JP2000063327A - Method for producing reactive hemiacetal ester, reactive hemiacetal ester produced by the method, and cured product thereof - Google Patents

Abstract

(57) Abstract: A method for easily producing a low-viscosity and highly reactive reactive hemiacetal ester, and a film-forming material such as paint and ink, or a sealant, a molding agent, an adhesive, Provide a reactive hemiacetal and a cured product thereof that can be used as a resin material such as an adhesive. A method for producing a reactive hemiacetal ester, which comprises reacting a (meth) acrylic compound having a carboxyl group with a vinyl ether compound (C) having two or more vinyl ether groups, is produced by the method. A reactive hemiacetal ester having a (meth) acryloyl group, and a cured product obtained by irradiating the reactive hemiacetal ester with an active energy ray.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a film forming material such as paint or ink, or a sealant, which has excellent fluidity and curability.
Reactive hemiacetal ester that can be used in a wide range of fields as a raw material for molding agents, adhesives, pressure-sensitive adhesives, etc. and can obtain a cured product by heat or active energy rays, a method for producing the same, and a cured product thereof Is.

[0002]

2. Description of the Related Art Acrylic compounds are used in a wide variety of fields such as raw materials for various curable resin products or cross-linking agents when synthesizing resin emulsions for paints, inks and adhesives. In recent years, in particular, due to the growing interest in the global environment and working environment, the tendency toward solvent-free active energy ray curing systems and water systems has become remarkable. Among them, the active energy ray curing system triggered by active energy rays such as ultraviolet rays and electron beams is a solvent-free one, and the drying time is much shorter than that of the solvent type. Is recognized. However, since solventless resin products have low molecular weight reactive diluents as their main components,
It is a reality that the expansion of the market is limited due to problems such as curing shrinkage, substrate adhesion and abrasion resistance. In order to solve this problem, various studies have been made so far.

Part of this is the development of various reactive compounds and the development of water-based active energy ray-curable materials.
In particular, regarding the former development, many kinds of reactive compounds centering on urethane acrylic compounds, epoxy acrylic compounds, and ester acrylic compounds have been produced by material manufacturers. However, conventional reactive compounds have been forced to undergo a high-temperature, long-time manufacturing process. Further, also in terms of physical properties, the epoxy acrylic compound excellent in adhesiveness has high viscosity due to the presence of a hydroxyl group, low water resistance, and the urethane acrylic compound excellent in coating film physical properties such as abrasion resistance and mechanical strength is However, due to its extremely high viscosity, there are some formulation problems, such as in the case of applications requiring coating processability, it is not possible to formulate the composition until its performance is fully utilized.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for simply producing a reactive hemiacetal ester having low viscosity and high reactivity. Further, the present invention is a coating, a film forming material such as ink, or a sealing agent, a molding agent,
An object of the present invention is to provide a reactive hemiacetal that can be used as a resin material such as an adhesive and a pressure-sensitive adhesive and a cured product thereof.

[0005]

Means for Solving the Problems The present inventors have utilized a reaction between a vinyl ether group and a carboxyl group to contain a polyfunctional vinyl ether compound and a carboxyl group-containing (meth) group.
When reacted with an acrylic compound, unlike the conventional synthesis of epoxy acrylic compounds and urethane acrylic compounds, it has a low viscosity reactivity under extremely mild conditions and a similar molecular weight. The inventors have found that a hemiacetal ester can be obtained, and completed the present invention. Furthermore, the present inventors have found that when the obtained reactive hemiacetal ester is cured with active energy rays such as ultraviolet rays and electron rays, it has excellent curability and coating film performance.

The reaction between the vinyl ether group and the carboxyl group is completed within a few hours at a temperature of about 25 to 50 ° C. in the presence of a phosphoric acid type catalyst such as an alkyl phosphoric acid compound, and the hemiacetal ester can be obtained in high yield. It is a known reaction that can be obtained (Chemical Abstract, 43, 6576d, 1949), and has recently been used to block a highly reactive carboxyl group. The block carboxylic acid thus obtained is being widely used mainly in the coating field as a one-pack type thermosetting resin composition mixed with an epoxy compound (Y.Nakane, M. Ishidoya, Progress in Organic Coati
ongs 31,113-120, 1997.EP296507, JP 4-68009, JP
4-72324).

