JPH11349516A - Phenolic novolak-type vinyl ether and polymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a phenolic novolak-type vinyl ether containing phenolic novolak-type vinyl ether compounds of tetra-nuclear form and binuclear form at specific ratios and useful as a composition for ink, etc., giving a cured material exhibiting low skin stimulation and excellent adhesion. SOLUTION: The objective compound contains >=30 wt.% of a tetranuclear phenolic novolak-type vinyl ether compound expressed by formula I [R is a vinyl ether group of (R1 )p -O-}q -CH=CH2 (R1 is a 1-10C alkylene; (p) is 1-10; (q) is 0-10) or H]; the ratio of H atom/vinyl ether group is 0/100 to 70/30 (molar ratio) as an average over the whole molecule of formula I} and <=15 wt.% of a binuclear phenolic novolak-type vinyl ether compound of formula II. The objective compound can be produced by reacting a phenolic novolak with a haloalkylenoxy vinyl compound of formula III (X is a halogen) in the presence of a basic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phenolic novolak type vinyl ether compound and a polymerizable composition thereof.

[0002]

2. Description of the Related Art At present, polymerizable compositions containing an ultraviolet curable resin, an electron beam curable resin and the like are mainly used in many fields such as inks, paints, adhesives, resists and plate-making materials. . An acrylate monomer or a polyfunctional acrylate compound is used as the main agent, and a radical generating initiator is used as the polymerization initiator.

[0003]

However, the acrylate compound has a problem in odor, and the curing reaction by the radical generating initiator may be inhibited by oxygen in the air.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems and completed the present invention. That is, the present invention relates to (1) a phenolic novolak-type vinyl ether having the formula (1)

[0005]

Embedded image

(Wherein R is a hydrogen atom or a general formula-
{(R ₁ ) _p —O—｝ _q —CH ＝ CH ₂ (R ₁ is a linear or branched alkylene group having 1 to 10 carbon atoms;
Represents an integer of 1 to 10, and q represents an integer of 0 to 10, respectively. ) Represents a vinyl ether group. Further, the ratio of hydrogen atom / vinyl ether group is 0/100 to 70/30 (molar ratio) as an average value of the whole molecule of the formula (1). Phenolic novolak-type vinyl ether compound represented by the formula (2):

[0007]

Embedded image

(Wherein R represents the same meaning as in formula (1)), wherein the amount of the binuclear phenol novolak type vinyl ether compound represented by the formula (1) is 15% by weight or less. (2) A polymerizable composition containing the compound described in (1) above, a vinyl ether compound and a polymerization initiator other than the above, (3) a polymerizable compound described in (2) above containing a resin component, and (4) lubricity. The polymerizable composition for coating according to any one of (5), (2), (3), and (4), wherein the polymerizable composition according to the above (2) or (3) contains a imparting agent. Is what you do.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The phenolic novolak type vinyl ether compound of the present invention contains at least 30% by weight of a tetranuclear phenolic novolak in which all Rs of the formula (1) are represented by hydrogen atoms, R is all represented by a hydrogen atom 2
A phenol novolak having a core phenol novolak content of 15% by weight or less has a general formula (3)

[0010]

X- (R ₁ ) _p -O-｝ _q -CH −CH ₂ (3)

(In the formula, X represents a halogen atom.) It is easily obtained by reacting a haloalkyleneoxyvinyl compound represented by the formula (1) in the presence of a basic compound. The method for producing the phenol novolak used in the present invention includes a dimethylol derivative of a binuclear phenol such as phenol, o-, m- and p-cresol (a compound in which all Rs are hydrogen atoms in the formula (2)). With phenols. Specifically, phenol novolaks obtained according to the method described in JP-A-63-77915 can be used, and a tetranuclear phenol novolak is used as a main component and a binuclear phenol novolak is used. Other than these, phenolic novolaks containing five or more nuclei.

Specific examples of the compound of the formula (3) that can be used include chloroethyl vinyl ether, chlorobutyl vinyl ether, bromoethyl vinyl ether and the like. The amount of the compound of the formula (3) used is usually 0.1 mol or more per 1 mol equivalent of the OH group of the phenol novolak,
It is preferably at least 0.3 mol, particularly preferably 1 to 3 mol.

