JPH01213347A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide the above composition composed of a plurality of specific (meth)acrylic acid esters, having improved stability of monomer and cured product and excellent water-resistance and electrical properties and useful as a paint, etc., in a field to use a UV curing means. CONSTITUTION:The objective composition is composed of (A) a (meth)acrylic acid ester produced by carrying out addition esterification reaction of (i) (meth) acrylic acid and (ii) a novolak phenolic resin of formula [R1 is H, CH2OH or CH2-O-(CH2-CHR4-O)r-H (r is 1-5; R4 is H or CH3); R2 is CH2 or CH2OCH2: R3 is alkyl(substituted)phenyl; m and n are 1-5; p is 0-2; q is 1-3] at a COOH /OH ratio of >=1.0, neutralizing the reaction liquid with an alkaline agent after the completion of the reaction and washing the product with water and (B) a (meth)acrylic acid ester containing one or more (meth)acryloyl groups in one molecule and having a molecular weight of <=1,000.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to irradiation with ultraviolet rays (hereinafter referred to as UV), electron beams (hereinafter referred to as EB), etc., or in the presence of a radical polymerization initiator at room temperature or heating. Acrylic acid or/and methacrylic acid ester (hereinafter referred to as
(referred to as meth)acrylic acid ester) type curable resin composition, the curable resin composition is suitable for coatings,
It provides curable resins that can be used in various industrial fields as inks, adhesives, sealants, etc.

[Conventional technology]

Conventionally, (meth)acrylic acid esters of polymer polyols that do not leave hydroxyl groups in the molecule structure have been provided for the purpose of developing coating materials that are quick-drying and have excellent emulsification resistance against dampening water (Japanese Patent Publication No. 1983-1999). No. 5625).

According to the examples described in the above publication, the charging ratio C00H/OH of carboxyl groups and hydroxyl groups is lower than 1 in all examples, that is, the esterification reaction is carried out with excess alcohol, and furthermore, the reaction liquid is not subjected to any treatment process. without going through (meta)
Acrylic acid ester is obtained.

[Problem that the invention seeks to solve]

The (meth)acrylic ester thus obtained.

i) A hydroxyl group is always included in the molecule.

(2) The (meth)acrylic acid ester contains unreacted (meth)acrylic acid and esterification catalysts such as sulfuric acid and ρ-toluenesulfonic acid.

Due to these two points, not only is there room for improvement in water resistance, but also the stability of the obtained (meth)acrylic ester is very poor. In the case of ii), in the monomer, turbidity occurs due to precipitation of insoluble matter such as crystals,
Hydrolysis due to moisture absorption during storage and cured products may cause various problems such as loss of gloss, whitening, swelling, peeling, and especially when the base material is metal, rusting may occur. or,
When N-vinylpyrrolidone, (meth)acrylic acid ester of an amino group-containing alcohol, urethane (meth)acrylate, etc. coexist, various problems such as hydrolysis and thickening occur.

[Means for solving problems]

The present invention, as a means to solve the above-mentioned conventional problems, provides a curable resin that can be cured by a curing means such as UV, EB, or thermal energy as a result of intensive research, and the curable resin composition. consists of the [A] component and the (Bl component), in the alkylene oxide adduct esterification reaction of the novolac type phenol resin represented by the following formula (I) with the [A] acid component acrylic acid or/and methacrylic acid,
The charging ratio of carboxyl groups and hydroxyl groups (COOH/OH
acrylic acid or/and methacrylic acid ester obtained by carrying out the reaction at a ratio (ratio) of 1.0 or more, neutralizing the reaction solution with an alkaline agent after the reaction, and further washing with water, formula (1) in which R1 is -H, -CM, OH.

-CH, -〇+CH, -CHR4-〇　+F-H.

However, r is a positive number of 1 to 5, and R8 is -CH, -.

-CH, OCH, -1R1 is an alkyl group, 7) Il-substituted phenyl group, R4 is -H, -CH, m is a positive number from 1 to 5, n is 1. A positive number of ~5, p is a positive number of 0 to 2, q
represents a positive number from 1 to 3.