That is, the present invention relates to a method for producing a reactive hemiacetal ester by reacting a (meth) acrylic compound having a carboxyl group with a vinyl ether compound (C) having two or more vinyl ether groups. Further, the present invention is the above-mentioned reactivity, wherein the (meth) acrylic compound having a carboxyl group is a half ester obtained by reacting a cyclic acid anhydride (A) with a (meth) acrylate compound (B) having a hydroxyl group. The present invention relates to a method for producing a hemiacetal ester.

The present invention also relates to a reactive hemiacetal ester represented by the following general formula (1) produced by the above method.

[Chemical 5] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a direct bond, an alkylene group having 2 to 15 carbon atoms, or an organic residue represented by the following general formula (2-1) or (2-2), R ³
Is an organic residue represented by the following general formulas (3-1) to (3-7), x1 is 1 or 2, x2 is an integer of 1 to 3, and x3 is 1.
Is an integer of 4 and x4 is an integer of 1 to 6, respectively. )

[0009]

[Chemical 6] (In the formula, R ⁴ is an organic residue selected from the following general formulas (a) to (g), p is an integer of 2 to 15, q is an integer of 2 to 15,
m is an integer of 1 to 20, n is an integer of 0 to 10, and r is 1 to 1.
An integer of 0 is shown. )

[0010]

[Chemical 7] (In the formula, R ⁵ and R ^{5 ′} represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms.)

[0011]

[Chemical 8] (In the formula, x1 is 1 or 2, x2 is an integer of 1 to 3, x3
Is an integer of 1 to 4, x4 is an integer of 1 to 6, y2 is an integer of 0 to 2, y3 is an integer of 0 to 3, y4 is an integer of 0 to 5, and s is 2
Each represents an integer of -25. Further, the present invention relates to a cured product obtained by irradiating the reactive hemiacetal ester with an active energy ray.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The (meth) acrylic compound having a carboxyl group used in the production method of the present invention is a compound having a carboxyl group and a (meth) acryloyl group, for example, β- (meth) phthalate. Acryloxyethyl monoester, isophthalic acid β- (meth) acryloxyethyl monoester, terephthalic acid β- (meth) acryloxyethyl monoester, succinic acid β- (meth)
Examples thereof include acryloxyethyl monoester, β-carboxyethyl (meth) acrylate, acrylic acid, methacrylic acid and the like.

The (meth) acrylic compound having a carboxyl group is prepared by adding the cyclic acid anhydride (A) and the (meth) acrylate compound having a hydroxyl group (B), if necessary, in the presence of a tertiary amine catalyst. It can also be obtained by reacting with a known method. The cyclic acid anhydride (A) is a cyclic acid anhydride of dicarboxylic acid, and includes, for example, oxalic acid, malonic acid,
Succinic acid, alkyl or alkenyl succinic acid, cyclic acid anhydride of aliphatic dicarboxylic acid such as glutaric acid, maleic acid, cyclohexyldicarboxylic acid anhydride, cyclohexenyldicarboxylic acid anhydride, methylcyclohexyldicarboxylic acid anhydride, bicyclohexyldicarboxylic acid Examples thereof include acid anhydrides, cyclic acid anhydrides of alicyclic dicarboxylic acids such as bicyclohexenyl dicarboxylic acid anhydride, and aromatic cyclic acid anhydrides such as phthalic anhydride.

The (meth) acrylate compound (B) having a hydroxyl group is a (meth) acrylate compound having a hydroxyl group and a (meth) acryloyl group, and a compound represented by the following general formula (4) can be used. .

[Chemical 9] (In the formula, R ¹ is a hydrogen atom or a methyl group, and p is 2 to 15
Of n, q is an integer of 1 to 15, m is an integer of 1 to 20, n
Represents an integer of 0 to 10, respectively. )

The compound represented by the general formula (4) is roughly classified into a hydroxyalkyl (meth) acrylate compound, an alkylene glycol mono (meth) acrylate compound, and a lactone-modified (meth) acrylate compound. Specific examples of the hydroxyalkyl (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 2-
Examples thereof include hydroxybutyl (meth) acrylate.

