WO2005085317A1

WO2005085317A1 - Ultraviolet-curing composition

Info

Publication number: WO2005085317A1
Application number: PCT/JP2005/003351
Authority: WO
Inventors: Kazumasa Inata; Nobuaki Koike
Original assignee: Toagosei Co., Ltd.
Priority date: 2004-03-04
Filing date: 2005-03-01
Publication date: 2005-09-15
Also published as: JPWO2005085317A1; TW200609262A; JP4548415B2; TWI366576B; KR101111372B1; KR20070012386A

Abstract

Disclosed is a resin hardly suffering from yellowing and thus applicable to optical uses where colorlessness and transparency are strictly demanded. Also disclosed are a cationically curable ultraviolet-curing composition enabling to obtain such a resin and a method for producing the same. The ultraviolet-curing composition is characterized by containing at least one compound represented by the formula (1) below, a compound A having two or more cationically polymerizable groups and a cationic photopolymerization initiator. (1) In the formula (1), R1 represents a hydrogen atom or a methyl group; n represents an integer of 0-20; B represents an alkyl group having 1-6 carbon atoms, an alkoxy group having 1-6 carbon atoms or a halogen atom; L that is the number of substituents of B represents an integer of 0-5; m that is the number of substituents of B represents an integer of 0-4; and Z represents the formula (2) or the formula (3) below. (2) In the formula (2), R2 represents a hydrogen atom or an alkyl group having 1-6 carbon atoms. (3) In the formula (3), R3 represents a hydrogen atom or a methyl group.

Description

Specification

UV curable composition

Technical field

The present invention relates to a cation-curable ultraviolet-curable composition suitable as a display such as a liquid crystal display, a plasma display, and a touch panel, and an optical material such as an optical lens that requires transparency.

Furthermore, the present invention relates to a novel biphenyl derivative having an oxetane ring capable of cationic polymerization and a method for producing the same.

Background art

[0002] An ultraviolet curable composition is widely used as an optical material because of its features such as excellent productivity and easy application of a cured product having a fine shape. For example, for a lens sheet for a liquid crystal display, a UV curable composition is poured into a mold having fine irregularities, covered with a transparent plastic substrate, cured by irradiating UV rays, and cured. By releasing the material together with the UV-curable resin, a lens sheet to which the shape of the mold has been transferred is formed. Further, the ultraviolet-curable composition is also used as a binder for a diffusion sheet or a material for bonding various films.

[0003] Most of the raw materials of the ultraviolet curable composition are acrylic compounds, and acrylic compounds occupy most of the optical applications as described above. However, in recent years, various types of optical members and methods for producing the same have been devised using ultraviolet-curable compositions, and accordingly, strict performance is required for ultraviolet-curable compositions. . For example, UV curable compositions! On the other hand, there are demands for a conventional acrylic compound having good adhesion to a substrate which is difficult to adhere to, a material having a low shrinkage upon curing, and a material having a low water absorption. The cationically curable composition using the epoxy conjugate compound and the oxetane conjugate compound has better and better performance in terms of these physical properties than the acrylic compound. However, these cationically curable ultraviolet-curable compositions are more difficult to reduce yellowing during curing than acrylic compounds. For this reason, cationically curable UV-curable compositions are used for optical applications such as displays that require strict transparency. It was difficult to do.

[0004] Oxetane conjugates are compounds that have attracted attention in recent years as monomers that can be cured by cationic polymerization or the like, and many oxetane conjugates have been reported. For example, a bisoxetane ether conjugate obtained by contacting a 3-alkyl 3-hydroxymethyloxetane with an α, ω-dibumoalkane in the presence of an aqueous alkali metal hydroxide solution and a phase transfer catalyst has been reported. (For example, for example, Non-Patent Document 1, Non-Patent Document

See 2, Non-patent Document 3 and Patent Document 1. ) ₀ The three alkyl 3 Haromechiruokise tongue and Bisuoki cetane ether I匕合obtained by contacting the alkali metal Fuenorato divalent phenols have been reported (e.g., see Patent Document 2).

[0005] Also, various bisoxetane ethereal conjugates have been reported (see, for example, Patent Document 3, Patent Document 4, Patent Document 5, Patent Document 6, Patent Document 7, etc.).

Also, an oxetanei conjugate represented by the formula (a) has been reported (for example, see Patent Document 8).

[0006] [Formula 1]

In the formula (a), R—R represents a hydrogen atom or a methyl group, and R and R represent a hydrogen atom or

1 4 5 6

Represents an alkyl group having 1 to 6 carbon atoms.

[0008] Although there has been no mention of biphenyl derivatives having one osetan ring in one molecule in any of these known documents, there is no suggestion or suggestion.

[0009] The cationically curable composition includes a cationically polymerizable conjugate, which is an epoxy conjugate or a Z or oxetane conjugate, a glycidyl group or a 3-ethyl-3,3-xentanylmethyl group having an ether bond. An aromatic etherified compound such as phenylene and naphthalene, and a photo-thione curable composition containing a photo-thione initiator have been reported (for example, see Patent Document 9). . In addition, a transmission type characterized by containing a bisphenol type epoxy (meth) acrylate and / or urethane (meth) acrylate, a vinyl ether conjugate, a photodynamic thione polymerization initiator and a photoradical polymerization initiator. An ultraviolet curable composition for a screen has been reported (for example, see Patent Document 10). Further, a polymerizable conjugate in which 5-95% of epoxy groups in the epoxy compound are (meth) acryloyl and 5-60% of hydroxyl groups in Z or phenoxy resin are a, β-unsaturated monoisocyanate. Curable compositions for use in Fresnel lenses and the like containing a polymerizable conjugate obtained by reacting with a polymerizable compound, a photoradical polymerization initiator, and a thione polymerization initiator. See Patent Document 11).

Patent Document 1: JP-A-6-16804

Patent Document 2: German Patent No. 1021858

Patent Document 3: JP-A-7-53711

Patent Document 4: JP-A-7-173279

Patent Document 5: JP-A-8-245783

Patent Document 6: JP-A-9-309950

Patent Document 7: JP-A-10-212343

Patent Document 8: JP 2001-31665 A

Patent Document 9: JP-A-2003-096184

Patent Document 10: JP-A-07-199359

Patent Document 11: JP 2001-163939 A

Non-patent Document l: Bull.Chem.Soc.Jpn., 61, pp. 1653 (1989)

Non-Patent Document 2: Pure Appl.Chem., A29 (10), pp. 915 (1992)

Non-Patent Document 3: Pure Appl.Chem., A30 (2 & 3), pp. 189 (1993)

Disclosure of the invention

Problems to be solved by the invention

[0011] The problem to be solved by the present invention is to provide a resin having a small yellowing that can be used for optical applications where colorless and transparent properties are strictly required. And a method for producing the same.

Yet another object of the present invention is that cationic polymerization is possible, and that one An object of the present invention is to provide a novel biphenyl derivative having a tan ring and a method for producing the same. Another object of the present invention is to provide a composition containing the novel biphenyl derivative and a cured product thereof.

Means for solving the problem

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by the following means (1), and have completed the present invention. These are described below together with preferred embodiments (2) to (7).

(1) an ultraviolet-curable composition comprising at least one compound represented by the following formula (1), a compound A having two or more cationically polymerizable groups, and a photoactive thione polymerization initiator;

[0013] [Formula 2]

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 20, B represents an alkyl group having 1 to 16 carbon atoms, and an alkoxy group having 1 to 16 carbon atoms. Or a halogen atom, the number L of substituents of B represents an integer from 0 to 5, the number m of substituents of B represents an integer from 0 to 4, and Z represents the following formula (2) or the following formula: (Represents (3).)

[0015] [Formula 3]

(In the formula (2), R ² represents a hydrogen atom or an alkyl group having 116 carbon atoms.) [0017] [Formula 4]

(In the formula (3), R ³ represents a hydrogen atom or a methyl group.)