When the phenol novolak is reacted with the compound of the formula (3), specific examples of the basic compound that can be used include alkali metal compounds such as sodium hydroxide, potassium hydroxide and sodium hydride, and sodium methylate. And alkali metals such as alkali metal alcoholates and sodium metal, and the amount thereof is usually 0.5 to 10 mol, preferably 1.0 to 1.0 mol equivalent to 1.0 mol equivalent of the OH group of phenolic novolak. 3.0 mol. At this time, tetrabutylammonium bromide, benzyltriethylammonium chloride, trioctylammonium chloride, tetrabutylammonium hydrogensulfate, dicyclohexyl-18-crown-6, dibenzo-18-crown-6, 18-crown-6, polyethylene The reaction is further accelerated when a phase transfer catalyst such as glycol 400 is used in combination. The amount of the phase transfer catalyst used is usually 0.1 to 20 mol%, preferably 0.5 to 1.0 mol equivalent of the OH group of the phenol novolak.
-10 mol%.

The above reaction may be carried out in an inert solvent, for example, a solvent such as dimethyl sulfoxide, dimethyl sulfone, dimethylformamide, N-methylpyrrolidone, aprotic polar solvent such as N, N-dimethylimidazolidone. . The reaction temperature is usually 30 to 150 ° C, preferably 60 to 110 ° C, and the reaction time is generally 5 to 12 hours, preferably 7 to 10 hours. Further, the reaction can be allowed to proceed while removing the water generated by the reaction out of the reaction system. After completion of the reaction, the reaction mixture is cooled to room temperature, the organic layer is extracted with methyl ethyl ketone, methyl isobutyl ketone, or the like, and the organic layer is washed with water several times to obtain the unreacted formula (3).
To obtain the phenolic novolak-type vinyl ether of the present invention by removing the solvent, under reduced pressure, after drying the organic layer with a drying agent such as anhydrous sodium sulfate, and removing the by-product inorganic salt. Can be.

The polymerizable composition of the present invention comprises the phenolic novolak type vinyl ether of the present invention, other vinyl ether compounds, a polymerization initiator and, if necessary, a resin component, a lubricity-imparting agent and various polymerizable compounds, It can be obtained by mixing a sensitizer, a dye, a pigment, a plasticizer, an inorganic filler, an antioxidant, an organic solvent and the like.

There are no particular restrictions on the vinyl ether compound that can be used in the present invention. For example, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, butyl vinyl ether, ethylene glycol monovinyl ether, butanediol monovinyl ether, ethylene glycol butyl vinyl ether, triglycol Ethylene glycol methyl vinyl ether, cyclohexane dimethanol monovinyl ether, cyclohexane dimethanol divinyl ether,
2-ethylhexyl vinyl ether, t-butyl vinyl ether, t-amyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether,
Cyclohexyl vinyl ether, butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,3-butenediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1 , 4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol trivinyl ether,
Pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, dipentaerythritol penta and hexavinyl ether, ethylene glycol diethoxy vinyl ether, triethylene glycol diethoxy vinyl ether, ethylene glycol dipropylene vinyl ether, trimethylolpropane triethoxy vinyl ether, pentaerythritol tetra Polyfunctional vinyl ethers such as ethoxy vinyl ether, dipentaerythritol penta and hexaethoxy vinyl ether, organic polyisocyanates (for example, tolylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) and hydroxyl group-containing vinyl ethers (for example, , 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4
-Hydroxybutyl vinyl ether, pentaerythritol trivinyl ether, etc.) or the organic polyisocyanate, the hydroxyl group-containing vinyl ether and a polyol (for example, 2,2-bis (4-hydroxydiethoxyphenyl) propane, 2,2- Screw (4-
(Hydroxydiethoxyphenyl) sulfide, 2,2
-Bis (4-hydroxypentaethoxyphenyl) propane, 2,2-bis (4-hydroxydiethoxy-
Urethane vinyl ether, which is a reaction product of 3,5-dibromophenyl) propane, polytetramethylene glycol, neopentyl glycol, polyester polyol, and the like. The vinyl ether compounds that can be used in the present invention are not limited to these, and one or more of them can be used in combination. In the polymerizable composition of the present invention, the mixing ratio of the phenolic novolak-type vinyl ether of the present invention (hereinafter, compound (A)) and the other vinyl ether compound (hereinafter, compound (B)) is as follows:
Usually (compound (A)) / (compound (B)) =
5/95 to 90/10, preferably 15/85 to 50 /
50.