Further, alkylene glycol mono (meth)
Specific examples of the acrylate compound include diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, Examples include dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, and polytetramethylene glycol mono (meth) acrylate.

Further, specific examples of the lactone-modified (meth) acrylate compound include 2- (meth) acryloyloxyethyl hydrogencaprolactonate, 2-
(Meth) acryloyloxyethyl hydrogen dicaprolactonate, 2- (meth) acryloyloxyethyl hydrogen poly (polymerization degree 3-5) caprolactonate, 2- (meth) acryloyloxyethyl-2-
Hydroxy-6 hesanolactonate and the like can be mentioned.

Further, as the (meth) acrylate compound (B) having a hydroxyl group, in addition to the compound represented by the general formula (4), 2- (meth) acryloyloxyethyl 2
-Hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylene Oxide-modified pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, ethylene oxide-modified trimethylolpropane mono (meth) acrylate, etc. can be used.

The vinyl ether compound used in the production method of the present invention is a compound having two or more vinyl ether groups, and a divinyl ether compound or a trifunctional or higher functional polyvinyl ether compound can be used. Specific examples of the divinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and tripropylene glycol. Divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6
-Hexanediol divinyl ether, glycerol divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxycyclohexane divinyl ether, 1,4-dihydroxymethylcyclohexane divinyl ether, hydroquinone divinyl ether, hydroquinone diethoxydivinyl ether, resorcin diethoxydivinyl ether , Bisphenol A diethoxydivinyl ether, bisphenol S diethoxydivinyl ether, and the like.

Specific examples of the trifunctional or higher functional polyvinyl ether compound include glycerol trivinyl ether,
Sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane tetravinyl ether, ditrimethylolpropane polyvinyl ether, polyester polyvinyl ether, polyurethane polyvinyl Examples include ether.

The reactive hemiacetal ester obtained by the production method of the present invention is a hemiacetal ester having a (meth) acryloyl group, and its chemical structure varies depending on the starting materials used, but a typical structure is as described above. It is represented by the general formula (1). In the general formula (1), R ¹ is a hydrogen atom or a methyl group, but when high reactivity is required, it is preferably a hydrogen atom which becomes an acrylic compound. R ² is a direct bond, an alkylene group having 2 to 15 carbon atoms, preferably 2 to 8 carbon atoms, or the above general formula (2
-1) or an organic residue represented by (2-2). The organic residue represented by the general formula (2-1) has a carboxyl group obtained from the cyclic acid anhydride (A) represented by the general formula (4) and the hydroxyl group-containing (meth) acrylate compound (B). It is derived from the (meth) acrylate compound that it has.

The above general formulas (2-1) and (2-2)
Among them, p is an integer of 2 to 15, preferably 2 to 6, and if it is larger than this, the reactivity decreases. q is an integer of 2 to 15, preferably 4 to 7, and this range is suitable from the viewpoint of versatility of raw materials and physical properties. m is 1 to 20, preferably 1 to
It is an integer of 5, and if it is larger than this, the reactivity decreases.
n is an integer of 0 to 10, preferably 1 to 5, r is 1 to 1
It is an integer of 0, preferably 1 to 5, and if it is larger than this, the reactivity decreases. R ⁴ is a cyclic acid anhydride (A)
And an organic residue represented by the above general formulas (a) to (g). In formulas (a) to (g), R ⁵ and R ^{5 ′} represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms. Above all, the structure represented by (a) or (b) is preferable when low viscosity is required, and the cyclic structure represented by (c) to (g) is represented when adhesion is required. preferable.