[B] Component contains one or more acryloyl group or/and methacryloyl group in one molecule, and has a molecular weight of 1000
The following acrylic acid and/or methacrylic acid esters.

(1) [A] Component The component [A] is expressed by the following formula (denoted by N.

formula([) In the formula, R4 is -H, -CH, OH or -CH yo 10÷CH, -CHR4-0+H.

However, r is a positive number of 1 to 5, and R1 is -CH, -.

-CH, OCH, -, R3 is an alkyl group, a phenyl group,
t-alkyl-substituted phenyl group, R4 is -H1-cn, m is a positive number of 1 to 5, n is a positive number of 1 to 5, p is a positive number of O to 2,
q represents a positive number from 1 to 3.

(1) Novolac-type phenolic resin The novolak-type phenolic resin used in the present invention is obtained by a condensation reaction of a phenol represented by formula 1'' and formaldehyde.

Formula (n) where R3 and p are the same as in formula (1), but q' is 1
It is a positive number of ~5.

The novolak type phenol resin obtained by the above condensation reaction is represented by the following formula (nl).

In the formula, Ryo represents -H2 or -CH,OH, and the others represent the formula (
Same as [).

Exemplary compounds of the phenols represented by formula (II) include phenol, cresol, ethylphenol, propylphenol, and butylphenol.

Examples include hexylphenol, octylphenol, nonylphenol, phenylphenol, and cumylphenol. The condensation of these phenols and formaldehyde is usually carried out under an acidic catalyst. m in formula (m) is preferably in the range of 1 to 5; if it is 6 or more, the solubility of the novolac type phenol resin in organic solvents decreases or it becomes insoluble. This is not preferable because the alkylene oxide addition reaction and the esterification reaction with (meth)acrylic acid are substantially impossible.

(2) Alkylene oxide addition reaction The alkylene oxide addition reaction to the above-mentioned novolac type phenolic resin is carried out under the catalyst of an alkaline compound such as sodium hydroxide at 80°C to 150°C and normal pressure to about 1.
The process is carried out under a pressure of 0 kg/aJG, and the alkylene oxides used are generally ethylene oxide and propylene oxide, which are easily available industrially.
n in 13 represents the number of moles of alkylene oxide added per phenolic hydroxyl group, and n is preferably 1 to 5. As n increases, hydrophilicity becomes stronger, and when it is 6 or more, the number of moles of alkylene oxide added per phenolic hydroxyl group increases. Neutralization of the esterification reaction solution and emulsification during washing with water make liquid-liquid separation impossible. In addition, the above range is preferable since the mechanical strength and heat resistance of the obtained (meth)acrylic acid ester cured product may be reduced.

(3) Esterification reaction The charging ratio of (meth)acrylic acid and alkylene oxide adduct of novolac type phenol resin during the esterification reaction is expressed as the ratio of total carboxyl groups to total hydroxyl groups, C00H/OH ratio. /OH ratio>1.
0 is preferable, and 1.1 to 1.5 is more preferable in consideration of economic efficiency. On the other hand, C00H/OH<
1. If the esterification reaction is carried out in O, that is, a system with an excess of hydroxyl groups, an acrylate having a hydroxyl group at the end is produced, and liquid-liquid separation is likely to become impossible due to emulsification during neutralization of the reaction solution and washing with water, and the esterification reaction Michael addition reaction, in which a hydroxyl group is added to the double bond of (meth)acrylic acid, sometimes occurs as a side reaction, but this reaction is more likely to occur in a system with an excess of hydroxyl groups, resulting in a decrease in the double bond concentration and an increase in the product This is undesirable because it causes an increase in the molecular weight of the reaction solution, which also affects the difficulty of liquid-liquid separation during reaction solution washing.

The esterification reaction in the present invention is a dehydration esterification reaction of an alkylene oxide adduct of (meth)acrylic acid and a novolac type phenol resin.

As the reaction catalyst, sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, ion exchange resin having a sulfonic acid group, etc. are used. Examples of the polymerization inhibitor include phenols such as hydroquinone and hydroquinone monomethyl ether, quinones such as benzoquinone, phenothiazine, and copper salts.