The polymerization initiator that can be used in the present invention is not particularly limited as long as it can cause radical polymerization or ionic (cationic) polymerization of a thermal polymerization initiator or a photopolymerization initiator. Specific examples of the thermal polymerization initiator that can be used include benzoyl peroxide, acetyl peroxide, lauroyl peroxide,
Examples thereof include t-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, azobis-2-4-dimethylvaleronitrile, and azobiscyclohexanecarbonitrile. Specific examples of the photoradical polymerization initiator that can be used include 2,4-diethylthioxanthone, benzophenone, 4-dimethylaminoisoamylbenzoate, 4-dimethylaminoethylbenzoate and the like. Specific examples of the cationic photopolymerization initiator that can be used include JP-B-53-32831, JP-B-52-14277, JP-B-52-14278, JP-B-52-14279, and JP-B-52-25686.
JP-B-61-34752, JP-A-54-53181
No., JP-A-54-95686, JP-B-61-3653
0, JP-B-59-19581, JP-B-63-656
No. 88, JP-A-55-164204, JP-B-60-3
0690, JP-B-63-36332, JP-B 1-3
No. 9423, No. 2-10171, No. 5-15
No. 721, Tokiko 4-62310, Tokiko 62-57
No. 653, No. 3-12081, No. 3-120
No. 82, Tokuhei 3-16361, Tokubo 63-120
No.92, JP-B-63-12093, JP-B-63-12
No. 095, Tokiko 63-12094, Tokiko 2-37
No. 924, No. 2-35764, No. 4-133
No. 74, Tokuhei 4-75908, Tokuhei 4-7342
No. 8, JP-B-53-32831, JP-A-2-1-1508
No. 48, JP-A-2-296514, U.S. Pat.
Nos. 69,055, U.S. Pat. No. 4,069,056, U.S. Pat. No. 3,703,296, etc., sulfonium salts, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, arsonium salts, iron And arene complexes. These photopolymerization initiators and thermal polymerization initiators may be used alone or in combination of several types. The amount of the polymerization initiator to be used is generally 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total weight of the compound (A) and the compound (B).

The polymerizable composition of the present invention may contain a resin component for improving the adhesion. Specific examples of the resin component that can be used in the present invention include terpene resins, ketone formaldehyde resins, xylene formaldehyde resins, and the like, with terpene resins being preferred. Examples of the terpene resin include YS-Polystar T115 and YS-Polystar T manufactured by Yashara Chemical Company.
145, Mighty Ace G125 and the like. Ketone formaldehyde resin is, for example, Syx manufactured by Huls Co.
neticicAP, Synthetic
resin SK, Synthetic resin
BL1201 and the like. Xylene formaldehyde resin is, for example, Nikanol GH manufactured by Mitsubishi Gas Chemical Company.
P-160, Nicanol HP-120, Nicanol HP
-210 and the like. Resin component (hereinafter referred to as resin (C))
Is usually (compound (A) + compound (B)) / resin (C) = 95/5 to 40/60, preferably 90/10 to 60/40 in weight ratio.

In order to improve the adhesion of the polymerizable composition of the present invention, a lubricating agent may be added. Specific examples of the lubricity imparting agent include silicone-based wax, fluorine-based wax, animal-based wax, and plant-based wax. Examples of the silicone wax include, for example,
Nippon Konika's Silwet L-7001, Silwet L-7604, Silwet FZ-2105, Silwet Y-7006, Dow Corning's Paintad 29, Paintad 32, Shin-Etsu Silicone's Shin-Etsu Silicone KF-96 The fluorine-based wax includes, for example, Shamrock Wax ST-1MG manufactured by Shamrock Chemicals, Florad FC-430 manufactured by Sumitomo 3M, and Florard FC manufactured by Sumitomo 3M Limited.
-431 and the like. Specific examples of the animal-based wax include, for example, beeswax and wool wax, and specific examples of the plant-based wax include, for example, carnauba wax,
Cotton wax and the like. These lubricity imparting agents may be used alone or in combination of several kinds. The amount of the lubricity imparting agent to be used is 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total of compound (A) and compound (B).

The polymerizable composition of the present invention can be obtained by heating, mixing and dissolving the above components at a predetermined ratio. The cured product of the present invention can be obtained by heating or irradiating the polymerizable composition of the present invention with active energy rays, or a combination thereof, and is preferably used as a coating composition.