In the general formula (1), R ³ is derived from a vinyl ether compound and has the general formulas (3-1) to (3-).
It is an organic residue represented by 7). General formula (3-1)-
In (3-7), x1 is 1 or 2, x2 is an integer of 1 to 3, x3 is an integer of 1 to 4, x4 is an integer of 1 to 6, y2 is an integer of 0 to 2, and y3 is 0 to 3. And y4 each represent an integer of 0 to 5. In addition, in the general formula (3-1), s is 2
To 25, preferably an integer of 4 to 16, and represented by the general formula (3
-2), p is 2 to 15, preferably an integer of 2 to 6, q
Represents an integer of 2 to 15, preferably 4 to 7, respectively.

The chemical structure of the reactive hemiacetal ester obtained by the production method of the present invention is selected according to the required physical properties and curability. When immediate curing and high hardness are required, a structure using a vinyl ether compound having a large number of functional groups as a raw material, that is, R ³ in general formula (1) is represented by general formulas (3-3) to (3-). A structure which is an organic residue represented by 7) is preferable. Further, when flexibility is required, a structure having two vinyl ether groups and using a relatively long chain vinyl ether compound as a raw material, that is, R ³ in the general formula (1) is represented by the general formula ( 3-1) or a structure which is an organic residue represented by (3-2), an alkylene group in which R ² has 4 to 15 carbon atoms, further 8 to 12 carbon atoms, or a general formula (2-
1) an organic residue (wherein m is 2 to 5 and n is 1 to
A structure in which 5 and r are 2 to 10) is preferable. In addition, the presence of vinyl ether groups that have not reacted with the (meth) acrylic compound having a carboxyl group is not preferable because the reactivity decreases when the number exceeds the number of (meth) acryloyl groups introduced into the molecule. In the case of the following, the reactivity may be improved as compared with the case of using the (meth) acryloyl group alone.

In the production method of the present invention, a catalyst can be used, if necessary, when producing the reactive hemiacetal ester. As a catalyst that can be used, a phosphoric acid ester-based acid catalyst, for example, di-n-butyl phosphate,
2-Ethylhexyl phosphate, monooctyl phosphate, etc. can be mentioned. The amount of the catalyst added is preferably 0.01 to 3 parts by weight, more preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the (meth) acrylic compound having a carboxyl group. The reaction can be carried out in a solventless system, but a general-purpose organic solvent can be used to control the reaction. In that case, the active ingredient concentration is 20 to 9
It is preferably 5% by weight, more preferably 30 to 90% by weight. If the concentration is lower than this range, the reactivity is lowered, which is not preferable.

The molecular weight and viscosity of the reactive hemiacetal ester produced by the present invention are not particularly limited, but the number average molecular weight is 200 to 5,000, and further 2
When it is from 00 to 2000, it may be preferable in terms of compatibility with other components and viscosity. The viscosity is not particularly limited as long as the composition containing the reactive hemiacetal ester is in a viscosity range capable of forming a film, but is preferably a liquid at 25 ° C. in terms of handling, and a viscosity of 20 to 50,000 cps. (30 ° C.) is preferable.

The reactive hemiacetal ester produced according to the present invention can be used alone as a curable solventless liquid resin as a coating material, a film forming material such as ink, a molding material and an adhesive. In addition, one or two of active energy ray-curable compounds such as other (meth) acrylic compounds, vinyl ether compounds, and oxetane compounds.
By blending more than one species, it is possible to adjust viscosity, film-forming property and film performance. In addition, for the same reason, amino resin, phenol resin, polyamide resin, cellulose derivative, vinyl resin, polyolefin, natural rubber derivative, acrylic resin, epoxy resin, polyester, polystyrene, urethane acrylic resin, epoxy acrylic resin, alkyd resin, General purpose resin materials such as rosin-modified alkyd resin and linseed oil-modified alkyd resin, and drying oil such as linseed oil, tung oil and soybean oil may be blended. However, the blending amount of each of them is preferably 60% by weight or less, more preferably 40% by weight or less based on the total amount of the composition.