Examples of azeotropic dehydrating agents that also serve as solvents during the reaction include n-hexane, cyclohexane, benzene, toluene, xylene,
Examples include trichlorethylene and tetrachlorethylene.

(4) Neutralization and water washing of the reaction solution After the reaction, the reaction solution is washed with an alkaline agent to remove unreacted acidic components such as (meth)acrylic acid and esterification catalyst. The agent can be neutralized using an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, etc., and then subjected to liquid-liquid separation or oxidized. It is also possible to adsorb it on a solid base such as magnesium and filter it, or to treat it with an ion exchange resin. What kind of alkaline agent do you use?

In the case of an alkaline aqueous solution, the amount is equivalent to or more than the acid value determined by neutralization titration of the reaction solution, and even considering economic efficiency, it is 1.
1 to 1.5 times equivalent is sufficient. In the case of solid bases and ion exchange resins, it is necessary to set appropriate conditions because they vary depending on operating conditions such as temperature, contact time, and adsorption capacity. After neutralization, it is washed again with an aqueous solution of a neutral salt. Examples of water detergents used at this time include sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, Although an aqueous solution of ammonium sulfate or the like is used, it is also possible to use water in which no of these inorganic salts is dissolved. Add the above-mentioned polymerization inhibitor used during the esterification reaction to the washing solution after neutralization and washing with water, and distill off the reaction solvent under reduced pressure (desolventization).
(meth)acrylic acid ester [A] is obtained. At this time, it is also possible to remove the solvent by adding the Bl component (of the present invention) to the washing solution after neutralization and washing with water.Others, [A], CB)
There are methods such as mixing the respective reaction solutions, neutralizing and washing with water as described above, and removing the solvent [A] and [B] separately removing the solvent and then mixing them. Either method is possible.

(2) CB) Component The (meth)acrylate of the novolak type phenolic resin alkylene oxide adduct of the component [A] above has a high viscosity, so it easily gels when the solvent is removed after washing the reaction solution.
It is necessary to dilute it with the low-viscosity (meth)acrylate component (Bl), which is the other component of the present invention. This is also preferable from a work point of view.

Contains one or more (meth)acryloyl groups in one molecule,
Exemplary compounds of the [B] acid component which are (meth)acrylic esters with a molecular weight of 1000 or less include neopentyl glycol, 1,4 butanediol, 1.6 hexanediol, trimethylolethane, trimethylolpropane, and pentaerythritol. , polyols such as ditrimethylolpropane and dipentaerythritol, monofunctional alcohols such as butanol, hexanol, and octatool, and their fullylene oxide adducts, (meth)acrylics of alkylene oxide adducts of bisphenol A, phenol, and alkylphenols. Examples include acid esters.

The molecular weight of component [B] is preferably 1000 or less.

More preferably, 200 or more and 800 or less,
This is because when the molecular weight exceeds 1ooo, its own viscosity increases and dilution hardening decreases.If the molecular weight is too low, the viscosity is low, but the vapor pressure is high.
Strong odor, UV.

In the case of EB, environmental measures 1, such as a decrease in curing speed,
This is not very desirable in terms of workability.

It is also possible to use a mixture of two or more types of this [B] component. In particular, for applications that require heat resistance, polyfunctional (
Meta) acrylate will be awarded.

Next, the present invention will be explained in more detail by showing examples, reference examples, and comparative examples, but the present invention is not limited to these examples.

[Examples, reference examples and comparative examples]

Reference Example 1 (Production of alkylene oxide adduct of novolac type phenolic resin) In a flask equipped with a stirrer, a dropping funnel, a condenser, and a thermometer, phenol novolac resin Barkum TD-2131 manufactured by Dainippon Ink Chemical (average degree of condensation formula ( m in 1) = 3.2) 125g, sodium hydroxide 1.25
g, toluene/methyl isobutyl ketone (weight ratio = 2
/1) Charge 350 g of mixed solvent, and add 75 g of propylene oxide through the dropping funnel while refluxing at 110°C.
It was added dropwise in 0 minutes and reacted for 300 hours. Furthermore, 15 g of propylene oxide was added dropwise over 15 minutes and reacted for 15 hours. 2 g of 96% sulfuric acid was added to neutralize the sodium hydroxide and concentrated, resulting in a non-volatile content of 46% and a hydroxyl value of 16 in terms of solid content.
8 g/eq (n=1.05) of resin was obtained.

