JPS6335608A - Production of curable resin composition having ethylenically unsaturated group - Google Patents

Abstract

PURPOSE:To produce the title composition having a relaxed shrinkage strain upon radiation curing and excellent flexibility, rigidity and adhesiveness, by reacting a specified polymer with a carboxylic acid anhydride and an epoxy monomer having an ethylenically unsaturated group. CONSTITUTION:A polymer (A) having 0.1-10 hydroxyl groups per 1,000 of MW in the molecule and having an MW >=5,000 (e.g., phenoxy resin) is reacted with part of a carboxylic acid anhydride (B) (e.g., succinic anhydride), and the free carboxyl groups formed in this reaction are reacted with the glycidyl groups of an epoxy monomer (C) having an ethylenically unsaturated group [e.g., glycidyl (meth)acrylate] or alternately, components B and C are added to component A, and the mixture is reacted at 80-150 deg.C in a nitrogen gas atmosphere in the presence of a catalyst (e.g., NaOH).

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a method for producing a curable resin composition having an ethylenically unsaturated group.

(Prior Art) Radiation-curable resin compositions have been researched in the fields of coatings for metals, plastics, etc., photosensitive resin plates, and the like. Especially in the paint field.

Durability, processing adhesion, heat resistance, weather resistance, and chemical resistance.

At present, a resin composition that satisfies the requirements for various physical properties such as water resistance, high-speed coating properties, and low-energy curing properties has not yet been completed.

That is, in order to improve curability, should a resin with a higher content of ethylenically unsaturated groups be used?

It is said that it is better to increase the amount of polymerizable diluent used.

However, in such systems, the cured coating film is generally brittle and has poor physical properties such as processing adhesion and durability.

Furthermore, the trade-off that curability cannot be ensured when emphasis is placed on physical properties has not been resolved.

In addition, generally used radiation-curable resins include a method in which a resin having an active hydroxyl group is reacted with an isocyanate compound having an ethylenically unsaturated group, or a method in which (meth)acrylic acid is subjected to an esterification reaction. However, when attempting to introduce a large amount of ethylenically unsaturated groups, the presence of diisocyanate compounds that exist as impurities in the former causes a crosslinking reaction, resulting in high viscosity and problems in paintability; In this case, the reaction must be carried out at a low temperature at which radical polymerization does not occur, and unreacted (meth)acrylic acid monomer must be removed, and odor also becomes a problem.

[Structure of the invention]

(Means for Solving the Problems) The present invention solves the above problems and uses a polymer (A) having a molecular weight of 5,000 or more having hydroxyl groups in 9 molecules, a carboxylic acid anhydride (B) and an epoxy monomer (C) having an ethylenically unsaturated group, in a method for producing a curable resin composition having an ethylenically unsaturated group, in which a carboxylic acid anhydride (B) is added to the polymer (A).
After pre-reacting a part of.

Alternatively, it relates to a production method characterized in that the carboxylic acid anhydride (B) and the epoxy monomer (C) are added and reacted without reacting.

In the present invention, the molecular weight is 5.0, which has hydroxyl groups in two molecules.
Examples of the polymer (A) of 00 or higher include acrylic polyols, saponified vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl acetate-(meth)hydroxyalkyl copolymers, cellulose resins, phenoxy resins, and polyvinyl acetal resins. , phenolic resins, partially saponified products of polyvinyl acetate, polyesters having hydroxyl groups, and the like. The molecular weight of these resins is 5.000
If it is less than that, the effect coating will become brittle and there will also be problems in adhesion. The polymer (A) has a molecular weight of 10.0
It is preferable to use 00 or more. As the upper limit of the molecular weight, it can be used as long as it can be dissolved in a solvent that does not participate in the reaction, and the solvent in this case may be a monomer having an ethylenically unsaturated group.

The number of hydroxyl groups is 0.1 to 10 per molecular weight 1,000.
, preferably 0.3 to 5.

In the present invention, the carboxylic anhydride (B) includes saturated or unsaturated aliphatic dicarboxylic anhydride, aromatic dicarboxylic anhydride, alicyclic dicarboxylic anhydride, etc. may be substituted with an unsaturated hydrocarbon group, a ring group, a halogen group, a heterocyclic group, or the like. Examples include maleic anhydride, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, itaconic anhydride, glutaric anhydride, succinic anhydride, methylhimic anhydride, tetrachlorophthalic anhydride, het's acid anhydride, etc. Also, trimellitic anhydride can be used.