Further, water, an organic solvent, a compatibilizer, a surfactant or a lubricant may be added for the purpose of controlling fluidity. These compounding amounts are based on the total amount of the composition.
It is preferably 20% by weight, more preferably 10% by weight or less. In addition, the reactive hemiacetal ester produced by the present invention includes a coloring agent composed of a dye or a pigment such as carbon black, titanium white, phthalocyanine, an azo dye, or quinacridone, an inorganic filler such as Si-based fine particles, mica, or calcium carbonate. It can be used as various printing inks or colored paints by adding an appropriate amount of the above. When the reactive hemiacetal ester produced by the present invention is cured by irradiation with radiation, known photopolymerization sensitizers and initiators can be added.

The reactive hemiacetal ester produced according to the present invention is a plate, a film, or a plate made of various metals, plastics, papers, ceramics or composite materials thereof.
A sheet-shaped substrate is coated with a roll coater, a bar coater, a knife coater, or a printing method such as offset printing, gravure printing, letterpress printing, or silk screen printing to form a film having a thickness of 0.1 to 500 μm or Can be filled. The coating film formed or filled by the above method can be cured by irradiating or heating an active energy ray such as electron beam, ultraviolet ray, visible ray or infrared ray.

When curing by electron beam irradiation,
Preferably 10 to 300 kV, more preferably 30 to
An electron beam irradiation device having an accelerating voltage in the range of 100 kV is used. Irradiation with an electron beam having an accelerating voltage of 100 kV or less is preferable because it causes less damage to the coating film and the substrate. Further, in the electron beam irradiation device having a low accelerating voltage in the range of 30 to 70 kV, the energy is concentrated on the surface, so the curing of oxygen is likely to be inhibited by oxygen. Since it is possible to improve the property, it is effective and particularly preferable for curing the thin film. In addition, the electron beam irradiation dose (DOS
E) is preferably in the range of 1 to 1000 kGy, more preferably 5 to 200 kGy. If it is less than this range, it is difficult to obtain a sufficiently cured product, and if it is more than this range, the coating film or the base material is greatly damaged, which is not preferable.

When it is cured by heat, it is preferably cured at 30 to 120 ° C, more preferably 50 to 90 ° C. When the curing temperature exceeds 120 ° C., the decomposition reaction of the reactive hemiacetal ester produced by the present invention proceeds, which is not preferable. Further, if the temperature is lower than 30 ° C, the curing reaction is difficult to proceed, which is not preferable. It is preferable to use a known reaction catalyst at the time of heat curing.

[0032]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. ◎ Purity, number average molecular weight and viscosity measuring method 1) Purity, number average molecular weight (Mn): Gel permeation chromatography (Tosoh Corporation: SC-8020) 2) Viscosity (30 ° C): Rheometer (Rheometrics: RDS-II, RFS-II) Rheometer RDS-II (high viscosity type) manufactured by Rheometrics, or RFS-I according to the viscosity of the sample.
Steady-state viscosity measured by I (low viscosity type) (sliding speed = 1
The value of -10 / sec) was adopted.

◎ Electron beam irradiation device and irradiation conditions 1) Area beam type electron beam irradiation device Curetron EBC-200
-20-30 (manufactured by Nisshin High Voltage Co., Ltd.) Electron beam acceleration; 150 kV absorbed dose (Dose); Adjusted by the amount of current in the range of 5 to 50 kGy. 2) MIN-EB (manufactured by AIT) Electron beam acceleration; 50 kV absorbed dose (Dose); 5 to 20 kGy was adjusted by the transport speed.

The abbreviations of the following compounds used in Examples and Comparative Examples are shown below. 1) Vinyl ether compound (C) HDDV; 1,6-hexanediol divinyl ether TPGDV; tripropylene glycol divinyl ether TMPTV; trimethylolpropane trivinyl ether 2) (meth) acrylic compound AA having a carboxyl group; acrylic acid SA; Succinic acid β-acryloxyethyl monoester

3) Raw material cyclic acid anhydride (A) SAH; succinic anhydride HPAH; cis-1,2 cyclohexanedicarboxylic acid used when synthesizing a (meth) acrylic compound having a carboxyl group (Synthesis Examples 1 to 9) Anhydrous PAH; Phthalic anhydride hydroxyl group-containing (meth) acrylate compound (B) 4HBA; 4-Hydroxybutyl acrylate PPG6A; Polypropylene glycol (repeating unit = 6)
Monoacrylate PPG2A; dipropylene glycol monoacrylate FA2; 2- (meth) acryloyloxyethyl hydrogen dicaprolactonate PE3A; pentaerythritol triacrylate