Reference Example 2 (Production of alkylene oxide adduct of novolak type phenol resin) Nonylphenol novolak resin Shonol CRM-0909 (m = 1, 5) 192 manufactured by Showa Kobunshi Co., Ltd.
The reaction was carried out in the same manner as in Reference Example 1 using 1.9 g of sodium hydroxide, 350 g of toluene/methyl isobutyl ketone (weight ratio = 271), and 65 g of propylene oxide, resulting in a nonvolatile content of 46%.

Hydroxyl value in terms of solid content: 301 g/eq (n = 1
．． Resin 2) was obtained.

Reference Example 3 (Production of alkylene oxide adduct of novolak type phenol resin) Showa polymer layer Cresol novolac resin Showol CRG-951 (m=2.3) 134 g, sodium hydroxide 1.3 g, toluene/methyl isobutyl ketone A reaction was carried out in the same manner as in Reference Example 1 using 350 g (weight ratio = 2/1) and 85 g of propylene oxide, resulting in a non-volatile content of 57% and a hydroxyl value of 204 g/eq (n
= 1.45) was obtained.

Example 1 (Preparation of curable resin composition fA) In a reactor equipped with a stirrer, a thermometer, an air blowing pipe, and a water separator, an ethylene oxide adduct of nonylphenol novolac resin (
In formula (I), m=2, n=5. Non-volatile content 100%, hydroxyl value 449g/eq) 880g (2 equivalents of hydroxyl group), acrylic acid 172.8 (2.4 mol), p-toluenesulfonic acid 21g hydroquinone monomethyl ether (
(hereinafter referred to as MQ) 1.04 g, toluene 1040 g
The ratio of carbosyl groups to hydroxyl groups at this time was C00H/OH=1.2.

Air was blown into the reactor at a rate of 50 sfl/min, and heating was started with stirring. When the liquid temperature reached 107°C, water produced by the reaction began to distill out as an azeotrope with toluene. The azeotropic mixture was cooled and separated into a toluene layer and an aqueous layer, the toluene layer was returned to the reactor, and the aqueous layer was wiped out of the system. 0 As the reaction progresses, the liquid temperature rises.
After an hour, the liquid temperature became 115°C and 37.5 Q of water was distilled out (dehydration rate 104%).The reaction liquid was then cooled and [A
] Reaction solution containing components with an acid value of 10.3-gKOH/g 20
47g was obtained. Add this reaction solution to 180 g of a 10% aqueous sodium hydroxide solution (1.2 times equivalent to the acid value of the reaction solution).
The solution was neutralized with water, allowed to stand for 2 hours, and the separated aqueous layer was wiped off.

The neutralized organic layer was washed with 500 g of a 10% aqueous ammonium sulfate solution, left to stand for 2 hours, and the separated aqueous layer was wiped off. The organic layer washed with water contains [A] component, and the organic layer contains [B].
] 300 g of trimethylolpropane triacrylate and 5 g of MQo were added as components, and the reaction solvent was distilled off by vacuum distillation at a bath temperature of 70° C. to obtain 1150 g of a curable resin composition. The obtained curable resin composition was a brown liquid, had a viscosity of 730 cp/25°C, an acid value of 0.09 gKOH/g, and a residual solvent of 0.53 wt%.

Examples 2 to 5 Curable resin compositions shown in Table 1 were obtained in the same manner as in Example 1.

Comparative Example 1 (comparison of [A] component) 880 g of ethylene oxide adduct of the nonylphenol novolac resin used in Example 1 (2 equivalents of hydroxyl groups), 126 g of acrylic acid (1.75 mol), p-toluene Sulfonic acid 20.2g, MQl, 01g, toluene 101
An esterification reaction was carried out in the same manner as in Example 1 using 0 g as the raw material. At this time, the charging ratio of carboxyl groups and hydroxyl groups is C00H/OH=0.875, 0 reaction solution is 1
977 g was obtained, the acid value of which was 3.9+ag KOH/
It was g.

