JP3056918B2 - New methoxymethyl group-containing phenol compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenol compound containing a methoxymethyl group.

[0002]

2. Description of the Related Art It has been known that phenol compounds containing a hydroxymethyl group are used for various purposes. For example, DH SOLOMON's book "THE CHEMISTRY
OF ORGANIC FILM FORMERS "is used in many fields such as lithographic printing plates, photoresists, adhesives, molding materials, laminate materials, binders, etc. The phenol-formalin-resole resin or the compound described in JP-B 1-49932, specifically, compounds such as bishydroxymethyl p-cresol and tetrakishydroxymethylbisphenol A are often used. Such conventionally known hydroxymethyl group-containing phenol compounds,
A large number of methylol groups acting as crosslinkable groups could not be introduced into the molecule. In addition, there is also a problem that the solvent solubility is deteriorated with the introduction of the hydroxymethyl group.
Further, the phenol-formalin-resole resin has a small number of reactive hydroxymethyl groups contained in the molecule, so that when both were used for a paint or a photosensitive printing plate, sufficient hardening performance could not be obtained. In order to satisfy the hardening performance, it was necessary to add a large amount of a phenol compound having a hydroxymethyl group and a resole resin.

[0003]

Accordingly, an object of the present invention is to provide a conventional phenol compound containing a hydroxymethyl group,
An object of the present invention is to provide a methoxymethyl group-containing phenol compound which has sufficient hardening performance with a small amount as compared with a resole resin and is excellent in solvent solubility.

[0004]

The phenol compound containing a methoxymethyl group of the present invention is represented by the following structural formula (I).

[0005]

Embedded image

In the formula, R represents CH ₂ OCH ₃ , CH ₂ OH or H.
However, at least three of R are CH ₂ OCH ₃ or CH ₂ OH, and at least one of them is CH ₂ OCH ₃ . Preferably, four or more of R are CH ₂ OCH ₃ or CH ₂ O
H, more preferably 5 or more CH ₂ OCH ₃ or
CH ₂ OH, most preferred are compounds wherein all R are CH ₂ OCH ₃ or CH ₂ OH, in each case at least one of which is CH ₂ OCH ₃ .

The methoxymethyl group-containing phenol compound represented by the structural formula (I) of the present invention is obtained by reacting a phenol compound of the structural formula (II) with formaldehyde in the presence of a basic catalyst, and then reacting the phenol compound in methanol with an acid catalyst. It can be obtained by reacting below.

[0008]

Embedded image

A phenol compound represented by the structural formula (II), that is, 4-4 '-[1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethylidene]
Bisphenol may be commercially available, for example, one commercially available from Honshu Chemical Industry Co., Ltd. under the name "TrisP-PA". As formaldehyde used in the present invention, both formalin and paraformaldehyde are suitable. In the first step of the synthesis of the phenolic compound of the present invention, the charged molar ratio of the phenolic compound of structural formula (II) to formaldehyde (HCHO) is 1: 2 to
1:30 is suitable, and further 1: 6 from the viewpoint of yield.
１ ： 1: 18 is preferred. As the basic catalyst, either an inorganic base or an organic base can be used. Specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, ammonia (water), tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylamine, diethylamine,
Monoethylamine, trimethylamine, dimethylamine, monomethylamine and the like can be suitably used. The amount of the basic catalyst used is generally 50 to 300 mol% based on the phenol compound of the structural formula (II). Therefore, it can be appropriately increased or decreased according to the solvent used. The reaction temperature is suitably from 0 to 60 ° C, more preferably from 0 to 45 ° C. When the temperature is lower than 0 ° C., the rate of the condensation reaction becomes slow. When the temperature exceeds 60 ° C., gelation occurs. The reaction time varies depending on the reaction temperature.
In the case of 5 ° C., 4 to 36 hours are preferable. In this case, if the reaction time is too long (for example, 48 hours or more), there is a possibility of gelation. The acid catalyst used in the second stage of the synthesis of the phenolic compound of the present invention includes inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, benzenesulfonic acid, p
-Any of organic acids such as toluenesulfonic acid and acetic acid may be used. The reaction temperature is suitably from 0 to 65 ° C.
~ 65 ° C is preferred. The reaction is slow below 0 ° C. The reaction time varies depending on the reaction temperature, the concentration and the amount of the acid catalyst, but for example at 65 ° C., preferably 0.5 to 36 hours.

