JPH11171816A - New benzyl derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a photopolymerization initiator, having excellent curing properties and improved compatibility with a resin, providing a cured material having a slight smell and not bleeding out from a cured coated film. SOLUTION: This compound is shown by formula I (R is a 1-9C alkyl; A and B are each a transcyclohexane ring or benzene ring; Ph is a benzene ring; (p) and (q) are each 0 or 1 with the proviso that a case in which both are 0 is omitted). The compound is obtained by subjecting an alkyl-substituted bicyclic or tricyclic structural benzene derivative of formula II and oxalyl chloride in the molar ratio of 0.2-1, preferably 0.5 to Friedel-Crafts reaction in an inert solvent (preferably carbon disulfide) in the presence of a catalyst (preferably anhydrous aluminum chloride in a molar ratio of 1-3) at -10 to 30 deg.C for 1-10 hour. For example, trans-1-propyl-4-phenylcyclohexane may be cited as the compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel benzyl derivative which is useful as a photopolymerization initiator and as a raw material for photopolymerization initiators, ultraviolet absorbers, liquid crystals, drugs, agricultural chemicals and the like.

[0002]

BACKGROUND OF THE INVENTION Benzyl is industrially produced by oxidizing benzoin. This benzyl is useful as a raw material for various organic compounds, and is particularly widely used as a raw material for 2,2-dimethoxy-2-phenylacetophenone (benzyldimethylketal), which is produced by methylating the benzyl.

[0003]

The above-mentioned 2,2-dimethoxy-2-phenylacetophenone has characteristics that it has good compatibility with various photopolymerizable monomers and a very high curing speed. It is widely used worldwide as a photopolymerization initiator. However, this has problems in use, such as a strong odor of a cured product obtained by using the same, and bleed out of an excessive photopolymerization initiator from a coating film. Accordingly, there is a need for the development of a photopolymerization initiator which has excellent curability, has good compatibility with a resin, and gives a cured product having a low odor, and which does not bleed out from a cured coating film.

[0004]

In order to solve the above-mentioned problems,
After intensive studies, the present invention has been accomplished. That is, the present invention
(1) The following general formula (1)

[0005]

Embedded image ２R- (A) _p- (B) _q -ph-CO-｝ ₂ (1)

(Where R represents a C1-C9 alkyl group, and A and B are each a transcyclohexane ring or a benzene ring optionally having a fluorine atom or a methyl group, preferably a 1,4-bonded trans group. A cyclohexane ring or a 1,4-bonded benzene ring optionally having a fluorine atom or a methyl group, and ph is a benzene ring optionally having a fluorine atom or a methyl group as a substituent, preferably a fluorine atom as a substituent Or a 1,4-bonded benzene ring which may have a methyl group; p and q each represent 0 or 1 except when both are 0), and (2) R is n
The novel benzyl derivative according to claim 1, which is -propyl, n-pentyl or n-heptyl, (3) the novel benzyl derivative according to (1) or (2), wherein p is 1, (4) p is 1
Wherein the q is 1 and the novel benzyl derivative of (1) or (2), wherein (5) A and B are each a 1,4-bonded transcyclohexane ring of any one of (1) to (4). A novel benzyl derivative, (6) a novel benzyl derivative of (1) or (2), wherein p is 1 and q is 0, (7)
A and B each represent a 1,4-bonded transcyclohexane ring, p and q each represent 1; (1) or (2) a novel benzyl derivative; Wherein p is 1 and q is 0, the novel benzyl derivative of (1), (9) R is n-propyl, n-pentyl or n-heptyl,
A and B each represent a 1,4-bonded transcyclohexane ring, p and q each represent 1; (1) a novel benzyl derivative; (10) R represents an n-propyl group;
A pentyl group or an n-heptyl group, A is a transcyclohexane ring having 1,4 bonds, p is 1 and q is 0
A novel benzyl derivative of (1), wherein (11) R is n-
A propyl group, an n-pentyl group or an n-heptyl group, A is a 1,4-bonded benzene ring, p is 1 and q
A novel benzyl derivative according to (1), wherein

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the above general formula (1), examples of the C1-C9 alkyl group for R include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an n-pentyl group. A straight-chain C1-C9 alkyl group such as a hexyl group, an n-heptyl group, an n-octyl group and an n-nonyl group is preferred, and more preferably an n-propyl group, an n-pentyl group or an n-heptyl group. is there.

The benzene ring which may have a fluorine atom or a methyl group in A, B and ph is, for example, a 3-fluorobenzene-1,4-group, a 2,3-difluorobenzene-1,4-group. , 3-methylbenzene-
A 1,4-group and the like. The substitution positions of the fluorine atom or methyl group on the benzene ring are 2nd, 3rd, 2nd and 3rd
2nd and 5th, 2nd and 6th, 3rd and 5th,
Position and / or position 3 are preferred. Also, an adjacent group of a transcyclohexane ring or a benzene ring which may have a fluorine atom or a methyl group (R in the above general formula (1))
Alternatively, the bond between adjacent rings is preferably a 1,4 bond.
In the ring A of the general formula (1), the position where R is bonded is the first position.