In the present invention, examples of the epoxy monomer (C) having an ethylenically unsaturated group include glycidyl (meth)acrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexane motueboxide, 1.3
-butadiene monoepoxide, etc., and these are saturated or unsaturated hydrocarbon groups.

It may be substituted with an aryl group, a halogen group, a heterocyclic group, or the like.

In the production method according to the present invention, the hydroxyl groups in the polymer (A) and the acid anhydride in the carboxylic anhydride (B) react preferentially, and then the free carboxylic acid groups generated by this reaction and the epoxy monomer ( C) reacts with the glycidyl group. As is known per se, in this reaction, a secondary hydroxyl group is generated, this hydroxyl group reacts with the acid anhydride, and furthermore, the free carboxylic acid group generated by this reaction reacts with the glycidyl group, and so on. By adjusting the length of.

A desired number of ethylenically unsaturated groups can be introduced into the polymer (A) as branched chains. The resulting resin composition depends on the type of polymer (A), the number of hydroxyl groups in polymer (A), the type and amount of carboxylic anhydride (B) used, and the type and amount of epoxy monomer (C). can be designed. Furthermore, in the production method according to the present invention, ethylenically unsaturated groups are introduced into the graft chains of the polymer (A), so that while curability is imparted, the flexibility and rigidity that the polymer (A) originally has, Since adhesive properties are maintained even after curing, molecular design from a physical property perspective becomes easier.In particular, there are areas with dense crosslinking density and areas with sparse crosslinking density, which alleviates the shrinkage strain that conventionally tends to occur during radiation curing. It is possible to obtain a composition with characteristics such as:

In the present invention, the relationship between the number m of hydroxyl groups in the hydroxyl group-containing polymer (A), n moles of carboxylic acid anhydride (B), and 11 moles of epoxy monomer (C) is particularly fixed if n#6. Instead of 1, for example m≦nl=+1
In this case, some of the hydroxyl groups in the polymer (A) may remain unreacted.

In the production method of the present invention, in a nitrogen gas atmosphere.

One reaction is carried out at 80-150°C, preferably 100-120°C, using a known catalyst such as sodium hydroxide.

Potassium hydroxide, lithium chloride, triethylamine, tetra(n-butoxy)-titanium, N,N-dimethylbenzylamine, etc. can also be used.

Known radical polymerization inhibitors 2, such as hydroquinone,
It is preferable to use monomethoxyhydroquinone or the like.

Moreover, if the polymer (A) is solid, it is necessary to melt it and react with a solvent that does not participate in the two reactions.

The resin composition according to the present invention is diluted with an unsaturated solvent or a volatile solvent as necessary and applied to the target substrate, and in the case of a volatile solvent, the resin composition is evaporated and then irradiated with radiation. Let it harden. In the case of ultraviolet curing, a known sensitizer such as benzoin ethers such as benzoin methyl ether or benzophenones such as benzophenone is added. Electron beam.

When using ionizing radiation such as α-rays, β-rays, γ-rays, and X-rays, no special sensitizer is required.

In addition, the resin composition according to 9 the present invention may contain pigments,
Colorants such as dyes, surfactants, fillers, magnetic iron oxide,
Additives such as plasticizers are used as appropriate.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In the examples, 2 parts and % are respectively parts by weight and % by weight.
shows.

Example 1 A reactor equipped with a stirrer, a cooler, a thermometer, and a dropping funnel was purged with nitrogen gas, and then methyl isobutyl ketone 3
29 parts and 329 parts of cyclohexanone were charged, and while stirring, 154 parts of phenoxy resin (Bakelite PKHI+, trade name manufactured by Union Carbide) was gradually added and dissolved. Next, 13.5 parts of succinic anhydride was added and reacted at the same temperature, and the disappearance of the absorption peaks of the acid anhydride (1790 and 1B70c1m-1) was confirmed in the infrared spectrum, and then 13.5 parts of succinic anhydride and glycidyl were added. Gradually add 3 parts of methacrylate js, 0.04 part of hydroquinone and 0.11 part of N,N-dimethylbenzylamine, react at the same temperature for 200 hours, confirm that the acid value is 4 or less, and make one molecule. A resin (A) having an ethylenically unsaturated group of about 27 (gil) and a molecular weight of about 22,100 was obtained.