(2) The ultraviolet-curable composition according to (1), further comprising a compound B having one cationically polymerizable group.

(3) the ultraviolet curable composition according to (1) or (2), which is a sulfonate salt of a photoinitiated thione polymerization initiator;

(4) a cured product obtained by irradiating the composition according to (1) or (2) with ultraviolet light,

(5) a cured product obtained by irradiating the composition according to (3) with ultraviolet light,

(6) the cured product according to (4), wherein the cured product is an optical material,

(7) The cured product according to (5), wherein the cured product is an optical material.

[0020] Further, it has been found that the above problem can be solved by the following means (8) and (10). It is described below together with the preferred embodiment (9).

(8) a compound represented by the following formula (4),

[0021] [Formula 5]

(In the formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, n represents an integer of 0 to 20, and B represents a carbon number. It represents an alkyl group of 1 to 6, an alkoxy group of 1 to 6 carbon atoms, or a halogen atom, the number of substituents of B represents an integer of 0 to 5, the number of substituents of B is an integer of 0 to 4. Represents.) (9) A force-thione curable composition containing a compound represented by the formula (4) according to (8) and a cationic polymerization initiator,

(10) A method for producing a compound represented by the formula (7), which comprises reacting a compound represented by the formula (5) with a compound represented by the formula (6) in the presence of an alkali. is there.

[0024] [Formula 6]

In the formula (5), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 20, B represents an alkyl group having 16 carbon atoms, and B represents an alkyl group having 11 carbon atoms. 6 represents an alkoxy group or a halogen atom, the number of substituents L of B represents an integer from 0 to 5, and the number of substituents m of B represents an integer from 0 to 4.

[0026] [Formula 7]

In the formula (7), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or a carbon atom. N represents an alkyl group of 1 to 6, n represents an integer of 0 to 20, B represents an alkyl group having 16 carbon atoms, an alkoxy group having 16 carbon atoms, or a halogen atom; L represents an integer from 0 to 5, and B represents an integer from 0 to 4.

The invention's effect

[0030] The cationically curable ultraviolet-curable composition of the present invention has very little yellowing after curing, so that it can improve the transparency of display materials such as liquid crystal displays, plasma displays and touch panels, and optical lenses. It can be suitably used as a required optical material. The compound represented by the formula (4) can be suitably used as a raw material of a cured product requiring transparency.

Brief Description of Drawings

[FIG. 1] Slide glass and polyethylene terephthalate used in Examples and Comparative Examples

3 shows an ultraviolet-visible absorption spectrum of a (PET) film.

FIG. 2 shows an ultraviolet-visible absorption spectrum in evaluation of transparency of a cured product (part 1).

FIG. 3 shows an ultraviolet-visible absorption spectrum in evaluation of transparency of a cured product (part 2).

FIG. 4 shows an ultraviolet-visible absorption spectrum in evaluation of transparency of a cured product (part 2). Explanation of symbols

The horizontal axis of FIG. 14 is wavelength (nm), and the vertical axis of FIG. 14 is transmittance (%).

Solid line in Fig. 1: Slide glass

Dashed line in Figure 1: PET film

Thick and solid line in FIG. 2: transmittance of the composition of Example 3 sandwiched between glass slides and cured.

Dashed line in Fig. 2: Permeability of the composition of Example 4 sandwiched between glass slides and cured

One-dot broken line in Fig. 2: The transmittance of the composition of Example 5 sandwiched between glass slides and cured.

Thin solid line in Fig. 2: Transmittance of the composition of Comparative Example 1 sandwiched between glass slides and cured

Thick solid line in Fig. 3: transmittance of the composition of Example 3 cured on PMMA Thin solid line in Fig. 3: Transmittance of the composition of Comparative Example 2 cured on PMMA Fig. 3 Dashed line: Transmittance of the composition of Comparative Example 3 cured on PMMA Thick solid line in Fig. 4 Transmittance of the composition obtained by curing the composition of Example 3 on PMMA Thin and solid line in FIG. 4: Transmittance of the composition obtained by curing the composition of Comparative Example 4 on PMMA Dashed line in FIG. 4: Composition of Comparative Example 5 Of PMMA cured on PMMA Best mode for carrying out the invention

Hereinafter, the present invention will be described in detail.

The ultraviolet-curable composition of the present invention comprises at least one compound represented by the following formula (1),

It is characterized by comprising a compound A having two or more cationically polymerizable groups and a photoinitiated thione polymerization initiator. The ultraviolet-curable composition of the present invention forms a cationically polymerizable resin.

[0034] [Formula 9]

In the formula (1), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 20, B represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, Or, represents a halogen atom, the number L of substituents of B represents an integer from 0 to 5, the number m of substituents of B represents an integer from 0 to 4, and Z represents the following formula (2) or the following formula ( Represents 3).

[0036] [Formula 10]

In the formula (2), R ² represents a hydrogen atom or an alkyl group having 116 carbon atoms. [0038] [Formula 11]

O (3)

In the formula (3), R ³ represents a hydrogen atom or a methyl group.

The compound of the present invention is represented by the following formula (4), and the compound represented by the formula (4) can be suitably used for cation polymerization.

[0041]

[0042] In the formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 116 carbon atoms, and n represents an integer of 0-20. And B represents an alkyl group having 16 carbon atoms, an alkoxy group having 16 carbon atoms, or a halogen atom, the number of substituents L of B represents an integer from 0 to 5, and the number m of substituents m of B is Represents an integer from 0 to 4.

The compound represented by the formula (4) is a compound represented by the formula (1), wherein Z of the compound is the formula (2). Therefore, description of the compound represented by the formula (4) is omitted.

[0044] 化合物 Compound represented by formula (1)

N in the formula (1) represents an integer of 0 to 20, preferably 0 to 5, and particularly preferably 0. When n is 20 or less, the effect of reducing the yellowing of the cured product with a high concentration of the biphenyl skeleton is high, which is preferable. In particular, when n in the formula (1) is 0, the effect of reducing yellowing is not only high, but the raw material power is cheaper than that of のもの = 1 or more, and the formula (2) or the formula (3) It is particularly preferable from this point because the introduction is easy.

In the above formula (1), B represents a monovalent substituent at any position on the aromatic ring, The number of substituents L represents an integer from 0 to 5, and the number of substituents m of B represents an integer from 0 to 4.

B preferably represents an alkyl group having 16 carbon atoms, an alkoxy group having 16 carbon atoms, or a halogen atom, and is not limited to other groups as long as the cationic polymerization of the compound represented by the formula (1) is not inhibited. Any monovalent substituent can be selected. The alkyl group and the alkoxy group may have a branch. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among them, a methyl group, a methoxy group, a methyl group which is preferably a fluorine atom or a bromine atom is particularly preferable.

When m and L are 0, it means that there is no B on the aromatic ring; when m is 1 to 4, it means that there are 1 to 4 B's bonded to the aromatic ring, respectively, L In the case where is 1 to 5, it means that B is bonded to each of 5 to 5 on the aromatic ring. When substituted on the aromatic ring, L B and m B can be independently selected from the same or different substituents.

L and m in the formula (1) are preferably 0 or 2. When L and m in the formula (1) are 2, those bonded to the 3, 5, 3, 5, and 5 positions are preferred.

[0046] Z of the compound represented by the formula (1) is preferably a force Z represented by the formula (2) or (3), and preferably has an oxetane ring represented by the formula (2).

The bonding position of the compound having an oxetal group or an epoxy group in the above formula (1) of the present invention is at the 2-, 3- or 4-position, preferably at the 2- or 4-position.

[0047] The compound represented by the formula (1) is obtained by converting the compound represented by the formula (5) and the oxetane compound represented by the formula (6) or the epoxy conjugate represented by the formula (8) to an alkali. It can be obtained by reacting in the presence. A solvent may be used if necessary in this reaction. Further, a phase transfer catalyst may be used. [0048]

In the formula (5), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 20, B represents an alkyl group having 1 to 6 carbon atoms, and B represents an alkyl group having 1 to 16 carbon atoms. Represents an alkoxy group or a halogen atom, the number of substituents L of B represents an integer from 0 to 5, and the number of substituents m of B represents an integer from 0 to 4.