Next, the hydroxymethyl group-containing ferrite of the present invention is described.
An example of the synthesis of knol (I) is shown. (Synthesis Example 1) 20 g of the phenol compound of the structural formula (II)
Dissolve in 100 ml of potassium hydroxide aqueous solution (10%)
Was. 60 ml of formalin (37%) was added to this reaction solution at room temperature.
The solution was added dropwise over 1 hour with stirring. Reaction solution at room temperature
After further stirring for 6 hours, the mixture is poured into an aqueous sulfuric acid solution and crystallized.
I let it. After thoroughly washing the obtained paste-like precipitate with water,
The product was recrystallized from 30 ml of ethanol, and the target product was converted into a white powder.
I got it. Yield 20 g. ¹ H NMR (DMSO-d6) δ 1.58 (s, 6H), 2.00 (s, 3H), 4.
42-5.52 (m, 12H), 5.16-5.24 (m, H), 6.83-7.08 (m, 10
H), 8.38 (s, 2H), 8.42 (s, 2H) Reversed-phase HPLC (Column: Shimpac CLC-ODS (Shimadzu Corporation)
Solvent): Solvent: methanol / water = 60/40 → 90/10)
And the purity was measured.
2%. Next, this hexahydroxymethyl compound 2
0 g was dissolved in 1000 ml of methanol while heating, and 1 ml of concentrated sulfuric acid was dissolved.
Was added and heated under reflux for 12 hours. After cooling the reaction solution,
After adding 2 g of lithium and stirring, the mixture was concentrated and concentrated with ethyl acetate.
After adding 300 ml of chill, washing with water and drying, the solvent was distilled off.
Was obtained as a colorless oil. Yield 22g.¹ H NMR (CDC1_Three) δ1.62 (s, 6H), 2.07 (s, 3H), 3.38
(s, 18H), 4.49 (s, 18H), 4.49 (s, 8H), 4.55 (s, 4H)
 , 6.80 (s, 4H), 6.90 (d, 2H), 6.98 (s, 2H), 7.06
(d, 2H), 7.64 (s, 1H), 7.70 (s, 2H) Reversed-phase HPLC (Column: Shimpac CLC-ODS (Shimadzu Corporation)
Solvent): Solvent: methanol / water = 60/40 → 90/10)
And the purity was measured.
%Met.

[0011]

The methoxymethyl group-containing phenol compound of the structural formula (I) thus obtained is represented by the structural formula (I)
In which all R's have better solvent solubility than compounds having a CH ₂ OH group.
Compared with compounds such as p-cresol, it has sufficient hardening performance in a small amount, and is used as a base material of a paint, a molding material, an adhesive, a binder,
It is well used as an additive for photosensitive printing plates.

Hereinafter, application examples will be described. Application Example 1 (lithographic printing plate) A 0.3 mm-thick aluminum plate (material 1050) was washed with trichloroethylene and degreased, and then the surface was grained with a nylon brush and a 400 mesh Pumice-water suspension. Washed well with water. 25% of this plate at 45 ° C
The wafer was immersed in an aqueous sodium hydroxide solution for 9 seconds, etched, washed with water, and further immersed in 20% nitric acid for 20 seconds, and washed with water. At this time, the etching amount of the grained surface is about 3 g / m ^2.
Met. Next, this plate was provided with a 3 g / m ² DC anodic oxide film at a current density of 15 A / dm ² using 7% sulfuric acid as an electrolytic solution, and then washed with water and dried. Next, the following undercoat liquid was applied to this aluminum plate, and dried at 80 ° C. for 30 seconds. The coated amount after drying was 10 mg / m ² . (Undercoat solution) β-alanine 0.1 g Phenylphosphonic acid 0.05 g Methanol 40 g Pure water 60 g Further, the following photosensitive solution was applied to this aluminum plate, and
After drying at 0 ° C. for 2 minutes, a positive photosensitive lithographic printing plate was obtained.
The coating weights after drying were all 1.8 g / m ² .