This reaction solution was mixed with 10% sodium hydroxide aqueous solution 66.0
Although the solution was washed with 1.2 times the equivalent of the acid value of the reaction solution, the entire solution remained in an emulsified state and liquid-liquid separation was impossible even after it was allowed to stand overnight (16 hours). Since static separation was not possible, centrifugation was performed for 10 minutes at a centrifugal force of approximately 5000 G to forcibly separate the aqueous layer. A portion of the organic layer was taken into a test tube and a small amount of 10% sodium sulfate aqueous solution was added to wash it, but it became emulsified as in the case of neutralization.
The following process was discontinued because liquid-liquid separation was not possible.

The acrylic ester for this [A] component is C00
Since the esterification reaction was carried out at an H/OH ratio of 1.0 or less, liquid-liquid separation during neutralization of the reaction solution and washing with water was extremely poor. It is also believed that the product has a high molecular weight due to the Michael addition reaction.

Comparative Example 2 (Comparison of curable resin compositions) An esterification reaction was carried out in the same manner as in Example 1, and after the reaction was completed, neutralization and water washing were not carried out, and 300 g of trimethylolpropane triacrylate, MQo, Immediately after adding 5 g, the reaction solvent was distilled off under reduced pressure at a bath temperature of 70°C to obtain 1314 g of acrylate corresponding to the curable resin composition of the present invention. This acrylate is a dark brown liquid with a viscosity of 713 centipoise (at 25°C) and an acid value of 13.
．． It was 7 mgKOH/g, and the residual solvent was 0.46%.

Example 6 (chloride spray test) 3 parts of Irgacure 651 (trade name, manufactured by Ciba Geigy) was added as a photoinitiator to 100 parts of the curable resin composition of Examples 1 to 5 and Comparative Example 2, and mixed well. , melted, and coated on a cold rolled steel plate using a bar coater #10. They were irradiated with ultraviolet rays and cured by passing them through an ozone-type high-pressure mercury lamp with an output of 80 W/I at a conveyor speed of 10 m/min, which was equipped with a reflector to condense the light onto the conveyor. Next, the periphery of the test piece was coated with paraffin wax, and two intersecting diagonal lines reaching the fabric of the test piece were drawn with the tip of a cutter knife, and this was used as a test piece for the salt spray test. JIS
According to K-5400, this test piece was used to perform a salt water spray test by spraying a 5% aqueous sodium chloride solution at 35° C. for 24 hours. The results are shown in Table 2.

24th IE Example 7 (Storage Stability) 10 g of the (meth)acrylic esters of Examples 1 to 5 and Comparative Example 2 were weighed into a 18 mm diameter test tube.

Storage stability was evaluated by immersing the sample in an oil bath maintained at 90°C to force gelation. The results are shown in Table 3.

Table 3 Example 8 1% of the above-mentioned Irgacure 651 was dissolved in the curable resin compositions of Examples 1 to 5 and Comparative Example 2.

A sample was prepared by pouring this composition onto a polyester film with a 1 m thick rubber frame attached thereto so as not to create air bubbles, covering it with a polyester film, and fixing it between transparent glasses from above and below. This sample was irradiated with ultraviolet rays for 3 minutes on each of the front and back sides under a high-pressure mercury lamp (Ushio Electric Co., Ltd., ozone-less parallel light type) with an output of 60 W/Ql at a distance of 2 oal I. Next, a glass plate,
The polyester film was removed, and the curing operation was completed by irradiating each front and back for 3 minutes to produce a sheet of 1 w x 50 tm x 50 wn. JISK-7 using this sheet
The water absorption rate was measured according to 209 (Test method for water absorption rate and boiling water absorption rate of plastics). Conclusion [Effects of the Invention] The curable resin composition according to the present invention, after the esterification reaction,
Since the slightly acidic esterification catalyst and unreacted (meth)acrylic acid are removed by neutralizing the reaction solution and washing with water, the stability of the monomer and cured product is greatly improved. Furthermore, since the resin does not have a hydroxyl group at the end, it is expected to improve the water resistance, electrical properties, etc. of the resin.

