[In the formula (2), n represents an integer of 0 to 3, and R ³ represents a vinyl group, a vinyl ether group, or an ethynyl group. ]

Next, specific examples of the polymerizable functional groups will be shown.
However, of course, the present invention is not limited to these.

[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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In the calixarene represented by the above formula (1) or its derivative, A structural units (a) and B
A polymerizable functional group (alkenyl group or alkynyl group) is introduced into a phenolic hydroxyl group of a part or all of the phenol units among the phenol units in the individual structural units (b). Table 2 shows specific examples of the O-substituted calixarene or a derivative thereof substituted with a group or an alkynyl group). However, of course, the present invention is not limited to these.

[0053]

[Table 2]

Compound Example 5 shown in Table 2 means a mixture in which the sum of A and B is any of 3 to 8, and other compound examples are those in which A + B is a constant constant in the table. Means a mixture.

The polymerizable oligomer for a photocurable resin of the present invention comprises the above-mentioned O-substituted calixarene of the present invention or a derivative thereof as an active ingredient.

The photocurable composition of the present invention comprises the above-mentioned O-substituted calixarene of the present invention or a derivative thereof. In the photocurable composition of the present invention,
Usually, a photopolymerization initiator that absorbs light energy to generate active species such as radicals and cations is contained.

Further, the photocurable composition of the present invention includes:
In addition, fillers (for example, calcium carbonate, titanium dioxide, kaolin, talc, silica, antimony oxide, magnesium oxide, aluminum oxide, glass fiber carbon fiber, etc.), coloring agents (for example, titanium white, titanium yellow, ultramarine, Inorganic pigments such as cobalt blue, red iron, aluminum powder and bronze powder or metal powders; carbon black, quinophthalone, hansa yellow, rhodamine 6G
Organic pigments such as lake, quinacridone, rose bengal, phthalocyanine pigment, pyrrolopyrrole pigment; various oil solutions such as azo dye, quinophthalone dye, anthraquinone dye, xanthene dye, triphenylmethane dye, phthalocyanine dye Organic dyes such as dyes or disperse dyes), and polymerizable monomers as reactive diluents (for example, butoxyethyl acrylate, methyl diethylene glycol acrylate, ethyl diethylene glycol acrylate, methyl triethylene glycol acrylate, butyl triethylene glycol acrylate, benzyl acrylate) , Tetrahydrofuryl acrylate,
Monofunctional monomers such as phenoxyethyl acrylate, acrylate of a phenol derivative mixture, diethylene glycol diacrylate, triethylene glycol, polyethylene glycol # 200 diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, 1,4 Butanediol diacrylate, 1,5 pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, diacrylate of ethylene oxide 4 mol adduct with bisphenol A), Photopolymerization initiator (for example, benzoin ether derivative, acetophenone derivative, oxime ketone derivative, acylphosphine oxide derivative) Body, acyl phosphafluorene diisocyanate derivatives,
S-phenyl thiobenzoate derivative, titanocene derivative,
Benzophenone derivative, Michler's ketone derivative, thioxanthone derivative, benzyl derivative, quinone derivative, 3
Aromatic ketones such as ketocoumarin derivatives) and unsaturated group-containing oligomers (eg, rosin-modified epoxy acrylate oligomer, aromatic epoxy acrylate oligomer, polyester acrylate oligomer, rosin-modified urethane acrylate oligomer, etc.). .

The photocurable composition of the present invention can be prepared, for example, by mixing the O-substituted calixarene of the present invention or a derivative thereof and other necessary materials with a mixer (eg, a kneader, a blender, a homogenizer, an emulsifier, a ball mill, a mixer, etc.). ) Or by mixing and dispersing and / or dissolving using a stirrer or the like.

In the photocurable composition of the present invention, an O-substituted calixarene or a derivative thereof having a polymerizable functionalization (for example, O-alkenylation or O-alkynylation) ratio of 10% to 100% is used. It is desirable to use.
In this case, since the solubility of the O-substituted calixarene or a derivative thereof to the photopolymerizable monomer is high, a mixing ratio capable of obtaining a photocurable composition having good uniformity (O-substituted calixarene of the present invention) Or the mixture ratio of the derivative and the photopolymerizable monomer) is wide, the photocurable composition can be cured at a high curing rate, and the cured product after photocuring has heat resistance and other properties. It has excellent adhesion and the like.