In the above general formula (1), R, A, B,
Preferred examples of the combination of p and q include, for example, those described in the above (2) to (11). Next, Table 1 shows specific examples of the novel benzyl derivative represented by the above formula (1) of the present invention. In Table 1, C-HE represents a transcyclohexane ring, and ph represents a benzene ring.

[0010]

Table 1 Table 1 Compound No. RA B phpq 1 n-C3H7 1,4-C-HE 1,4-C-HE 1,4- 11 2 n-C5H11 1,4-C-HE 1,4-C-HE 1, 4- 1 1 3 n-C7H15 1,4-C-HE 1,4-C-HE 1,4- 1 1 4 n-C3H7 1,4-C-HE 1,4- 1 0 5 n-C5H11 1 , 4-C-HE 1,4- 10 06 n-C7H15 1,4-C-HE 1,4- 1 0 7 n-C3H7 1,4-ph 1,4- 10 08 n-C5H11 1, 4-ph 1,4- 1 0 9 n-C7H15 1,4-ph 1,4- 1 0 10 n-C3H7 1,4-C-HE 1,4-C-HE 1,4- (3-F ) 1 1 11 n-C5H11 1,4-C-HE 1,4-C-HE 1,4- (3-F) 1 1 12 n-C3H7 1,4-C-HE 1,4- (2- F, 3-F) 10 13 n-C3H7 1,4-C-HE 1,4- (3-CH3) 10

The novel benzyl derivative represented by the above formula (1) is represented by the following formula (2)

[0012]

Embedded image R- (A) _p- (B) _q -ph (2)

(Wherein R, A, B, ph, p, and q have the same meanings as described above). A benzene derivative having an alkyl-substituted 2-3 ring structure and 0.2 to 1.0 mol Oxalyl chloride in an inert solvent, particularly preferably in carbon disulfide, in the presence of a catalyst, preferably 1.0 to 3.0 molar ratio of anhydrous aluminum chloride, It can be obtained by performing a Friedel-Crafts reaction at 10 to 30 ° C. for 1 to 10 hours. still,
Many of the compounds represented by the formula (2) are obtained as commercial products. (For example, manufactured by Kanto Chemical Co., Ltd.)

[0014]

【Example】

Now, the present invention will be described in further detail with reference to Examples. Parts in Examples are parts by weight.

Example 1 Trans-1-propyl-4 in 400 parts of carbon disulfide
-40.4 parts of phenylcyclohexane and 50 parts of anhydrous aluminum chloride are added, and 12.7 parts of oxalyl chloride is added dropwise at 5 ° C or less over about 30 minutes. The reaction is carried out at 5 ° C or lower for 4 hours and at 15-25 ° C for 3 hours and poured into 600 parts of ice water. Carbon disulfide is distilled off, cooled and filtered to obtain 40 parts of a solid. This is recrystallized from cyclohexane,
The above No. A purified product of compound 4 is obtained. Melting point 94-97
° C.

Example 2 Trans-1-pentyl-4 in 400 parts of carbon disulfide
-Add 46 parts of phenylcyclohexane and 50 parts of anhydrous aluminum chloride, and add oxalyl chloride 1 at 5 # C or less.
2.7 parts are added dropwise over about 30 minutes. The reaction is carried out at 5 ° C or lower for 4 hours and at 15-25 ° C for 3 hours and poured into 600 parts of ice water. The carbon disulfide is distilled off, cooled and filtered to obtain 40 parts of a solid. This was recrystallized from cyclohexane. A purified product of compound 5 is obtained. Melting point 100-10
3 ° C.

Example 3 Trans-4- (trans-) was added to 400 parts of carbon disulfide.
4-Pentylcyclohexyl) cyclohexylbenzene (31.2 parts) and anhydrous aluminum chloride (25 parts) are added, and oxalyl chloride (6.36 parts) is added dropwise at 5 ° C. or lower over about 30 minutes. The reaction is carried out at 5 ° C or lower for 4 hours and at 15-25 ° C for 6 hours, and the mixture is poured into 400 parts of ice water. After distilling off carbon disulfide and cooling, the aqueous layer was removed by decantation to obtain an oily substance 32.
Get the part. The compound was dissolved in cyclohexane, fractionated and purified by column chromatography. A purified product of compound 2 is obtained. 155-157 ° C.

EXAMPLE 4 4-Propyl-biphenyl 3 in 400 parts of carbon disulfide
9.2 parts and 40 parts of anhydrous aluminum chloride are added, and 12.7 parts of oxalyl chloride is added dropwise at 5 ° C. or lower over about 30 minutes. The reaction is carried out at 5 ° C or lower for 4 hours and at 15-25 ° C for 3 hours and poured into 600 parts of ice water. The carbon disulfide is distilled off, cooled and filtered to obtain 40 parts of a solid. This was recrystallized from cyclohexane. A purified product of compound 7 is obtained. 173-174 ° C.