After mixing and melting 20 parts of a monomer having an ethylenically unsaturated group (Ester 14G for N, trade name manufactured by Shin Nakamura Chemical Co., Ltd.) in 100 parts of a solution of resin (A), 2 parts of the solid content were placed on a tin plate.
After coating the film so as to have a particle diameter of 0μ and volatilizing the volatile solvent, it was irradiated with an electron beam irradiation device CB15O-15-10 (Energy Science Co., Ltd.) at an acceleration voltage of 165KV and 3Mra.
It was irradiated and cured at d. The physical properties of the cured coating film are shown in Table 1.

Example 2 The same reactor as in Example 1 was replaced with nitrogen gas.

473 parts of methyl isobutyl ketone and 473 parts of cyclohexanone were charged, and while stirring, 200 parts of the same resin as in Example 1 (Bakelite PKIIH) was gradually added and dissolved. Next, 1048 parts of 1,2-cyclohexanedicarboxylic anhydride was added and reacted at the same temperature, and disappearance of the absorption peak of the acid anhydride was confirmed in the infrared spectrum, and then 49.2 parts of 1,2-cyclohexanedicarboxylic anhydride
Department.

55.4 parts of glycidyl methacrylate, 0.06 parts of hydroquinone and 0.0 parts of N,N-dimethylbenzylamine.
16 parts were gradually added and reacted at the same temperature for 15 hours to confirm that the acid value was 4 or less.
B) was obtained.

20 parts of a monomer having an ethylenically unsaturated group (Anilox 1200, trademark name of Toagosei Co., Ltd.) and 10 parts of Kayarad DPIIA (trade name of Nippon Kayaku Co., Ltd.) were mixed and melted in 280 parts of a solution of resin CB), and then carbon black ( 70 parts of MA-11 (manufactured by Mitsubishi Kasei) were added and dispersed in a sand mill with 100 parts of glass beads to make a black paint.
This coating material was applied onto a polyethylene terephthalate film having a thickness of 15 .mu.m so that the solid content was 5 .mu.m, and after the volatile solvent was evaporated, it was cured by electron beam irradiation in the same manner as in Example 1.

Example 3 84 parts of xylene, 56 parts of butyl acetate, and 300 parts of OH-containing acrylic resin (Acrydec-811. Trade name manufactured by Dainippon Ink Chemical Co., Ltd.) were mixed in advance with 1.8 parts of succinic anhydride in the same manner as in Example 1. React 1 then succinic anhydride 16
．． 2 parts, 38.3 parts of glycidyl methacrylate, 0.03 parts of hydroquinone and 0.001 parts of triethylamine.
1 part was gradually added and reacted at the same temperature for 22 hours until the acid value reached 5.
Confirm that the resin (C) has 18 ethylenically unsaturated groups in one molecule and has a molecular weight of approximately 19,500.
I got it.

After mixing and dissolving 15 parts of a monomer having an ethylenically unsaturated group (NK Ester NPC, trade name manufactured by Shin Nakamura Chemical Co., Ltd.) and 1 part of benzophenone in 87.5 parts of a solution of resin (C), the solid content was poured onto a tin plate. Paint it to be 25μ.

After evaporating the volatile solvent, place 10 cm below an 80 L'c+m ultraviolet light pump at l m/win,
It was cured by irradiating it twice at a line speed of .

Example 4 289.9 parts of methyl ethyl ketone, ) Luene 2B
9.9 parts of vinyl chloride/vinyl acetate copolymer resin and 200 parts of a partially saponified vinyl chloride/vinyl acetate copolymer resin (Vinyrite VAG II, trade name manufactured by Union Carbide) were charged, and anhydrous 1,2-cyclohexane dicarbonate was prepared in the same manner as in Example 1 while stirring. Add 8.4 parts of acid and react.9 Then anhydride 1.2-
16.8 parts of cyclohexanedicarboxylic acid, 23.2 parts of glycidyl methacrylate, 0.02 parts of hydroquinone and 0.12 parts of triethanolamine were gradually added and reacted at the same temperature for 25 hours to confirm that the acid value was 4 or less. After confirmation, a resin (D) having about 20 ethylenically unsaturated groups in one molecule and a molecular weight of about 31,000 was obtained.