When the polymerizable composition of the present invention is used as a coating agent, a coating film is obtained by applying the composition of the present invention to various substrates by various coating methods, and then irradiating with ultraviolet light or irradiating with ultraviolet light and heating. be able to. Specific examples of the substrate include, for example, paper, plastics (for example, polycarbonate, acrylic, ABS,
Polyester, polypropylene, etc.), metals (eg, iron, copper, aluminum, zinc, chromium, tin, etc.), glass, wood, rubber, stone, concrete and the like. Specific examples of the coating method include, for example, spin coating, spraying, electrostatic coating, roll coating, curtain flow coating, brush coating, bar coating, gravure printing, screen printing, offset printing, and the like. No. Examples of the ultraviolet irradiation source include a high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight.

[0022]

The phenolic novolak type vinyl ether of the present invention is a polymerizable composition which gives a cured product having low skin irritation and excellent adhesiveness, including coating agents, inks, paints, adhesives, resists and plate making. It is extremely useful in various fields such as materials.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Synthesis Example 1 A dimethylol compound of binuclear o-cresol 200 was placed in a reactor equipped with a thermometer, a reflux condenser, a nitrogen introducing device and a stirring rod.
g and 750 g of o-cresol were charged and stirred at room temperature. Next, 2 g of p-toluenesulfonic acid (1.0% by weight based on the o-cresol binuclear dimethylol compound) was added slowly, paying attention to heat generation, so that the liquid temperature did not exceed 50 ° C. After the addition, the mixture was reacted at 50 ° C. for 2 hours, then 500 ml of methyl isobutyl ketone was added, and the mixture was transferred to a separating funnel and washed with water. After washing with water until the washing water showed neutrality, the organic layer was concentrated under reduced pressure to obtain 306 g of a pale yellow viscous substance. This solidified when left at room temperature. Softening temperature of product (JIS K2
425 environmental law) at 810 ° C with hydroxyl equivalents (g / mo)
l) was 119. As a result of analyzing the product by GPC, the contents of tetranuclear and binuclear phenol novolaks were 84% by weight and 0.7% by weight, respectively.

Example 1 The product 100 obtained in Synthesis Example 1 was placed in a reactor equipped with a thermometer, a reflux condenser, a dropping funnel, a nitrogen introducing device, and a stirring device.
g and 100 ml of dimethyl sulfoxide were dissolved therein, and then 44 g of sodium hydroxide was added thereto, followed by stirring at 70 ° C. for 30 minutes. Then, 2-chloroethyl vinyl ether 11
While maintaining the temperature inside the reactor at 70 ° C., 2 g
The mixture was dropped over a period of minutes, and further reacted at 75 to 80 ° C. for 5 hours. The reaction solution was cooled to room temperature, and methyl ethyl ketone 50
g, 150 g of water were added, and the target compound was extracted into the organic layer.
Inorganic salts and unreacted raw materials were dissolved in the aqueous layer. The aqueous layer was separated with a separating funnel, and the organic layer was washed with water five times. Anhydrous sodium sulfate was added to the organic layer, and the mixture was allowed to stand overnight. After filtration, methyl ethyl ketone and excess chloroethyl vinyl ether were distilled off under reduced pressure to obtain 140 g of a product. The infrared absorption spectrum of this product shows 1610 cm ⁻¹ , 9
Absorption by vinyl group at 75 cm ^-1 , 1200 cm ^-1
3400 cm
It was confirmed that the target phenol was a novolak type vinyl ether from the complete disappearance of the absorption by the hydroxyl group near ^-1 . In the obtained phenolic novolak vinyl ether, R in the formulas (1) and (2) is a hydrogen atom or-{(CH ₂ ) ₂ -O-}-CH =
CH ₂ , a hydrogen atom of the entire compound / − ／ (CH ₂ )
_2- O-｝-CH = CH ₂ = 8/92 (molar ratio).

Example 2 36 g of sodium hydroxide, 2-chloroethyl vinyl acetate
Synthesis was performed in the same manner as in Example 1 except that the amount was changed to 90 g.
125 g of product were obtained. The infrared absorption spectrum of this product
1610 cm for the spectrum^-1, 975cm -1
Absorption by Nyl group, 1200cm^-1To ether bond
Absorption was observed. The resulting phenolic novolak
The vinyl ether of formula (1) and (2)
Is a hydrogen atom or-｛(CH₂)₂-O-｝-CH = C
H₂ And a hydrogen atom of the entire compound /-｛(CH₂)
₂-O-｝-CH = CH₂= 25/75 (molar ratio)
Was.