The photocurable composition of the present invention preferably contains a polymerizable monomer as a reactive diluent in an amount of from 0 to 90% by weight of the O-substituted calixarene of the present invention or a derivative thereof.

The photocurable composition of the present invention can be used for various purposes, for example, paints, medical materials, adhesives, electric / electronic materials (printed circuit boards), photoresists, and the like.

[0062]

According to the present invention, the O-substituted calixarene or a derivative thereof according to the present invention has good storage stability and can be cured at a high curing rate by being contained in a photocurable composition. Also, the cured product after photo-curing can be excellent in heat resistance, adhesion to other materials, and the like.

The photocurable composition of the present invention can be prepared by using the O-
Since the composition contains a substituted calixarene or a derivative thereof, the composition can be cured at a high curing rate together with good storage stability of the composition before curing. Excellent adhesion with other materials.

[0064]

Next, the present invention will be described in detail with reference to examples, but it is needless to say that the present invention is not limited to these examples. In the following description, “parts by weight” is replaced by “parts”.
Abbreviated.

In Examples 1 to 6, a method for producing the O-substituted calixarene of the present invention or a derivative thereof will be described.

[0066]Example 1  t-butyl / t-octyl calix (8) arene
2.34 g (1.54 × 10^-3mol) in toluene
PEG400 (polyethylene)
Len glycol average molecular weight 400) diethyl ether
0.25 g and ground potassium hydroxide 2.65
g (0.05mol) and vigorously stirred under a nitrogen stream
While heating, the temperature was raised to 50 ° C. Allyl bromide there 2.
78 g (0.023 mol) were added, and then 105 ° C.
Reaction for 2 hours, then unreacted by thin-layer chromatography.
I confirmed that there was no response. Cool the reaction solution from outside
After cooling to room temperature, it was poured into 100 ml of water.
The formed toluene layer was washed sequentially with hydrochloric acid and water.
Thereafter, it was separated and dried with anhydrous magnesium sulfate overnight.
This is separated and filtered, and the filtrate is evaporated to dryness.
The purified product was purified using isopropanol-methanol.
2.56 g of white powder (yield: 9
0.3%). This white powder was prepared using the following IR and NM
O-allyl compound having a substitution rate of 100% by R
Was confirmed.

(A) Spectrum of generated O-allyl-substituted t-butyl / t-octylcalix (8) arene IR (KBr): 1647 cm ⁻¹ (νC = C), 12
01 cm ^-1 (νC-OC), ¹ H-NMR without OH stretching (CD ₂ Cl ₂ ) δ6.6 to 7.1 (m, 2, Ar-H) δ5.4 to 6.1 (m, 1, -CH =) δ4.5 to _{5.2 (m, 2, = CH} 2) δ3.5 to 4.2 (br m, 4, ArCH 2 Ar and _O-CH 2) δ0.5 to 1. _{7 (m, 13, t-} C 4 H 9 and _{C 8}
H ₁₇ ) Elemental analysis Calculated: C, 83.43 H, 9.63 Found: C, 82.07 H, 9.97

[0068] (b) the raw material of t- butyl / octyl calix (8) spectrum of the arene IR (KBr): OH group stretching ^{3234cm -1 1 H-NMR (CD2Cl2} ) δ9.5 (br s, 1, ArOH) δ7 .1 (s, 2, ArH) δ 4.3 (br d, 1, ArCH ₂ Ar) δ 3.5 (br d, 1, ArCH ₂ Ar) δ 1.6 (s, 1, CH ₂ , (t-octyl) group)) δ1.2 (s, 4.5, C (CH 3) 3, (t- butyl group)) δ1.2 (s, 3, ArC (CH 3) 2, (t- octyl group)) [delta] 0 _{.6 (s, 4.5, C (} CH 3) 3, (t- octyl group))

[0069]Example 2  t-butyl / t-octyl calix (8) arene
2.34 g (1.54 × 10^-3mol) in toluene
PEG400 (polyethylene)
Len glycol average molecular weight 400) diethyl ether
0.25 g and ground potassium hydroxide 2.65
g (0.05mol) and vigorously stirred under a nitrogen stream
While heating, the temperature was raised to 50 ° C. There propargyl bro
Add 2.78 g (0.023 mol) of Mide, and add
After reacting at 60 ° C for 5 hours, thin-layer chromatography
It was confirmed that there was no unreacted material. Remove the reaction solution
Part, cool it to room temperature, then put it in 100 ml of water
Added. The formed toluene layer is washed with hydrochloric acid and water.
And dried over anhydrous magnesium sulfate overnight.
Let dry. This is separated and filtered, and the filtrate is evaporated.
Is purified using hot methanol
As a result, white powder 2.43 g (yield: 86.5%)
I got This white powder is IR and¹By H-NMR
It was confirmed that it was the target product (substitution rate 100%).
Was.