[0050] [Formula 14]

In the formula (6), R ² represents a hydrogen atom or an alkyl group having 116 carbon atoms.

[0052] [Formula 15]

[0053] Te you, the equation (8), R ³ represents a hydrogen atom or a methyl group.

[0054] In the compound represented by the formula (1), those other than η-force O are 2-phenylphenol, 3-phenylphenol or 4-phenylphenol, and their nucleus-substituted products are ethylene oxide or propylene oxide. (Compound represented by the formula (5)). The number of n in the compound represented by the formula (1) is controlled by controlling the amount of ethylene oxide or propylene oxide to be added. can do.

Further, the substituent B can be introduced into the nucleus of the raw material phenol by a known method, for example, a methyl group can be introduced by a Friedel-Crafts reaction.

When the compound represented by the formula (1) is a single compound, n is an integer, but when it is a mixture of different numbers of n, n may be represented by a number having a decimal point. is there . In this case, n represents the average value of a mixture of compounds represented by the formula (1) having different numbers of n.

[0055] Examples of the oxetane compound represented by the formula (6) used in the present invention include 3-alkyl 3-chloromethyloxetane and 3-chloromethyloxetane. Examples of the 3-alkyl 3-chloromethyloxetane include 3-chloromethyl-3-methyloxetane, 3-chloromethyl-3-ethyloxetane, and 3-chloromethyl-3-propyloxetane. In the present invention, 3-alkyl-3-chloromethyloxetane is preferred, and 3-chloromethyl-3-methyloxetane or 3-chloromethyl-3-ethyloxetane is more preferred.

In the present invention, the compound represented by the formula (5) and the compound represented by the formula (6) or (8) are also used when synthesizing the compound represented by the formula (1). Examples of the alkali include an alkali metal, an alkali metal hydroxide, an alkali metal carbonate, an alkaline earth metal hydroxide, an alkaline earth metal carbonate, and an alkali metal hydride. Metal, alkali metal hydroxide or alkali metal hydride. A plurality of these alkalis may be used in combination. Specific examples of alkalis used in this synthesis include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, and sodium metal. , And metallic potassium. Among these, sodium hydroxide and potassium hydroxide are preferred also because of the reason that a sufficient transfer ratio can be obtained in a short time.

[0057] The amount of the alkali to be used is preferably 1 mol or more, more preferably 18 mol, particularly preferably 1 mol, to 1 mol of the compound represented by the formula (5). It is. In consideration of the post-treatment, one mole of the alkali is added to one mole of the compound represented by the formula (5). Can be used. When used as an aqueous solution or suspension of an alkali, the alkali concentration is preferably from 1 to 96% by weight, more preferably from 20 to 96% by weight.

As the alkali metal hydroxide, preferably, a 5-60% by weight aqueous solution or a powdered sodium hydroxide or potassium hydroxide is used, and more preferably, a 40-50% by weight aqueous solution. Is used.

[0058] As a solvent for use in synthesizing the compound represented by the formula (1), a solvent inert to the raw materials and the reaction products can be used. This solvent is preferably a solvent that azeotropes with water generated in the system during synthesis. Examples of the solvent include benzene, toluene, xylene, ethylbenzene, methylcyclohexane, ethylcyclohexane, n-butynoleatel and the like. The reaction time can be reduced by distilling the water generated in the synthesis system together with the solvent. The amount of the solvent is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 20 parts by weight, based on 1 part by weight of the total of the raw material and the reaction product in the reactor. When the amount of the solvent is within the above range, the yield per unit volume is high, the energy for recovering the solvent is small, and it is economical. For the synthesis of the compound represented by the formula (1), toluene, xylene, methylcyclohexane, ethylcyclohexane and the like are suitably used.

As the phase transfer catalyst that can be used in the synthesis of the compound represented by the formula (1), known phase transfer catalysts (for example, WP Weber, GW Gokel, Iwao Tabushi, Takako Nishitani, “ ! (Shift catalyst) and those described in “Chemical Doujin Co., Ltd.) can also be used. Among these, organic quaternary ammonium salts and phosphonium salts are preferred because of their high catalytic ability. Specific examples include tetra-n-butylammonium-bromobromide, benzyltriethylammonium-bromobromide, trioctylmethylammo-bromochloride, tetra-n-butylphospho-bromochloride, trioctylethylphospho-pambromide and tetraphenylphospho-bromochloride. And the like.

[0060] The reaction temperature at the time of synthesizing the compound represented by the formula (1) is preferably from 80 to 150 ° C, particularly preferably from 100 to 120 ° C. The reaction time for synthesizing the compound represented by the formula (1) depends on the reaction temperature and whether or not a phase transfer catalyst is used, but is preferably 4 to 50 hours. After the completion of the reaction, the reaction solution cooled to room temperature is washed with water, distilled, and the like, whereby the target compound (target substance) represented by the formula (1) can be obtained. The desired product can be confirmed by ^J HN MR and ¹³ C-NMR spectrum.

[0062] In the compound of the present invention represented by the formula (1), Z is preferably represented by the formula (2) or from the curability of the power composition represented by the formula (2) or (3) or A compound represented by the formula (3), which is an R ³ methyl group, is more preferably a compound represented by the formula (2).

R ^{2 in the} formula (2) represents a hydrogen atom or an alkyl group having 116 carbon atoms, and the alkyl group may have a branch. R ² is preferably a methyl group or an ethyl group.

[0063] The composition of the present invention, but contains at least one compound represented by formula (1), and the kind of R \ R ^2, R ³ and substituents B, L, m, n number of It is possible to use a mixture of a plurality of compounds having different formulas, and it is also possible to use a mixture of compounds having different Z in the formula (1).

Further, when the compound represented by the formula (1) is L = m = n = 0 and the bond position of the compound having an oxetal group or an epoxy group is the 4-position, the compound is at room temperature. And is solid. On the other hand, when the bonding position is at the 2-position, the compound is liquid at room temperature, so that the composition is liquid even if the number of components is increased. Therefore, it is preferable that the compound having an oxetanyl group or an epoxy group be bonded at the 2-position.

Further, even when the compound has a substituent B, the binding site of the compound having an oxetanyl group or an epoxy group is preferably at the 2-position.

[0065] In the composition of the present invention, the total compounding amount of the compound represented by the formula (1) is not particularly limited, but is preferably from 10 to 99, based on 100 parts by weight of the cationically polymerizable component. Parts by weight, more preferably 20 to 90 parts by weight, particularly preferably 30 to 80 parts by weight. When the blending number is within the above range, the effect of reducing yellowing of the cured product is high! The cationically polymerizable components include a compound represented by the formula (1), a compound A having two or more cationically polymerizable groups, and a compound B having one cationically polymerizable group. Examples of the cationic polymerizable group include an epoxy group, an oxetane group, and a vinyl ether group.

The compound represented by the formula (1) can be used for applications where the transparency of the cured product is not required. I'm sorry.

[0066] The cationic polymerization initiator in the present invention acts so as to generate an acid component by being activated by adaptation of light or heat to induce cationic polymerization of the cationically polymerizable group in the composition. is there.

As the cationic polymerization initiator, it is preferable to use any light-powered thione polymerization initiator that is activated by irradiation with light and can induce polymerization of the cationically polymerizable group. Further, a photosensitizer can be used in combination. Further, as the cationic polymerization initiator, any thermal cationic polymerization initiator can be used as long as it is activated by heating and can induce polymerization of the cationically polymerizable group.

[0067] The photo-thione polymerization initiator in the present invention is a compound that generates an acid capable of undergoing cationic polymerization by irradiation with ultraviolet light. Examples of the photoinitiated thione polymerization initiator include oxalate salts and organometallic complexes.