Mix and dissolve 20 parts of a monomer having an ethylenically unsaturated group (Anilovx M-7100, trade name manufactured by Toagosei Co., Ltd.) and 5 parts of NK Ester A-TMPT, trade name manufactured by Shin Nakamura Chemical Co., Ltd.) in 25 parts of a solution of resin (D). Then, it was coated on a tin plate so that the solid content was 50 μm, and after the volatile solvent was evaporated, it was irradiated with an electron beam and cured in the same manner as in Example 1.

Comparative Example 1 289.9 parts of methyl ethyl ketone, 289.9 parts of toluene
and Vinylite VAG) 1200 parts, i
The mixture was dissolved while stirring, and 11.2 parts of acrylic acid and 0.06 part of P-)luenesulfonic acid were added thereto, and the mixture was reacted at 100° C. for 10 hours under a stream of air. The acid value was about 19, and about 40% of unreacted acrylic acid remained, resulting in a resin composition in which about 12 ethylenically unsaturated groups were introduced into one molecule. This resin composition had a strong odor from residual acrylic acid.

Comparative Example 1 150 parts of phenol resin (Bakelite CKl'12432. Trade name manufactured by Showa Union) was mixed with 1 part of methyl ethyl ketone.
Melt 28.3 parts of succinic anhydride and react with 112.5 parts of succinic anhydride at 80°C in the same manner as in Example 1. Then, 0.26 parts of triethanolamine was gradually added and reacted at the same temperature for 20 hours, and the acid value was confirmed to be less than 1O.
A resin (E) having ethylenically unsaturated groups and having a molecular weight of about 2,400 was obtained.

NK ester 14G 20 to 100 parts of resin (E) solution
The components were mixed and cured by electron beam irradiation in the same manner as in Example 1.

Comparative Example 2 100 parts of methyl ethyl ketone, 1000 parts of toluene and partially saponified vinyl chloride/vinyl acetate copolymer resin (
UCAR solution vinyl resin VYf! 200 parts of S, molecular weight 4°000, trade name manufactured by Union Carbide Co., Ltd.) were added, and anhydrous 1,
23.1 parts of 2-cyclohexanedicarboxylic acid was added and reacted.9 Then, 53.9 parts of 1,2-cyclohexanedicarboxylic acid anhydride, 71.0 parts of glycidyl methacrylate, 0.07 parts of hydroquinone and 0.18 parts of triethanolamine were added. was gradually added and reacted at the same temperature for 25 hours, and it was confirmed that the acid value was 4 or less.
A resin (F) having 3 ethylenically unsaturated groups and a molecular weight of about 31,000 was obtained.

A cured coating film was obtained in the same manner as in Example 4 using resin (F).

Table 1 Example MEK Pencil Adhesion Bending Glossiness Rubbing Hardness Processing 1100 times or more 3 H100/100 0 02 〃 -
〃 -0 3〃4H〃 ○ 0 4 〃 4H〃 ○ ○Comparative example 1 〃
3HO/100xx - Comparative Example 2 〃3H50
/100 xx - Note) MEK rubbing: Number of times the surface is rubbed with a cloth impregnated with methyl ethyl ketone until the object to be coated is exposed Pencil hardness; Mitsubishi Pencil Uni adhesion; - Number remaining after peeling off the adhesive tape after cutting (IOX 10) Bending processability; LT bending gloss; visual inspection

Claims (1)

[Claims] 1. An ethylenic polymer in which a polymer (A) with a molecular weight of 5,000 or more having a hydroxyl group in the molecule, a carboxylic acid anhydride (B), and an epoxy monomer (C) having an ethylenically unsaturated group are reacted. In the method for producing a curable resin composition having an unsaturated group, a carboxylic anhydride (B) is added to the polymer (A).
) A production method characterized in that after reacting a portion of (B) in advance or without reacting, carboxylic acid anhydride (B) and epoxy monomer (C) are added and reacted. 2. The production method according to claim 1, characterized in that a polymer (A) having a hydroxyl group in the molecule and having a molecular weight of 10,000 or more is used.