[0070]Example 3  t-butyl / t-octyl calix (8) arene
2.34 g (1.54 × 10^-3mol) in toluene
PEG400 (polyethylene)
Len glycol average molecular weight 400) diethyl ether
0.25 g and potassium carbonate 6.9 g (0.05 mol
l) and add to 50 ° C with vigorous stirring under a nitrogen stream.
The temperature was raised. There chloroethyl vinyl ether 2.
45 g (0.023 mol) are added and then at 60 ° C.
After reacting for 3 hours, unreacted by thin layer chromatography
I confirmed that there was nothing. Cool the reaction from outside
After cooling to room temperature, it was poured into 100 ml of water. form
The formed toluene layer was washed sequentially with hydrochloric acid and water.
Thereafter, it was separated and dried with anhydrous magnesium sulfate overnight.
This is separated and filtered, and the filtrate is evaporated to dryness.
The purified product was purified using isopropanol-methanol.
2.87 g of white powder (yield: 89.
4%). This white powder is IR and¹H-NMR
As a result, it was confirmed that the product was the target product (substitution rate 100%)
Was.

[0071]Example 4  t-butyl / t-amylcalix (8) arene
2.08 g (1.54 × 10^-3mol) in toluene
PEG400 (polyethylene)
Len glycol average molecular weight 400) diethyl ether
0.25 g and ground potassium hydroxide 2.65
g (0.05 mol) and add vigorous stirring.
The temperature was raised to ° C. 2.78 g of allyl bromide (0.
023 mol) and reacted at 80 ° C. for 3 hours.
After the reaction, there should be no unreacted substances by thin-layer chromatography.
It was confirmed. The reaction was cooled externally to room temperature
Later, it was poured into 100 ml of water. Formed tor
The ene layer was washed sequentially with hydrochloric acid and water, then separated,
Dry overnight over magnesium sulfate. This is separated and filtered
The filtrate was evaporated to dryness
Purification using roroform-methanol gave a white
2.26 g (yield: 87.6%) of a color powder was obtained. this
The white powder is IR and¹By H-NMR, the target substance (
(A conversion rate of 100%).

[0072]Example 5  t-butyl / t-octyl calix (8) arene
2.34 g (1.54 × 10^-3mol) in toluene
PEG400 (polyethylene)
Len glycol average molecular weight 400) diethyl ether
0.25 g and ground potassium hydroxide 2.65
g (0.05 mol) and add vigorous stirring.
The temperature was raised to ° C. There propargyl bromide 1.
Pour 43g (0.012mol) then at 80 ° C
After reacting for 2 hours, unreacted by thin layer chromatography
I confirmed that there was nothing. Cool the reaction from outside
After cooling to room temperature, it was poured into 100 ml of water. form
The formed toluene layer was washed sequentially with hydrochloric acid and water.
Thereafter, it was separated and dried with anhydrous magnesium sulfate overnight.
This is separated and filtered, and the filtrate is evaporated to dryness.
The purified product is purified using chloroform-methanol.
This gave 2.17 g of white powder (yield: 84.1).
%). This white powder is IR and¹H-NMR
It was confirmed that it was the target product (substitution rate 50%).
Was.

[0073]Example 6  t-butyl / t-octyl calix (8) arene
2.34 g (1.54 × 10^-3mol) in toluene
PEG400 (polyethylene)
Len glycol average molecular weight 400) diethyl ether
0.25 g and ground potassium hydroxide 2.65
g (0.05 mol) and add vigorous stirring.
The temperature was raised to ° C. There 0.93 g of allyl bromide (7.
7 × 10^{− 3}mol), then 80 ° C for 3 hours
After the reaction, the unreacted substance
I confirmed that Cool the reaction solution from the outside to room temperature
After that, it was poured into 100 ml of water. Formed
The toluene layer was washed with hydrochloric acid and water in that order, and then separated.
And dried over anhydrous magnesium sulfate overnight. This
The filtrate was separated by filtration and the filtrate was evaporated to dryness.
Is purified using isopropanol-methanol.
And 2.06 g (yield: 85.8%) of white powder
Obtained. This white powder is IR and¹By H-NMR,
It was confirmed that the product was the desired product (substitution ratio: 12.5%).