Examples of the organometallic complexes include an iron-allene complex, a titanocene complex, and an arylsilanol aluminum complex.

Illustrative examples of o-pium salts include diazo-pium salt, odonium salt, sulfo-pum salt, selenium salt, pyridi-p-m salt, ferrose-pum salt, phospho-pum salt, and Dipium salt and the like. In the present invention, since the use of a rhododium salt may cause a yellow coloration, sulfode such as an aromatic sulfo-dum salt, dialkylphenacyl sulfo-dum salt or the like is preferred in terms of curability and less yellowing. -Pham salts are preferred, aromatic sulfo-pam salts are more preferred, and triaryl sulfo-pam salts are particularly preferred.

[0068] When a photoinitiated thione polymerization initiator such as a rhododium salt or a sulfodium salt is used in the composition of the present invention, the anion is BF-AsF-

4, 6, SbF

6, PF-, and 6

B (C F) — and the like. Preferred are SbF— and PF—.

6 5 4 6 6

[0069] Commercially available triarylsulfo-pium salts include Cyracure UVI-6990, UVI-6992, and UVI-6974 manufactured by Dow Chemical Japan, and Asahi Denka Kogyo Co., Ltd. Adeki Optomatic SP-150, SP-152, SP-170, SP-172, etc., WP AG-593, WPAG-596, WPAG-640, WP AG-641, etc. manufactured by Wako Pure Chemical Industries, Ltd. And can be used in the present invention. [0070] Commercially available aromatic rhododium salts include UV-9380C manufactured by GE Toshiba Silicone, PHOTOINITIATOR2074 manufactured by Rhodia, WPI-116, WPI-113 and CD-1012 manufactured by Wako Pure Chemical Industries, Ltd. (trade names) And Sartoma Co., Ltd.).

[0071] Among these, UVI-6990 and UVI-6992 are particularly preferred in terms of curability and low yellowing.

[0072] The blending amount of the photo-induced thione polymerization initiator in the present invention can be appropriately adjusted according to the type and irradiation amount of ultraviolet rays. For example, with respect to 100 parts by weight of the cationically polymerizable component, 0.01 to 5 parts by weight is preferable, 0.1 to 5 parts by weight is more preferable, and 13 to 13 parts by weight is particularly preferable. . It is preferable that the amount of the photoinitiated thione polymerization initiator be within the above range, since sufficient curability can be obtained, and heat resistance after polymerization and low water absorption are also sufficient. In addition, it is preferable because the physical properties of the cured product are not reduced without reducing the amount of components truly required for curing, and other characteristics such as yellowing and heat resistance of the cured product are not reduced.

[0073] A sensitizer may be used in combination with the composition of the present invention in order to increase the activity of the photoinitiated thione polymerization initiator. As the sensitizer that can be used in the present invention, it is possible to use a compound disclosed by Krivero in Advanced in Polymer Science (Adv. In Plymer Sci., 62, 1 (1984)). Specific examples include pyrene, perylene, atalidine orange, thioxanthone, 2-cloth thioxanthone, and benzoflavin.

Further, a compound widely used as a photo-radical polymerization initiator can also be used. Particularly, when a compound having a radical-polymerizable group in a molecule is added to the composition of the present invention, the radical polymerization initiator is used. Can also be added. Examples of the radical polymerization initiator include compounds that generate a radical by heat, light, a redox reaction, or the like. Examples of such a substance include an organic peroxide, an azoi compound, a redox initiator, and the like. Specifically, benzoxanone such as benzophenone, 2,4 getylthioxanthone, 2 isopropylthioxanthone, 2,4 dichloromouth thioxanthone, benzoin ether such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Benzyldimethyl ketals such as 2,2-dimethoxy-1,2-diphenyl-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1 on, 1- (4-isopropylpropyl) -2-hydroxy-2- To methyl propane 1 on, 1-hydroxycyclo Α-Hydroxyalkylphenones such as xylphenol ketone; α-dicarboxylic conjugates such as camphorquinone; and the like.

[0074] However, in the composition of the present invention, since the yellowing of the cured product can be reduced, a sulfo-dimethyl salt is used as a photothione polymerization initiator and no sensitizer is used. Is preferred.

[0075] In the composition of the present invention, the wavelength range of ultraviolet light used for curing the composition is not particularly limited, but is preferably 200 to 380 nm in consideration of both curability and low yellowing. When importance is placed solely on the small amount of yellowing, it is preferably from 300 to 380 nm, particularly preferably from 320 to 380 nm.

[0076] The light source that can be used in the case of performing polymerization using an active energy ray is not particularly limited, but has a light emission distribution at a wavelength of 400 nm or less, such as a low-pressure mercury lamp, a medium-pressure mercury lamp, and a high-pressure mercury lamp. Mercury lamps, ultra-high pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like can be used. The light irradiation intensity of the composition is controlled for each target product and is not particularly limited.However, the light wavelength range effective for activating the cationic photoinitiator having photolatitude is used. It is preferable that the light irradiation intensity (depending on the polymerization initiator) is 0.1-100 mW / cm ² . It is preferable that the light irradiation intensity of the composition be within the above range, since the reaction time is appropriate. Further, it is preferable because the heat irradiated by the lamp power and the heat generated during the polymerization of the composition do not cause a decrease in cohesive strength, yellowing or deterioration of the support of the obtained cured product. The light irradiation time for the composition is controlled for each target product and is not particularly limited, and is expressed as a product of the light irradiation intensity and the light irradiation time in the light wavelength region. It is preferable that the integrated light amount is set to be 10-5, OOOmi / cm ² . When the integrated light amount of the composition is within the above range, the generation of the active species from the initiator is sufficient, and the characteristics of the obtained cured product are not deteriorated. Further, the irradiation time is short, which is preferable since productivity is improved. In addition, most of the compositions are dried to the touch by cationic polymerization 0.1 to several minutes after the irradiation with the active energy ray, but it is sometimes preferable to use heating in combination to promote the cationic polymerization reaction. Better. [0077] The compound A having two or more cationically polymerizable groups to be blended in the composition of the present invention preferably has 10 or less, more preferably 5 or less, thiothionizable groups. Examples of the compound A having two or more cationically polymerizable groups include a compound A having an epoxy group, a compound A having an oxetanol group, and a compound A having a vinyl ether group. Mixtures can be used. As the compound A having two or more cationically polymerizable groups, a bifunctional glycidyl ether-type epoxy compound is preferred when adhesion is important, and a difunctional or higher functional epoxy compound is preferred when curability is preferred. Preferred are cyclic epoxy conjugates and Z or oxetane compounds. When the elastic modulus at or above the glass transition temperature is to be improved, trifunctional or higher is preferred.

The compound A is preferably contained in an amount of 1 to 80 parts by weight, more preferably 5 to 60 parts by weight, based on 100 parts by weight of the compound component containing a cationically polymerizable group of the composition of the present invention. More preferably, it is contained in an amount of 10 to 50 parts by weight.