That is, according to Table 2, the curable resin compositions of Examples 1 to 5 did not generate rust along the line of the cutter knife for a distance of 5 m or less, whereas in Comparative Example 2, which was not neutralized or washed with water, The occurrence of rust was 15a++ or more, and according to Table 3, Example 1
The curable resin compositions of Examples 1 to 5 did not gel for more than 8 hours, but Comparative Example 2 gelled within 4 hours, and according to Table 4, the curable resin compositions of Examples 1 to 5 The water absorption rate is much lower than that of Comparative Example 2.

The curable resin composition according to the present invention uses UV as a curing means.
, paint in fields using EB or thermal energy,
The award is given to inks, adhesives, potting agents, sealants, etc.

Patent applicant: Toagosei Kagaku Kogyo Co., Ltd. Representative Tadao Usami Name: Curable Resin Composition 3, Relationship with the Amendment Case Patent Applicant Address: Mr. 1-14-1 Nishi-Shinbashi, Minato-ku, Tokyo
Name (303) Toagosei Kagaku Kogyo Co., Ltd. Representative Director Takashi Komori 4, Agent 467 Address 32-5 Tsukimigaoka, Yatomi-cho, Mizuho-ku, Nagoya City Date of amendment order Vol. 8 Contents of amendment 1 Page 6, line 9 [[A] Acid component is represented by the following formula [1]. ” [
[A] In the esterification reaction of the acid component acrylic acid or/and methacrylic acid and the alkylene oxide adduct of the novolac type phenol resin represented by the following formula [1], the charging ratio of carboxyl groups and hydroxyl groups (COOH/OH ratio) Acrylic acid or/and methacrylic acid ester is obtained by carrying out a reaction at a temperature of 1.0 or higher, neutralizing the reaction solution with an alkaline agent after one reaction, and washing with water. ” he corrected.

2. Page 12, line 14 r [A], [B] Mix the respective reaction solutions, and amend the above ``r'' to ``After mixing the respective reaction solutions [A] and [B], read the above.'' do.

3, page 12, line 15 [Neutralize with water and remove solvent [A], [B] J] [Neutralize with water and remove solvent. Or correct it as [A], [B]J.

4, page 14, line 2 The phrase "dilution hardening" is corrected to "dilution effect."

5, page 16, lines 17 to 18, rp-toluenesulfonic acid 21g hydroquinone methyl ether” was replaced with “p-toluenesulfonic acid 21g”.
1 g, hydroquinone monomethyl ether.”

6. In the first line from the bottom of page 16, the phrase "carbosyl group" is corrected to read "r carboxyl group."

7. In the 10th line from the bottom of page 26, the phrase "weakly acidic esterification catalyst" is corrected to "strongly acidic esterification catalyst."

that's all

Claims (1)

[Scope of Claims] A curable resin composition comprising component [A] and component [B], wherein the component [A] is acrylic acid or/and methacrylic acid and a novolac type represented by the following formula [I]. In the alkylene oxide adduct esterification reaction of phenolic resin, the charging ratio of carboxyl groups and hydroxyl groups (COOH/
It is an acrylic acid or/and methacrylic acid ester obtained by carrying out the reaction at a (OH ratio) of 1.0 or more, neutralizing the reaction solution with an alkaline agent after the reaction, and washing with water.Formula [I] ▲Math. , chemical formulas, tables, etc. ▼ In the formula, R_1 is -H, -CH_2OH, ▲ There are numerical formulas, chemical formulas, tables, etc. ▼, where r is a positive number from 1 to 5, and R_2 is -CH_2-, -C
H_2OCH_2-, R_3 is an alkyl group, alkyl-substituted phenyl group, R_4 is -H, -CH_3, m is 1 to 5
, n is a positive number from 1 to 5, p is a positive number from 0 to 2, q is 1
Represents a positive number between ~3. The component [B] contains one or more acryloyl groups and/or methacryloyl groups in one molecule, and has a molecular weight of 100
Curable resin composition characterized by containing 0 or less acrylic acid or/and methacrylic acid ester