In Examples 7 to 10 and Comparative Examples 1 to 3, photocurable compositions will be described.

[0075]Example 7  50 parts of the compound obtained in Example 1 butyl triethylene glycol acrylate (trade name:
BTG-A photopolymerizable monomer) 50 parts Lucilin MK (trade name of photopolymerization initiator manufactured by BASF)
 One copy

A cured product was obtained by irradiating the photocurable composition having the above composition with an ultrahigh pressure mercury lamp at an illuminance of 50 mW / cm ² for 120 seconds on a petri dish made of polytetrafluoroethylene resin.

[0077]Example 8  50 parts of the compound obtained in Example 2 butyl triethylene glycol acrylate (BTG-
A: Photopolymerizable monomer) 50 parts Irgacure 651 (photopolymerization manufactured by Ciba-Geigy Japan)
Initiator trade name) 1 copy

On a petri dish made of polytetrafluoroethylene resin, the photocurable composition having the above composition was irradiated with light from an ultrahigh pressure mercury lamp at an illuminance of 50 mW / cm ² for 120 seconds to obtain a cured product.

[0079]Example 9  70 parts of the compound obtained in Example 1 butyl triethylene glycol acrylate (trade name:
BTG-A photopolymerizable monomer) 30 parts Lucilin MK (trade name of photopolymerization initiator manufactured by BASF)
 One copy

A cured product was obtained by irradiating the photocurable composition having the above composition with light from an ultrahigh pressure mercury lamp at an illuminance of 50 mW / cm ² for 120 seconds on a petri dish made of polytetrafluoroethylene resin.

[0081]Example 10  50 parts of the compound obtained in Example 5 butyl triethylene glycol acrylate (trade name:
BTG-A photopolymerizable monomer) 50 parts Lucilin MK (trade name of photopolymerization initiator manufactured by BASF)
 One copy

A cured product was obtained by irradiating the photocurable composition having the above composition with light from an ultrahigh pressure mercury lamp at an illuminance of 50 mW / cm ² for 120 seconds on a petri dish made of polytetrafluoroethylene resin.

[0083]Comparative Example 1  t-butyl calix (8) arene octa O-ant
50 parts butyltriethylene glycol acrylate (trade name:
BTG-A photopolymerizable monomer) 50 parts Lucilin MK (trade name of photopolymerization initiator manufactured by BASF)
 One copy

A cured product was obtained by irradiating the photocurable composition having the above composition with light from an ultrahigh pressure mercury lamp at an illuminance of 50 mW / cm ² for 120 seconds on a petri dish made of polytetrafluoroethylene resin.

[0085]Comparative Example 2  Methyl calix (6) arene octa O-propal
Gil ether compound 50 parts Butyl triethylene glycol acrylate (trade name:
BTG-A photopolymerizable monomer) 50 parts Lucilin MK (trade name of photopolymerization initiator manufactured by BASF)
 One copy

A cured product was obtained by irradiating the photocurable composition having the above composition with an ultrahigh pressure mercury lamp at an illuminance of 50 mW / cm ² for 120 seconds on a polytetrafluoroethylene resin petri dish.

[0087]Comparative Example 3  Butyl triethylene glycol acrylate (trade name:
BTG-A photopolymerizable monomer) 100 parts Lucilin MK (trade name of photopolymerization initiator manufactured by BASF)
 One copy

A cured product was obtained by irradiating the photocurable composition having the above composition with light from an ultrahigh pressure mercury lamp at an illuminance of 50 mW / cm ² for 120 seconds on a petri dish made of polytetrafluoroethylene resin.

In Table 3 below, for Examples 7 to 10 and Comparative Examples 1 to 3, the storage stability of the photocurable composition and the measurement of the curing rate, thermal decomposition temperature, and adhesion of the cured product or The test results are shown.

[0090]

[Table 3]

Storage stability of photocurable composition: For the photocurable composition before curing, the curing rate by maintaining the temperature at 30 ° C. for 100 hours was measured by using an FT-IR (Fourier transform infrared spectrophotometer). ).