[0078] Examples of the compound A having an epoxy group include dicyclopentagendioxide, limonene dioxide, 4-butylcyclohexenedioxide, 3,4 epoxycyclohexylmethylenoleate 3,4-epoxycyclohexanyl ureboxylate, (3,4-epoxycyclohexyl) adipate, bisphenol A epoxy resin (bisphenol A diglycidyl ether), halogenated bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin , Bisphenol S diglycidyl ether, halogenated bisphenol S diglycidyl ether, hydrogenated phenol bisphenol S diglycidyl ether, bisphenol F type epoxy resin, halogenated bisphenol F type epoxy resin, hydrogenated bisphenol F-type epoxy resin, 1, 6 Hexanediol diglycidyl ether, polytetramethylenglycol diglycidyl ether, compounds in which both ends of polybutadiene are glycidyl etherified, o-, m-, p-cresol novolak epoxy resin and phenol nopolak epoxy resin, etc. Epoxy novolak resin, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4' epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclo) Xinole 5,5-spiro 3,4-epoxy) cyclohexane metadioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy 6— Methylcyclohexylmethyl) adipate, 3,4 epoxy 6-methylcyclohexyl 3 ', 4' epoxy 6'-methylcyclohexanecarboxylate, methylenebis (3,4 epoxycyclohexane), dicyclopentadiene epoxide, ethylene Glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), 1,4 butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Glycerin triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers; one or more alkylated aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; Polyglycidyl ethers of polyether polyols obtained by adding oxides; Diglycidyl esters of aliphatic long-chain dibasic acids; Internal epoxidized products of polybutadiene; Double bonds of styrene-butadiene copolymer were partially epoxidized A compound (eg, Epofrend, manufactured by Daiceli-Dagaku Kogyo Co., Ltd.), a compound obtained by partially epoxidizing a polyisoprene of an ethylenebutylene copolymer and a block copolymer of polyisoprene (eg, L-207 manufactured by KRATON), 4 Compounds having a structure in which the vinyl group of the ring-opened polymer of vinyl cyclohexene oxide is epoxidized (eg, EHPE3150 manufactured by Daiceli Gakugaku Kogyo Co., Ltd.), and epoxidized vegetable oils (epoxidized soybean oil, epoxidized flax oil, etc.) Etc. can be exemplified.

As the compound A having an oxetanyl group (in Kazuko, a product name or a product name, manufactured by Toagosei Co., Ltd.), 1,4bis {[(3-ethyl-3-oxeta-l) methoxy] methyl} benzene} aronoxetane OXT— 121 (XDO)), di [2- (3-oxeta-butyl) butyl] ether (aronoxetane OXT-221 (DOX)), 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene (HQOX) ), 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene (RSOX), 1,2-bis [(3-ethyloxetane-3-yl) methoxy] benzene (CTO II), 4,4, 1-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl (4,4,100), 2,2,1-bis [(3-ethylo-3-oxeta-l) methoxy] biphenyl ( 2, 2, 1ΒΡΟΧ), 3, 3 ', 5, 5'-tetramethyl [4, 4'bis (3-ethyloxetane 3-yl) Methoxy] biphenyl (ΤΜ-ΒΡΟΧ), 2,7-bis [(3-ethyloxetane-3-yl) methoxy] naphthalene (2,7-NpDOX), 1,6-bis [(3-ethyloxetane-3-yl) methoxy ] — 2, 2, 3 , 3,4,4,5,5—year-old octafluorohexane (OFH—DOX), 3 (4), 8 (9) —bis [(1-ethyl) -3-oxeta-l) methoxymethyl] —tricyclo [5.2.1.10 ² · ⁶ ] decane, 1,2 bis {2-[(1-ethyl-3-oxeta-l) methoxy] ethylthio} ethane, 4,4,1

Bis [(1-ethyl-3-oxetenyl) methyl] thiodibenzenethioether, 2,3-bis [(3-ethyloxetane-3-yl) methoxymethyl] norbornane (NDMOX), 2-ethyl 2- [( 3ethyloxetane—3yl) methoxymethyl] —1,3Obis [(1-ethyl3-oxeta-l) methyl] propane 1,3-diol (TMPTOX), 2,2 dimethyl 1,3-O— Bis [(3-ethyloxetane-3-yl) methyl] propane 1,3-diol (NPGOX), 2-butyl-2-ethyl-1,3-O-bis [(3-ethyloxetane-3-yl) methyl] Propane 1,3-diol, 1,4-O-bis [(3-ethyloxetane 3-yl) methyl] butane—1,4-diol, 2,4,6-O-tris [(3-ethyloxetane 3-di) Methyl) cyanuric acid, bisphenol A and 3-ethyl-3-chloromethyloxetane (O Etherified product of XC) (BisAOX), etherified product of bisphenol F and OXC (BisFOX), etherified product of phenol novolak and OXC (PNOX), etherified product of cresol novolac and OXC (CNOX), oxeta-lucyl Examples include sesquioxane (OX-SQ) and silicon alkoxide (OX-SC) of 3-ethyl-3-hydroxymethyloxetane.

Further, various kinds of oxetane conjugates described in JP-A-8-85775 and JP-A-8-134405 are exemplified, and among them, a compound having two or more oxetal groups can be used. it can.

[0080] Examples of the compound A having a butyl ether group include cyclohexane dimethanol dibutyl ether, triethylene glycol divinyl ether, and novolak type divinyl ether.

[0081] Examples of the compound B to be added to the composition of the present invention include a compound B having an epoxy group, a compound B having an oxetal group, and a compound B having a vinyl ether group. It can also be used.

Compound B is preferably contained in an amount of 5 to 60 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the compound component containing a cationically polymerizable group of the composition of the present invention. Is more preferable! / ,.

Examples of the compound B having an epoxy group include α-methyl phenylepoxide, phenylglycidyl ether, and 2-ethylhexyl, such as butylcyclohexene oxide, 4-butylepoxycyclohexane, and 1,2-epoxyhexadecane. Glycidyl ether, dodecyl glycidyl ether, glycidyl methacrylate, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, monoglycidyl ethers of higher aliphatic alcohols; phenol, cresol, butylphenol Or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide thereto; monoglycidyl esters of higher fatty acids;

[0083] As the compound having an oxetanyl group (Katsuko is a trade name or a developed product name, manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (aronoxetane 0-212110) ), 3-Ethyl-3- (hexyloxymethyl) oxetane, 3-Ethyl-3- (cyclohexyloxymethyl) oxetane (CHOX), 3-Ethyl-3- (dodecyl xymethyl) oxetane (OXR-12) 3-Ethyl-3 (octadecoxymethyl) oxetane (OXR-18), 3-Ethyl-3- (phenoxymethyl) oxetane (Alonoxetane ΟΧ Τ 211 (ΡΟΧ)), 3-Ethyl-3-hydroxymethyloxetane (ΟΧΑ) , 3-Ethyl-3- (chloromethinole) oxetane and the like.

Examples of the compound having a butyl ether group include hydroxyethyl butyl ether, hydroxybutynolebininoleatene, dodecinolebininoleatene, propeninoleatenolepropylene carbonate and cyclohexylvinyl And the like.

[0085] Of these, compounds having an oxetanyl group are excellent in curability, and thus can be preferably added to the composition of the present invention. In particular, when a monofunctional compound having an oxetanyl group, that is, a compound having one oxetal group in one molecule, is used, the cured product of the present invention can be applied to a substrate having difficult adhesion. Can also be preferably used in such applications because they exhibit excellent adhesion. Among them, a particularly preferable example is 3-ethyl-3- (phenoxymethyl) oxetane (aronoxetane II- 211 (II)).

[0086] In the cationically curable composition of the present invention, a compound having at least one radically polymerizable group in the molecule may be blended as a polysynthetic component. As such Are (meth) acrylates, (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide and N-methoxybutyl (meth) acrylamide. Compounds having a (meth) atalyloyl group; monoalkyl esters of unsaturated dicarboxylic acids such as monobutyl fumarate and monobutyl maleate; and maleic anhydride. The (meth) atalyloyl group means an atalyloyl group and a methacryloyl group.

[0087] Among the compounds having a (meth) atalyloyl group, compounds having one (meth) atalyloyl group include, for example, N-butylpyrrolidone, tetrahydrofurfuryl (meth) atalylate, and 2-ethylhexyl acrylate Hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and alkylene oxides of phenol, such as phenol and ethylene oxide (Meta) acrylates of adducts, (meta) acrylates of alkyl phenols such as noyulphenol, alkylene oxides such as ketene, etc. —Ethyl hexanol with ethylene oxide And (meth) acrylates of alkylene oxide adducts of aliphatic alcohols such as atalylate. The above-mentioned alkyl is a lower alkyl group which may have a branch, and specifically, has 16 to 16 carbon atoms such as ethyl and propyl. Further, the above-mentioned alkylene is a lower alkyl group which may have a branch, and specifically, an alkylene having a carbon number of 116 such as ethylene and propylene. The above-mentioned alkylene oxides are those composed of good lower alkylenes such as ethylene and propylene. In the cationically curable composition of the present invention, two or more of these compounds are used in combination.