4) Raw materials for monofunctional vinyl ether, epoxy acryl, urethane acryl, which were synthesized for comparison EVE; ethyl vinyl ether HDDG; 1,6-hexanediol diglycidyl ether HMDI; hexamethylene diisocyanate

(Synthesis examples 1 to 9) having a carboxyl group
Synthesis of (meth) acrylic compounds Stirrer, nitrogen introduction tube, temperature sensor, condenser
In a four-necked round bottom flask equipped with the cyclic acid anhydride shown in Table 1.
(A) and a hydroxyl group-containing (meth) acrylate compound
An equimolar charge of (B) (containing a hydroxyl group with a repeating structure)
The compounding amount of the (meth) acrylate compound is calculated from the hydroxyl value.
Added), and 0.5 phr of dimethylbenzylamine was added.
did. Set this in a hot water bath set at 90 ° C and heat
Stirring was started. Make sure that the reaction system is uniform.
Once the temperature of the hot water bath is lowered to 700 ℃, continue heating and stirring.
It was After 3 hours, the characteristic absorption of acid anhydride by IR (18
20 cm ^-1(Near) and the peak disappeared
So I removed it from the bath and let it cool down. The obtained product has GPC and acid value.
Was confirmed by the measurement. In Table 1, cyclic acid anhydride (A)
And a seed of a hydroxyl group-containing (meth) acrylate compound (B)
And a (meth) acryl having the obtained carboxyl group
Shows the acid value of the ruthenium compound.

[0038]

[Table 1]

Example 1 A four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser had HDDV and 2 moles of the carboxyl group obtained in Synthesis Example 1 (meta). ) An acrylic compound was charged, and 1 phr of dibutyl phosphate was further added. Room temperature (25
(° C). The acid value is measured every 1 hour, and 5 mgKOH / g
When the temperature became below, the reaction was stopped by removing it from the bath. The obtained compound was confirmed by the molecular weight measured by GPC and the residual ratio of the raw materials. The reaction of the (meth) acrylic compound having a carboxyl group obtained in Synthesis Example 1 was followed with time.
The GPC chart and the attribution of the peak are shown in FIGS. 1 and 2, and the GPC chart and the attribution of the peak in which the synthetic reaction of the reactive hemiacetal ester using the same is followed with time are shown in FIGS.

Example 2 A four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was used.
HDDV and 2 mole times the amount of the (meth) acrylic compound having a carboxyl group obtained in Synthesis Example 2 were charged, and 1 phr of dibutyl phosphate was further added. Room temperature (25 ℃)
It was stirred at. The acid value was measured every hour, and when the acid value became 5 mgKOH / g or less, the reaction was stopped by removing from the bath. The obtained compound was confirmed by the molecular weight measured by GPC and the residual ratio of the raw materials. GPC showing the reaction of the (meth) acrylic compound having a carboxyl group obtained in Synthesis Example 2 over time
The chart and the attribution of the peak are shown in FIGS. 5 and 6, and the GPC chart and the attribution of the peak are shown in FIGS. 7 and 8 in which the synthetic reaction of the reactive hemiacetal ester using the same is followed. For reference, GPC charts of raw materials are shown in FIGS.

Example 3 A four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser had HDDV and 2 mol times the amount of the carboxyl group obtained in Synthesis Example 3 (meta). ) An acrylic compound was charged, and 1 phr of dibutyl phosphate was further added. Room temperature (25
(° C). The acid value is measured every 1 hour, and 5 mgKOH / g
When the temperature became below, the reaction was stopped by removing it from the bath. The obtained compound was confirmed by the molecular weight measured by GPC and the residual ratio of the raw materials. The reaction of the (meth) acrylic compound having a carboxyl group obtained in Synthesis Example 3 was followed with time.
The GPC chart and the attributions of the peaks are shown in FIGS. 12 and 13, and the GPC charts and the attributions of the peaks which follow the synthetic reaction of the reactive hemiacetal ester using the same are shown in FIG.
4 and 15 respectively.