Curing rate: [100- (strength of polymerizable functional group after curing / strength of polymerizable functional group before curing)] × 100
Was measured by FT-IR (Fourier transform infrared spectrophotometer).

Thermal decomposition temperature (Td): For each cured product,
It was measured by TG / DTA (thermogravimetry / differential thermal analysis). In Examples 7 to 10 and Comparative Examples 1 and 2, 3
Exceeded 00 ° C.

Adhesion of cured product (cross-cut test): After curing each photocurable composition into a thin film on an iron plate, 1 cm
The corners were cut vertically and horizontally with a knife at 1 mm intervals, divided into 100 squares, and a cellophane adhesive tape was stuck thereon, and then the tape was peeled off at a stretch and the squares remaining without peeling Number.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 16/26 C08F 16/26 16/32 16/32 38/00 38/00 C08L 29/10 C08L 29 / 10 49/00 49/00 F term (reference) 4H006 AA01 AB49 GN03 GP01 GP03 4J002 BE041 BG071 DA037 DA097 DC007 DE076 DE097 DE117 DE126 DE136 DE137 DE146 DE236 DJ016 DJ036 DJ046 DL006 FA046 FD016 FD097 GB01 GH01 GJ01 GP03 PA03PA PA22 PB04 PB22 PB25 PC02 PC08 QA03 QA08 QA19 QA26 QA33 QA34 QA38 QA43 QA44 QA46 SA01 SA21 SA25 SA33 SA41 SA61 SA63 SA64 SA83 SA86 TA03 TA06 TA09 TA10 UA06 WA01 WA02 WA06 4J100 AE09P AE18P AE18P AE18P AE18P AE18P AE26P AT20P BA03P BA04P BA05P BA06P BA08P BA15P BA72P BB01P BB03P BB07P BB18P BC02P BC03P BC04P BC43P CA01 JA01 JA03 JA38 JA44 JA51

Claims (9)

[Claims] (1) a plurality of phenol units constituting a calixarene or a derivative thereof is composed of two or more phenol units, and a phenolic hydroxyl group in a part or all of the phenol units is a polymerizable functional group; Or an O-substituted calixarene or a derivative thereof. 2. The A structural units (a) and B in a calixarene or a derivative thereof represented by the following formula (1):
The O-substituted calixarene or derivative thereof according to claim 1, wherein a polymerizable functional group is introduced into a phenolic hydroxyl group of a part or all of the phenol units in the phenol units in the individual structural units (b). Embedded image ... (1) [In the formula (1), A structural units (a) and B structural units (b) are combined, and the combination of A and B is one or two.
Means one or more cyclic compounds that are at least one species,
In each cyclic compound, A and B are each an integer of 0 or more, and the sum of A and B is any of 3 to 8, and the bonding order of the structural units (a) and (b) is arbitrary. In the formula (1), R ¹ and R ² represent different substituents,
R ¹ and R ² each represent a hydrogen atom, an alkyl group which may be branched, an alkenyl group which may be branched, a phenyl group which may have a substituent, or an aralkyl which may have a substituent; Represents a group, an alicyclic group, a halogen, a nitro group, an acyl group, an alkoxy group, a trifluoromethyl group, or a trimethylsilyl group. ] 3. The O-substituted calixarene or a derivative thereof according to claim 1, wherein the polymerizable functional group is an alkenyl group or an alkynyl group. 4. The O-substituted calixarene or a derivative thereof according to claim 3, wherein the polymerizable functional group is a group represented by the following formula (2). Embedded image ... (2) [In formula (2), n represents an integer of 0 to 3, and R ³ represents a vinyl group, a vinyl ether group, or an ethynyl group. ] 5. The method according to claim 3, wherein the degree of O-alkenylation or O-alkynylation is from 10% to 100%.
-Acylated calixarene or a derivative thereof. 6. A polymerizable oligomer for a photocurable resin, comprising the O-substituted calixarene or a derivative thereof according to claim 1 as an active ingredient. 7. A photocurable composition comprising the O-substituted calixarene according to claim 1 or a derivative thereof. 8. A composition comprising a filler, a colorant, a polymerizable monomer as a reactive diluent, and a photopolymerization initiator.
The photocurable composition according to the above. 9. A polymerizable monomer as a reactive diluent,
9. The photocurable composition according to claim 8, comprising 0 to 90% by weight of the O-substituted calixarene or a derivative thereof.