Photosensitive solution (unit is grams) Naphthoquinone-1,2-diazide-5-sulfonic acid 0.90 Esterified product of chloride and pyrogallol-acetone resin Cresol-formaldehyde novolak (as described in Table 1) (meta: P-octylphenol-formaldehyde 0.02 novolak naphthoquinone-1,2-diazide-4-sulfonic acid 0.01 chloride phenol derivative (para ratio = 6: 4, weight average molecular weight 1800, unreacted cresol 0.5%) Tetrahydrophthalic anhydride 0.05 4- (p-N, N-diethoxycarbonylamino 0.02 phenyl) -2,6-bis (trichloromethyl) -s-triazine 4- (p- N- (p-hydroxybenzoyl) 0.02 aminophenyl) -2,6-bis (tric Dye Megafac F-177 (Dainippon Ink and Chemicals 0.15 Co., Ltd., fluorosurfactant) in which the counter ion of loromethyl) -s-triazine Victoria Pure Blue BOH is converted to 0.03-1-naphthalenesulfonic acid ) Methyl ethyl ketone 26

[0014]

[Table 1] ─────────────────────────────────── Lithographic printing plate cresol-form phenol derivative aldehyde novolak Usage (g) Formula Usage (g) ─────────────────────────────────── [A] 2 .10 Methoxymethylphenol compound (I) [B] 2.16 None-───────────────────────────── ──────

After exposing these positive-type photosensitive lithographic printing plates from a distance of 70 cm with a 30-amp carbon arc lamp, an 8-fold dilution of DP-4 (trade name, manufactured by Fuji Photo Film Co., Ltd.) was used. Automatic development at 25 ° C for 40 seconds (800
U: using an automatic developing machine manufactured by Fuji Photo Film Co., Ltd.). The appropriate exposure time at this point was such that the five steps were completely clear in a gray scale (manufactured by Fuji Photo Film Co., Ltd.) having a density difference of 0.15, and the sensitivity was determined as the sensitivity of the photosensitive lithographic printing plate. Further, the time required to change two steps from the solid number of gray scales at the time of developing for 40 seconds in vat development at 25 ° C. with an 8-fold dilution of DP-4 (hereinafter referred to as development tolerance) was determined. Table 2 shows the results of sensitivity (exposure time) and development tolerance of these positive photosensitive lithographic printing plates. Next, these photosensitive lithographic printing plates were exposed for 60 seconds through a positive original film on a transparent base using a halide lamp as a light source in a vacuum printing frame, and then a developer, DP-DP, manufactured by Fuji Photo Film Co., Ltd. 4 (1: 8), rinse solution FR-3 (1:
Processed through an automatic processor charged with 7). Further, the plate surface was wiped with a burning surface conditioning liquid BC-3 manufactured by Fuji Photo Film Co., Ltd., and the plate was treated with a burning device BP-1300 for 7 minutes. Next, gum GU- manufactured by Fuji Photo Film Co., Ltd.
The plate surface was treated with a liquid obtained by diluting No. 7 twice with water, and after one day, printing was performed with a Heidel KOR-D machine. Table 2 shows the burning temperature, the obtained number of printed sheets, and the degree of entanglement of the halftone image portion.