[0088] Among the compounds having a (meth) atalyloyl group, a compound having two or more atariloyl groups in one molecule includes a diatalylate of ethylene oxide-modified bisphenol F (for example, "Aronix M208 manufactured by Toagosei Co., Ltd.) )), Diatalylate of ethylene oxide-modified bisphenol A (for example, "Aronix M210" manufactured by Toagosei Co., Ltd.), and diatalylate of propylene oxide-modified bisphenol A (for example, "Light Atarilate BP" manufactured by Kyoeisha-Danigaku Co., Ltd.) — 4PA ”), ethylene oxide-modified isocyanuric acid diatalylate (eg, Seiko Co., Ltd. “Aronics M215”), polypropylene glycol diatalylate (eg, Toagosei Co., Ltd. “Aronics M225”), polyethylene glycol diatalylate (eg, Toagosei Co., Ltd. “Aronics M240”), Polytetramethylene glycol diatalylate (for example, “Kyoeisha-Danigaku Co., Ltd.“ Light Atarilate PTMGA-250 ”), pentaerythritol di-atalylate monostearate (eg, Toagosei Co., Ltd.“ Aronix M233 ”), Neopentyldaricole diatalylate, hexanediol diatalylate, nonanediol diatalylate, dimethylol tricyclodecane diatalylate (for example, “Kyoeisha Chemical Co., Ltd.“ Light Atalylate DCP-A ”), trimethylolpropane Acrylic acid benzoate (for example, Kyoeisha Co., Ltd. "Light Atarilate BA-134"), hydroxypivalic acid neopentyl cholesteric alcohol diatalylate (for example, Kyoeisha I-Danigaku Co., Ltd. "Light Atarilate HPP-A"), pentaerythritol triatalylate ( For example, “Aronix M305” manufactured by Toagosei Co., Ltd., trimethylolpropane triatalylate (eg, “Aronix M309” manufactured by Toagosei Co., Ltd.), and alkylene oxide-modified trimethylolpropanetriatalylate (eg, manufactured by Toagosei Co., Ltd.) "Alonics M310", "Alonics M350"), ethylene oxide-modified isocyanuric acid triatalylate (eg, Toagosei Co., Ltd. "Aronics M315"), glycerin triatalylate, alkylene oxide-modified triglycerol (eg, Nippon Kayaku Co., Ltd. O-303 ”), pentaerythritol tetraatalylate (eg,“ Aronix M450 ”manufactured by Toagosei Co., Ltd.), dipentaerythritol hexaatalylate (eg,“ Aronix M400 ”manufactured by Toagosei Co., Ltd.), ditrimethylolpropanetetra Atarilate (for example, "Aronix M458" manufactured by Toagosei Co., Ltd.), urethane atarilate (for example, "Aronix Ml100", "Aronix M1200", "Aronix M1600" manufactured by Toagosei Co., Ltd.), and polyester atelylate (for example, "Aronix M6100" and "Aguchi Nicks M7100" manufactured by Toagosei Co., Ltd., carohydrates of acrylic acid of alkylene glycol diglycidyl ether (for example, "Epoxyester 70PA" manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A diglycidyl Acrylic acid adduct of ether (for example, manufactured by Showa High Polymer Co., Ltd.) Lipoxy VR60 ”), acrylic acid adduct of phenol novolak type epoxy resin (eg,“ Lipoxy H600 ”manufactured by Showa Polymer Co., Ltd.), brominated bisphenol A diglycidyl ether with acrylic acid (eg, Showa High Polymer Co., Ltd.'s "Lipoxy SP510"). These compounds are optional. Two or more types may be used.

[0089] In addition to the above, various monomers, oligomers, polymers, and the like can be added to the composition of the present invention as long as they do not inhibit cationic polymerization.

[0090] The composition of the present invention may optionally contain a filler such as silica, alumina, and other metal oxides. Thereby, thixotropy can be imparted.

When used as an electrical insulating material or when a corrosive substrate is used, it is preferable to add a material having ion exchangeability, more preferably an inorganic material, and particularly preferably a negative electrode. It has ion exchange ability. Examples of suitable inorganic anion exchangers include IXE-500, IXE-530, IXE-550, IXE-700, and IXE-800 (V, the deviation is also manufactured by Toagosei).

[0091] Further, a coupling agent such as a silane coupling agent can be added to the composition of the present invention for the purpose of improving the adhesion of the cured product to an inorganic material. Suitable silane coupling agents include β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., ΚΒΜ-303), and γ-glycidoxypropyltrimethoxysilane (Shin-Etsu Rigaku Co., Ltd.) , ΚΒΜ-403), γ-glycidoxypropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., ΚΒΕ-403), γ-glycidoxypropylmethyljetoxysilane (Shin-Etsu Iridaku, ΚΒΜ-402), 3-ethylethyl 3 -— [[3- (triethoxysilyl) propoxy] methyl} oxetane (Toagosei Co., Ltd., XT-610) and the like.

[0092] An antioxidant can be added to the composition of the present invention for the purpose of improving heat resistance and the like. Examples of the antioxidant to be contained in the composition of the present invention include a phenolic antioxidant, a zeolite antioxidant, a phosphorus antioxidant, and an amine antioxidant, and particularly preferred are It is a phenol-based antioxidant.

[0093] Examples of the phenolic antioxidants include hydroquinone monomethyl ether, 2,6-di-t-butylhydroxytoluene (for example, BHT manufactured by Kawaguchi Chemical), 2,2-methylenebis (4-methyl-6-t-butylphenol), 4, 4'butylidenebis- (3-methyl-6-t-butylphenol), triethylene glycol bis- [3- (3,1-tert-butyl-4-hydroxy-5-methylphenol)] propionate, pentaerythritol-tetrakis [3 — (3,5-di-tert-butyl-4 —hydroxyphenyl) propionate] (Tinoku's Irgano manufactured by Specialty Chemicals) x 1010), n-octadecyl-3-([3,5, di-tert-butyl-4, -hydroxyphenyl) propionate], 4,4, -thiobis (3-methyl-6-tert-butyl) phenol, etc. Are mentioned.

[0094] When the composition of the present invention is used for applications where transparency is not required, a powdery reinforcing agent or filler such as metal oxides such as aluminum oxide and magnesium oxide may be used, if necessary. Substances, metal carbonates such as calcium carbonate and magnesium carbonate, diatomaceous earth powder, basic magnesium silicate, calcined clay, fine powdered silica, fused silica, crystalline silica and other metal compounds, and metal water such as aluminum hydroxide Oxides, other materials, such as kaolin, myriki, quartz powder, graphite, molybdenum disulfide, and other fibrous reinforcing agents and fillers such as glass fiber, ceramic fiber, carbon fiber, alumina fiber, and silicon carbide fiber , Boron fiber, polyester fiber, polyamide fiber and the like. These can be added in an amount of 10 to 900 parts by weight based on 100 parts by weight of the composition of the present invention.

Further, if necessary, a coloring agent, a pigment, and a flame retardant, for example, titanium dioxide, iron black, molybdenum red, dark blue, ultramarine, cadmium yellow, cadmium red, antimony trioxide, red phosphorus, and a bromide compound And triphenyl phosphate and the like. These can be added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the composition of the present invention.