(Examples 4 to 16) Using the raw materials shown in Table 2, synthesis was carried out in the same manner as in Example 1 to obtain a reactive hemiacetal ester.

(Comparative Examples 1 to 3) Stirrer, nitrogen introducing pipe,
A four-necked round bottom flask equipped with a temperature sensor and a condenser was charged with HDDG and 2 mole times the amount of the (meth) acrylic compound having a carboxyl group obtained in Synthesis Examples 1 to 3 and dimethylbenzylamine 0.5 phr. Was added. This was set in a hot water bath set at 85 ° C., and heating and stirring was started. When it was confirmed that the inside of the reaction system became uniform, the temperature of the water bath was further raised to 95 ° C., and heating and stirring were continued. The acid value was measured every hour, and when the acid value became 5 mgKOH / g or less, the reaction was stopped by removing from the bath. The obtained compound was confirmed by the molecular weight measured by GPC and the residual ratio of the raw materials.

(Comparative Example 4) A four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, a condenser and a dropping funnel was prepared, and HDDI was charged in the dropping funnel.
A round bottom flask was charged with 4 mol of 2HBA of 2 mol times of HDDI, and 0.01 phr of tin dimethylhexanoate was further added. This was set in a hot water bath set at 80 ° C., and heating and stirring was started. If it can be confirmed that the temperature inside the reaction system has reached 75 ° C, HDDI
Was started, and heating and stirring were continued while controlling the dropping rate so that the reaction temperature did not exceed 100 ° C. After completion of the dropping, the NCO value was measured every hour, and when the reaction rate reached 99.5% or more, the reaction was stopped by removing it from the hot water bath.

(Comparative Example 5) A four-necked round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, a condenser and a dropping funnel was prepared, and HDDI was charged in the dropping funnel.
A round bottom flask was charged with PE3A (the average molecular weight was recalculated from the hydroxyl equivalent) in an amount of 2 mol times that of HDDI, and 0.01 phr of tin dimethylhexanoate was further added. 80 ° C
The mixture was set in a hot water bath set to, and heating and stirring was started. When it was confirmed that the temperature in the reaction system reached 75 ° C, HDDI dropping was started, and heating and stirring were continued while adjusting the dropping rate so that the reaction temperature did not exceed 100 ° C. After the completion of dropping, the NCO value was measured every hour, and when the reaction rate reached 99.5% or more, the reaction was stopped by removing it from the hot water bath.

(Comparative Example 7) A four-neck round bottom flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a condenser was used.
EVE and acrylic acid were charged in equal amounts, and 1 phr of dibutyl phosphate was further added. This was stirred at room temperature (25 ° C). 1
The acid value was measured every hour, and when the acid value became 5 mgKOH / g or less, the reaction was stopped by removing it from the hot water bath. The obtained compound is GP
It was confirmed by the molecular weight measured by C and the residual ratio of the raw material.

Table 2 shows the number average molecular weight (Mn), viscosity and purity of the compounds obtained in Examples and Comparative Examples.

[Table 2]

The reactive hemiacetal ester, the epoxy acrylic compound, and the urethane acrylic compound obtained in Examples 1 to 16 and Comparative Examples 1 to 6 were coated on an aluminum plate with a # 6 bar coater to emit an electron beam. Irradiated. Table 3
In addition, the curing characteristics of the coating film obtained by electron beam irradiation conditions (irradiation dose, oxygen concentration, accelerating voltage) (tack test → ×:
With tack, △: Without tack, but with scratches on nails, ○: No scratch with nails, MEK rubbing test → Surface condition after rubbing absorbent cotton containing MEK 50 times with a load of about 500 g; ○: No change, △: surface whitening, ×: base can be seen)
The evaluation results of are shown.

[0049]

[Table 3]

[0050]

According to the present invention, excellent fluidity and curability,
Reactive hemiacetal that can be used in a wide range of fields as a film-forming material such as paints and inks, or as a raw material for sealants, molding agents, adhesives, pressure-sensitive adhesives, and can be cured by heat or active energy rays. The ester can now be easily produced.