Example 5 In the same manner as in Examples 1 to 4 and using the corresponding raw materials, 1, 3, 6, 8 to 13 benzyl compounds are obtained.

Application Examples 1-4, Comparative Examples 1-2 KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate and pentaacrylate, manufactured by Nippon Kayaku Co., Ltd.) 60 parts, KAYARAD R-114
(Epoxy acrylate, manufactured by Nippon Kayaku Co., Ltd.) 25 parts,
A varnish was prepared by mixing 15 parts of KAYARADTMPTA (trimethylolpropane triacrylate, manufactured by Nippon Kayaku Co., Ltd.) and 0.5 part of Modaflow (leveling agent, manufactured by Monsanto Co., Ltd.). Next, 15 parts of carbon black (pigment) based on 100 parts of the varnish,
After mixing 3 parts of each of the benzyl derivatives obtained in 4, and premixing,
The mixture was kneaded three times with a three-roll mill to obtain a photosensitive resin composition. These resin compositions were applied on a polyethylene terephthalate film (thickness: 75 μm) by an RI tester so as to have a thickness of 5 to 7 μm. Next, the film was passed through a place of 10 cm under a metal halide lamp of 80 W / cm and cured by irradiating ultraviolet rays, and the curability (mJ / cm ² ) of the resin composition and the odor of the cured product were evaluated. Table 2 shows the evaluation results.

[0021]

Table 2 Application examples Comparative examples 1 2 3 4 1 2 Compound of Example 1 3 Compound of Example 2 3 Compound of Example 3 3 Compound of Example 4 3 IRGACURE 651 * 1 3 Benzyl * 2 3} ─────────────────────── Surface curability (mJ / cm ² ) 70 70 70 70 90 90 Internal curability (mJ / cm ² ) 140 140 140 140 180 180 Odor of cured product ○ ○ ○ ○ △ ×

Note * 1 IRGAGURE 651: C
iba Geigy photopolymerization initiator 2,2-dimethoxy-2-phenylacetophenone * 2 C ₆ H ₅ COCOC ₆ H ₅

Curability: Each resin composition was treated with a RI tester on a polyethylene terephthalate film (thickness: 75 μm).
m) was applied so as to have a thickness of 5 to 7 μm. Next, this film was placed under an 80 W / cm metal halide lamp.
It was passed through 0 cm and irradiated with ultraviolet light. The curability was evaluated based on the surface curability by transferring the coated paper onto the cured surface of the coating and the internal curing by touching the finger, and the amount of ultraviolet light required to cure the coating ( mJ /
cm ² ) was measured.

Odor of the cured product: The difficulty of volatilization was evaluated based on the following criteria.・ ・ ・: There is almost no odor. Δ: There is a slight odor. ×: There is an odor.

As is clear from the above-mentioned application examples and comparative examples, the photosensitive resin composition containing the novel benzyl derivative of the present invention has excellent curability (photosensitivity) and gives a cured product having almost no odor.

[0026]

The novel benzyl derivative of the present invention has a function as a photopolymerization initiator. This novel benzyl derivative has a molecular weight of about 2-3 times that of the conventionally used 2,2-dimethoxy-2-phenylacetophenone, has a low vapor pressure, is difficult to volatilize, has almost no odor of the cured product, and has little odor. Bleeding out of the coating is also difficult. In addition, the compatibility with the monomer is improved, and the conventional technology can be greatly improved.

Claims (11)

[Claims] 1. The following general formula (1): {R- (A) _p- (B) _q -ph-CO-} ₂ (1) (where R is a C1-C9 alkyl group) A, B
Represents a transcyclohexane ring or a benzene ring which may have a fluorine atom or a methyl group,
h represents a benzene ring which may have a fluorine atom or a methyl group as a substituent. p and q represent 0 or 1, except when both are 0. A novel benzyl derivative represented by the formula: 2. The novel benzyl derivative according to claim 1, wherein R is n-propyl, n-pentyl or n-heptyl. 3. The novel benzyl derivative according to claim 1, wherein p is 1. 4. The novel benzyl derivative according to claim 1, wherein p is 1 and q is 1. 5. The novel benzyl derivative according to claim 1, wherein A and B are each a transcyclohexane ring. 6. The novel benzyl derivative according to claim 1, wherein p is 1 and q is 0. 7. The method according to claim 1, wherein A and B are each a transcyclohexane ring, and p and q are each 1.
New benzyl derivative of 8. A is a transcyclohexane ring, and p is
3. The novel benzyl derivative according to claim 1 or 2, wherein q is 0 and q is 0. 9. The novel benzyl according to claim 1, wherein R is n-propyl, n-pentyl or n-heptyl, A and B are both transcyclohexane rings, and p and q are each 1. Derivatives. 10. The novel benzyl derivative according to claim 1, wherein R is n-propyl, n-pentyl or n-heptyl, A is a transcyclohexane ring, p is 1 and q is 0. 11. The novel benzyl derivative according to claim 1, wherein R is n-propyl, n-pentyl or n-heptyl, A is a benzene ring, p is 1 and q is 0.