[0095] Further, various curable monomers, oligomers and synthetic resins can be added to the composition of the present invention for the purpose of improving the properties of the resin in the molded article and the like. For example, diluents for epoxy resin such as monoepoxy, phenol resin, alkyd resin, melamine resin, fluorine resin, chlorinated vinyl resin, acrylic resin, silicone resin, polyester resin, etc. Two or more combinations can be given. The mixing ratio of these resins is within a range that does not impair the cationic polymerizability, which is the original property of the composition of the present invention, that is, 50 parts by weight or less for 100 parts by weight of the composition of the present invention. Is preferred.

[0096] Examples of means for blending the composition of the present invention and optional components include heat-melt mixing, melt-kneading using a roll or a kneader, wet mixing using an appropriate organic solvent, and dry mixing.

[0097] The composition of the present invention is cured by heat when a thermal cationic polymerization initiator is used, or by an active energy ray when an active energy linear cationic polymerization initiator is used. In the case of thermal cationic polymerization, the thermal cationic polymerization initiator is usually carried out at a temperature not lower than the temperature at which the generation of cationic species or Lewis acid is started, usually at 50 to 200 ° C.

In the case of performing polymerization by heat, heat can be applied by a generally known method, and the conditions and the like are not particularly limited.

[0098] The composition containing the formula (1) of the present invention can be cured by irradiation with a small amount of active energy rays (ultraviolet rays or the like) since oxygen inhibition during polymerization is small. The same applies to polymerization by heat.

[0099] Examples of the method of using the composition of the present invention in which the formula (1) is blended include a method of applying the composition to a substrate and then irradiating the composition with ultraviolet light. Examples of the substrate include molded resin products (plastics) such as polycarbonate and polymethylmethacrylate, metals, glass, concrete, wood such as natural wood and synthetic wood, stone materials, and paper.

[0100] The cationically curable ultraviolet-curable composition of the present invention has very little yellowing after curing, so that it can improve the transparency of display materials such as liquid crystal displays, plasma displays and touch panels, and optical lenses. It can be suitably used as a required optical material. That is, the cured product of the composition of the present invention can be suitably used for an optical material. Examples of use of the composition of the present invention are illustrated below. For example, it can be used for a lens sheet light guide plate of a liquid crystal display and its surface. It is also used as a diffusion sheet when used as a binder for liquid crystal displays, etc., as a hard coat on the surface of various films such as deflection films for liquid crystal displays, etc. It can be used as a liquid crystal sealant. Other specific examples are as follows: as a material for covering the wiring of the plasma display touch panel, as a material for bonding the edge of the display screen, as a dot spacer for the touch panel, as a DVD substrate, as a DVD substrate, Used as an adhesive for DVDs, as a coating layer for DVDs, as a core / clad for optical waveguides, as a lens for various optical devices, as a sealing part for blue LEDs, and as a sealing part for white LEDs can do.

[0101] The cured product of the composition of the present invention has a high refractive index, and is excellent in curability, heat resistance, flame retardancy, and mechanical properties. Therefore, it can be used for paints and coating materials, adhesives and the like. [0102] <Example>

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited by these examples. The percentages described below are percentages by weight.

[0103] <Example 1>

— Synthesis of 2-[(3-ethyloxetane-3-yl) methoxy] biphenyl (2-BPMOX) In a 1000 ml four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, lmol of o-phenol was added. Rufenol, 1.2 mol of 3-chloromethyl-3-ethyloxetane (manufactured by Toagosei Co., Ltd.) and 0.02 mol of tetrabutylammonium-bromobromide were mixed together, and stirred at 75 ° C-90 ° C. A 48% potassium hydroxide aqueous solution (equivalent to 1.2 mol) was dropped. After completion of the dropwise addition, the mixture was stirred for 9 hours while maintaining the reaction solution at about 110 ° C. After the reaction solution was cooled to room temperature, 250 g of water was added for washing, and the mixture was separated into an organic layer and an aqueous layer. The obtained organic layer was washed once with 100 g of water. The obtained organic layer is purified by distillation under reduced pressure (173 ° C-174 ° C, 400 Pa), and 2-[(3-ethyloxetane-3-yl) methoxy] biphenyl (formula (9) below) is converted into a colorless transparent liquid. 220.7 g (yield: 82%, purity: 99%) was obtained.

NMR (CDC1; 270 MHz) δ (ppm): 7.50-7.29 (7H, m), 7.25-7.02

Three

(2H, m), 4.42 (2H, d, J = 6.1 Hz), 4.35 (2H, d, J = 6.1 Hz), 4.08 (2H, s), 1.73 (2H , q, J = 7.6Hz), 0.81 (3H, t, J = 7.6Hz).

[0104] [Formula 16]

〇4 Synthesis of [(3-ethyloxetane 3-yl) methoxy] biphenyl (4 BPMOX) In a 1000 ml four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, 1 mol of p-phenylphenol, 1.5 mol of 3-chloromethyl-3-ethyloxetane, and 0.04 mol of tetrabutylammonium-bromobromide, while stirring at 90 ° C, 140.3 g of 48% hydroxylamine An aqueous potassium solution (corresponding to 1.2 mol) was added dropwise. After completion of the dropwise addition, the reaction solution was stirred for 14 hours while maintaining the temperature at about 110 ° C. Thereafter, 0.3 mol of 3-chloromethyl-3-ethyloxetane and 0.02 mol of tetrabutylammonium-bromobromide were added to the reaction solution, and the reaction solution was stirred for further 3 hours while maintaining the reaction solution at about 110 ° C. After the reaction solution was cooled to room temperature, 250 g of water and 250 g of toluene were dried and extracted, and separated into an organic layer and an aqueous layer. The obtained organic layer was washed three times with 250 g of water. The solvent was distilled off from the obtained organic layer under reduced pressure to obtain 255 g of a crude product. The crude product was purified by distillation under reduced pressure (192 ° C-196 ° C, 400 Pa), and 4 [(3-ethyloxetane-3-yl) methoxy] biphenyl (formula (10) below) was converted to a white solid. 223. lg (yield: 83%, purity: 99%) was obtained.

NMR (CDC1; 270MHz) δ (ppm): 7.57-7.27 (7H, m), 7.04-6.9

Three

8 (2H, m), 4.59 (2H, d, J = 6.1 Hz), 4.50 (2H, d, J = 6.1 Hz), 4.12 (2H, s), 1.90 ( 2H, q, J = 7.6Hz), 0.95 (3H, t, J = 7.6Hz).

mp: 67.8-68.3 ° C

[0106] [Formula 17]

[0107] Preparation of composition

After mixing the components and their proportions shown in Table 1 according to a conventional method to prepare a cationically curable ultraviolet-curable composition, various physical properties were evaluated. The abbreviations in Table 1 indicate the following compounds. The values in Table 1 are parts by weight.

YD128: Bisphenol A type epoxy resin (Toto Kasei Co., Ltd.)

OPP-G: orthophenylphenol glycidyl ether (Sanko Co., Ltd.)

UVR6110: 3,4 Epoxycyclohexylmethyl-3,4 Epoxycyclohexane power 2-BPMOX: Compound synthesized above

4-BPMOX: Compound synthesized above

POX: 3-Ethyl-3- (phenoxymethyl) oxetane (Alonoxetane OXT- 211, manufactured by Toagosei Co., Ltd.)

2, 2'-BPDOX: Compound represented by the following formula (11) (Developed by Toagosei Co., Ltd.)

RSOX: Compound represented by the following formula (12) (developed by Toagosei Co., Ltd.)

HQOX: a compound represented by the following formula (13) (developed by Toagosei Co., Ltd.)

TMPOX: Compound represented by the following formula (14) (Developed by Toagosei Co., Ltd.)

A200: Athalylate having alicyclic epoxy group (Cyclomer A200, manufactured by Daicel Chemical Industries, Ltd.)

UVI-6992: Triaryl sulfo-dimethylhexafluorophosphate (Dow Chemical Nippon Co., Ltd., photo-induced thione polymerization initiator)

[Formula 18]

[Formula 19]

[0110] [Formula 20]

[0112] [Table 1]

[Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3: Comparative Example 4 Comparative Example 5

To YD128 20 100 - ² _. One _; ²⁰ j 20

POX 80

2, 2 '-BPDOX 80!