[0051]

[Brief description of drawings]

FIG. 1 GPC chart and peak assignment immediately after homogenization of the reaction system of Synthesis Example 1

2] GPC chart and peak assignment 2 hours after the start of reaction in the reaction system of Synthesis Example 1

FIG. 3 is a GPC chart and peak assignment immediately after the start of the reaction of the reaction system of Example 1.

FIG. 4 is a GPC chart and peak assignment of the reaction system of Example 1 3 hours after the start of the reaction.

FIG. 5: GPC chart and peak assignment immediately after homogenization of the reaction system of Synthesis Example 2

FIG. 6 is a GPC chart and peak assignment 4 hours after the start of reaction in the reaction system of Synthesis Example 2.

FIG. 7: GPC chart and peak assignment immediately after the start of reaction of the reaction system of Example 2

FIG. 8: GPC chart and peak assignment 5 hours after the start of the reaction in the reaction system of Example 2

[Figure 9] GPC chart of 4HBA

[Figure 10] HPAH GPC chart

FIG. 11: GPC chart of HFFV

FIG. 12: GPC chart and peak assignment immediately after homogenization of the reaction system of Synthesis Example 3

FIG. 13: GPC of the reaction system of Synthesis Example 3 5 hours after the start of reaction
Charts and peak attribution

FIG. 14: GPC chart and peak assignment immediately after the start of reaction of the reaction system of Example 3

FIG. 15: GPC of the reaction system of Example 3 3 hours after the start of reaction
Charts and peak attribution

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Teruo Shiono             Toyo Inn, 2-3-13 Kyobashi, Chuo-ku, Tokyo             Ki Manufacturing Co., Ltd. F-term (reference) 4H006 AA01 AA02 AA03 AB46 AC48                       BJ20 BJ30 BN10 BP10 KA11                 4J038 FA011 GA01 PA17                 4J040 DN061 FA141 FA151 FA161                       FA271 FA291 GA02 JB07                       JB08 LA01 LA11                 4J100 AL08P AL65P AL66P AL67P                       AL74P AL75P AR05P AR11P                       BA02P BA03P BA08P BA15P                       BA16P BC04P BC43P CA01                       JA01 JA03

Claims (4)

[Claims] 1. A method for producing a reactive hemiacetal ester, which comprises reacting a (meth) acrylic compound having a carboxyl group with a vinyl ether compound (C) having two or more vinyl ether groups. 2. The (meth) acrylic compound having a carboxyl group is a half ester obtained by reacting a cyclic acid anhydride (A) with a (meth) acrylate compound (B) having a hydroxyl group. The method for producing the reactive hemiacetal ester of. 3. A method manufactured by the method according to claim 1 or 2,
A reactive hemiacetal ester represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ is a hydrogen atom or a methyl group, R ² is a direct bond, an alkylene group having 2 to 15 carbon atoms, or an organic residue represented by the following general formula (2-1) or (2-2), R ³
Is an organic residue represented by the following general formulas (3-1) to (3-7), x1 is 1 or 2, x2 is an integer of 1 to 3, and x3 is 1.
Is an integer of 4 and x4 is an integer of 1 to 6, respectively. ) [Chemical 2] (In the formula, R ⁴ is an organic residue selected from the following general formulas (a) to (g), p is an integer of 2 to 15, q is an integer of 2 to 15,
m is an integer of 1 to 20, n is an integer of 0 to 10, and r is 1 to 1.
An integer of 0 is shown. ) [Chemical 3] (In the formula, R ⁵ and R ^{5 ′} represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms.) (In the formula, x1 is 1 or 2, x2 is an integer of 1 to 3, x3
Is an integer of 1 to 4, x4 is an integer of 1 to 6, y2 is an integer of 0 to 2, y3 is an integer of 0 to 3, y4 is an integer of 0 to 5, and s is 2
Each represents an integer of -25. ) 4. A cured product obtained by irradiating the reactive hemiacetal ester according to claim 3 with an active energy ray.