[0016]

[Table 2] ─────────────────────────────────── Lithographic sensitivity Development Burning temperature Printing plate (exposure time) Tolerance ──────────────────── (second) (minute) 200 ℃ 260 ℃ ────────────────── ── Printing endurance Printing endurance of the halftone image area Degree of entanglement in the halftone image area (10,000 sheets) Degree of entanglement (10,000 sheets) ──────────────────── ─────────────── [A] 40 625 A 40 B [B] 60 715 C 20 D ─────────────────程度 Degree of entanglement of the net image area A: Not at all, B: Almost no, C: Available, D: Violent

From the results shown in Table 2, it can be seen that the lithographic printing plate [A] to which the phenol derivative of the present invention has been added has a non-burning property at any temperature as compared with the lithographic printing plate [B] to which no phenol derivative has been added. It can be seen that there is almost no dirt on the image portion and the printing durability is improved. Further, the lithographic printing plate [A] to which the phenol derivative of the present invention is added has increased sensitivity (suitable exposure time is shorter) as compared with the lithographic printing plate [B], and there is no practical problem in development tolerance. From the above,
The phenol derivative of the present invention has a high sensitivity without significantly lowering the development tolerance, greatly reduces the stain on the non-image area during burning at any temperature, and further improves the printing durability. It turns out that it is excellent.

Application Example 2 (Photoresist) A photosensitive solution [C] having the following composition was prepared. Photosensitive solution [C] Cresol-formaldehyde novolak resin 1.0 g (meta / para ratio = 6: 4) Compound (I) of the present invention 0.1 g Triphenylsulfonium trichloromethanesulfonate 20 mg Ethyl cellosolve acetate 10 ml Separately described above [C] Among them, a comparative photosensitive solution [D] using 0.1 g of bishydroxymethyl p-cresol instead of the compound (I) of the present invention was prepared. The photosensitive liquids [C] and [D] were coated on a silicon wafer by a spinner and dried on a hot plate at 90 ° C. for 2 minutes. Next, the resist was exposed using a g-line stepper (436 nm) and developed with a 2.4% aqueous solution of tetramethylammonium hydroxide to obtain a 0.48 μm line and space resist pattern. The resist using the photosensitive solution [D] had a sensitivity of 170 mJ / cm ² , whereas the resist using the photosensitive solution [C] had a sensitivity of 100 mJ / cm ² , and the compound (I) of the present invention was used. It can be seen that the resist has high sensitivity.

Application Example 3 (Paint) 10 g of the compound of the structural formula (I) obtained in Synthesis Example 1 and 90 g of a phenol-formaldehyde-resole resin are dissolved in 350 ml of a mixed solvent of methanol-acetone-butyl alcohol (8: 1: 1). Thus, a coating liquid [E] was prepared. Similarly, instead of the compound (I), a coating solution [F] was prepared by dissolving 10 g of bishydroxymethyl p-cresol and 90 g of a phenol-formaldehyde-resol resin in 350 ml of the above mixed solvent. A 50% methanol solution of benzenesulfonic acid was added as a curing agent to the coating liquids [E] and [F] in an amount corresponding to 15% of the weight of the coating liquid, and then applied to the wood block. After the application, the coated sample which had passed for one week at room temperature was immersed in methanol, and the film surface was visually observed. as a result,
The sample using the coating liquid [F] had a whitened surface, but the sample using the coating liquid [E] did not change.
It was shown that the compound (I) of the present invention has an effect of improving the solvent resistance of a coating. Similarly, the acid resistance was evaluated by immersion in 50% acetic acid and the alkali resistance was evaluated by immersion in a 5% aqueous sodium hydroxide solution. ] Showed stronger acid resistance and alkali resistance than the coating film using the same.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-157385 (JP, A) JP-A-6-116191 (JP, A) JP-A-62-84035 (JP, A) (58) Investigation Field (Int.Cl. ⁷ , DB name) C07C 43/178 C07C 39/15 C07C 39/16 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A methoxymethyl group-containing phenol compound represented by the following formula (I). Embedded image In the formula, R represents CH ₂ OCH ₃ , CH ₂ OH or H. However, at least three of R are CH ₂ OCH ₃ or CH ₂ OH, and at least one of them is CH ₂ OCH ₃ .