RSOX; 80 40

HQOX 40

UVI-6992 2! 2 2: 2 2 [0114] Evaluation of transparency of cured product (Part 1)

Example 3 Transparency was evaluated for each of the compositions of Example 7 and Comparative Example 1 which were cured by irradiation with ultraviolet rays. That is, a double-sided tape was attached to one side of a 1-mm-thick slide glass to form a spacer, and the composition was placed between the two pieces of glass. The UV irradiation conditions were a 60 WZcm high-pressure mercury lamp, a lamp height of 30 cm (150 mWZcm ² ), an irradiation time of 20 seconds, and irradiation from only one side. The UV-visible absorption spectrum of the used slide glass is shown in Fig. 1 for reference. The thickness of the cured resin portion was about 0.25 mm.

The visible absorption spectrum of the cured product was measured without sandwiching a substrate or the like on the reference light side in a state of being sandwiched between two slide glasses. The measurement results are shown in Figure 2 (transmittance spectrum from 380 to 700 nm) and Table 3 (transmittance at 400 nm and 380 nm). In the example, the transmittance around 400 nm is clearly higher and the yellowing is smaller than that of the comparative example 1.

[0115] [Table 3]

400nm! 380nm

Example 3 87%; 83%

Example 4 86%! 82%

Example 5 86%! 82%

Example 6 86% 82%

Example 7 88% 83%

Comparative Example 1 83% ■ 77%

[0116] 評価 Evaluation of transparency of cured product (Part 2)

Example 3 and Comparative Example 2 Transparency was evaluated for each of the compositions of Comparative Example 5 which were cured by irradiation with ultraviolet rays. That is, a lmm-thick PMMA substrate is enclosed on one side with double-sided tape to form a spacer, the composition is placed in it, and a 50 μm-thick layer from the top is used to smooth the cured surface. A PET film (Lumirror 50-T60, manufactured by Toray Industries, Inc.) was laminated, irradiated with ultraviolet light, and cured. The UV irradiation conditions were a 60 WZcm high-pressure mercury lamp, a lamp height of 30 cm (150 mWZcm ² ), and an irradiation time of 30 seconds. Irradiation was performed only from the PET side. For reference, the UV-visible absorption spectrum of the PET film used is shown in FIG. Then, in order to see yellowing when directly irradiating light with a light source power, Removed and irradiated for 15 seconds. The thickness of the resin portion after curing was about 0.25 mm.

The visible absorption spectrum of this cured product was measured for each PMMA substrate, with the PMMA substrate inserted on the reference light side. Figures 3 and 4 show the measurement results. In Example 3, the transmittance near 400 nm is clearly higher and the yellowing is smaller than in Comparative Example 2—Comparative Example 5.

[0117] 硬化 Curing property and adhesion of coating film

Example 3 Each of the compositions of Example 5, Comparative Example 2 and Comparative Example 3 was evaluated for curability and adhesion.

That is, after coating each composition on a 50 μm thick PET film (Lumirror 50-T60, manufactured by Toray Industries, Inc.) with a bar coater to a thickness of 20 m, a 80 WZcm condensing high-pressure mercury At a lamp (1 lamp) and a lamp height of 10 cm, the film was passed once at a conveyor speed of 10 mZ or 30 mZ and irradiated with ultraviolet light, and the curability (state of the coating film) was examined by touch. Table 4 shows the results of this curability. In Table 4, "〇" indicates a cured coating film without tack, "△" indicates a cured coating film with tack, and "X" indicates liquid. As a result, the compositions of Examples 3 and 4 are more excellent in curability than the compositions of Example 5, Comparative Example 2 and Comparative Example 3. The atmosphere at the time of ultraviolet irradiation was 20 ° C and 54% RH.

Regarding the adhesiveness, a cross-cut peeling test was performed according to JIS K 5400, and the evaluation was as follows.

X: Fully peeled off at the interface between PET and UV-curable resin

△: Partly peeled

〇: No interfacial peeling and substrate ゃ No destruction of coating film

◎: No interfacial delamination and substrate (PET film) destruction Reference: No interfacial delamination and destruction of coating film (ultraviolet curable resin) Also, cured coating film (cured in 10 mZ) ) Was measured using an Abbe refractometer (25 ° C, sodium D line).

Table 4 also shows these results.

[0118] [Table 4] Curability Curability Adhesion Refractive index

(10mZ min) (30mZ min)

Example 3 Reference 1. 594

Example 4 〇 1 1.578

Example 5-△-----, XΔ1.580

Comparative Example 2 〇 Δ X 1.587

Comparative Example 3 〇 X X 1.57 1

[0119] Comparing the refractive indices of Example 3 and Comparative Example 3, Example 3 is higher. This indicates that it is better to use a compound having one oxetanyl group than a compound having two oxetanyl groups. Further, as shown in Examples 3 and 4, it is shown that a coating film having good adhesion and transparency can be obtained and the refractive index can be controlled.

Industrial applicability

[0120] The cationically curable ultraviolet-curable composition of the present invention has very little yellowing after curing, so that it can improve the transparency of display materials such as liquid crystal displays, plasma displays, touch panels, and optical lenses. It can be suitably used as a required optical material. In addition, the cured product obtained from the composition containing the compound represented by the formula (4) of the present invention has a high refractive index, and is excellent in curability, heat resistance, flame retardancy, and mechanical properties. It can be used for paints, coating materials, adhesives and the like.

Claims

Claims [1] An ultraviolet-curable composition comprising at least one compound represented by the following formula (1), a compound A having two or more cationically polymerizable groups, and a photoionic thione polymerization initiator. object. [Chemical 1]

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 20, B represents an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or Represents a halogen atom, the number L of substituents of B represents an integer from 0 to 5, the number m of substituents of B represents an integer from 0 to 4, and Z represents the following formula (2) or the following formula (3) Represents.)

[Formula 2]

(In the formula (2), R ² represents a hydrogen atom or an alkyl group having 116 carbon atoms.)

(In the formula (3), R ³ represents a hydrogen atom or a methyl group.) [2] The composition according to claim 1, further comprising a compound B having one cationically polymerizable group.

[3] The composition according to claim 1 or 2, which is a sulfonate salt of a photoinitiated thione polymerization initiator.

[4] A cured product obtained by irradiating the composition according to claim 1 or 2 with ultraviolet rays.

[5] A cured product obtained by irradiating the composition according to claim 3 with ultraviolet light.

[6] The cured product according to claim 4, wherein the cured product is an optical material.

[7] The cured product according to claim 5, wherein the cured product is an optical material.

[8] A compound represented by the following formula (4):

[Formula 4]

(In the formula (4), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, n represents an integer of 0 to 20, and B represents a carbon number. It represents an alkyl group of 1 to 6, an alkoxy group of 1 to 6 carbon atoms, or a halogen atom, the number of substituents of B represents an integer of 0 to 5, the number of substituents of B is an integer of 0 to 4. Represents.)

[9] A cationically curable composition comprising the compound represented by the formula (4) according to claim 8 and a cationic polymerization initiator.

[10] A method for producing a compound represented by the formula (7), which comprises reacting a compound represented by the formula (5) with a compound represented by the formula (6) in the presence of an alkali.

[Formula 5]

(In the formula (5), R ¹ represents a hydrogen atom or a methyl group, n represents an integer of 0 to 20, B is an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or Represents a halogen atom, the number L of substituents of B represents an integer from 0 to 5, and the number m of substituents of B represents an integer from 0 to 4.)

[Formula 6]

(In the formula (7), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, n represents an integer of 0 to 20, and B represents a carbon number. It represents an alkyl group of 1 to 6, an alkoxy group of 1 to 6 carbon atoms, or a halogen atom, the number of substituents of B represents an integer of 0 to 5, the number of substituents of B is an integer of 0 to 4. Represents.)