Examples 3 to 6 The composition of the present invention was blended according to the blending composition shown in Table 1 (numerical values indicate parts by weight), dissolved and mixed. It was applied on various substrates (glass, polyethylene film, paper on which oil-based ink was printed) with a 04 bar coater, and was irradiated with ultraviolet rays at 900 mJ / cm ² to be cured. Then
The adhesion of the cured product was evaluated. In addition, the evaluation method of adhesiveness is as follows. Table 1 shows the evaluation results.

Adhesion A peeling test was performed on the surface of the cured film using a cellophane tape to evaluate the adhesion. When the substrate is a glass or a film, ：: the cured film does not peel off. When the substrate was paper, the evaluation was performed by ○: peeling between paper and oil-based ink.

[0029]

Table 1 Example 34 45 56 Compound of Example 1 30 20 30 40 TMPTVE ^{* 1} 10 50 30 40 4-HBVE ^{* 2} 30 20 RAPI-CURE CHVE ^{* 3} 30 RAPI-CURE DVE-2 ^{* 4} 30 Vectomer 2020 ^{* 5} 10 10 Mighty Ace G-125 ^{* 6} 50 20 Mighty Ace G-150 ^* 65 YS Polystar T-145 ^{* 6} 27 27 YP-90LL ^{* 6} 10 2.55 Sylwet L-7006 ^{* 7} 75 Silwet L-7001 ^{* 7} 0.5 0.5 PCI-204 ^{* 8} 6.3 2.5 6.3 6.3 UVI-6990 ^{* 9} 2 Adhesive glass ○ ○ ○ ○ Polyethylene film ○ ○ ○ ○ Paper ○ ○ ○ ○

Note * 1: Trifunctional vinyl ether manufactured by BASF * 2: Monofunctional vinyl ether manufactured by Nippon Carbide * 3: Bifunctional vinyl ether manufactured by ISP * 4: Bifunctional vinyl ether manufactured by ISP * 5: Allide- Vinyl ether oligomer * 6: Yasuhara Chemical Co., terpene resin * 7: Nippon Conical Co., Ltd., silicon surfactant * 8: Nippon Kayaku Co., Ltd., photo cationic polymerization initiator * 9: Union Carbide Co., Ltd. Photo cationic polymerization initiator

Example 7 A photosensitive resin composition was obtained by mixing 10 g of the phenol novolak type vinyl ether of the present invention obtained in Example 2, 90 g of methyl ethyl ketone and 0.504 g of PCI-204. The composition was spin-coated on a glass substrate to a thickness of 2 μm and prebaked on a hot plate at 80 ° C. for 30 minutes. Next, a negative film having a resist pattern was brought into close contact with the coating film, and irradiated with ultraviolet rays using an ultraviolet exposure apparatus (exposure amount: 500 mJ / cm ² ). In addition, 0.
When developed with a 24% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, a good pattern was obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 290/06 C08F 290/06 C08G 8/36 C08G 8/36 C09D 4/00 C09D 4/00

Claims (5)

[Claims] 1. A phenolic novolak type vinyl ether, which is represented by the formula (1): ## STR1 ## (Wherein R is a hydrogen atom or a general formula-式 (R ₁ ) _p −
O-｝ _q -CH = CH ₂ (R ₁ is a linear or branched alkylene group having 1 to 10 carbon atoms, p is 1 to 10, q
Represents an integer of 0 to 10, respectively. ) Represents a vinyl ether group. Further, the ratio of hydrogen atom / vinyl ether group is 0/100 to an average value of the whole molecule of the formula (1).
70/30 (molar ratio). ), Containing 30% by weight or more of a tetranuclear phenolic novolak type vinyl ether compound represented by the formula (2): (Wherein R represents the same meaning as in formula (1)), wherein the amount of the binuclear phenol novolak type vinyl ether compound represented by the formula (1) is 15% by weight or less. 2. A polymerizable composition comprising the compound according to claim 1, another vinyl ether compound and a polymerization initiator. 3. The polymerizable composition according to claim 2, which contains a resin component. 4. The polymerizable composition according to claim 2, further comprising a lubricity imparting agent. 5. The polymerizable composition for coating according to any one of claims 2, 3 and 4.