JPH07173104A - Lactone-modified diketene (meth)acrylate and production thereof - Google Patents

Abstract

PURPOSE:To obtain an acrylate having a terminated acetylacetate group which is useful for various coating resins, adhesive, ink, photosensitive material for photography, pigments-dispersing agent, fiber-processing agent and rubber- modifier. CONSTITUTION:A lactone-modified diketene (meth)acrylate of formula I [R1 is H, CH3; R2 is a 1 to 10 C hydrocarbon; n is 1 to 20; X is a ring-opened unit of a lactone of formula II (z is 4-8; R<a> and R<b> are H, methyl[. The compound of formula I is obtained by reaction of a lactone-modified (meth)acrylate of formula III with a diketene at 20 to 140 deg.C, preferably in the presence of a Lewis acid or an amine. The compound of formula I can be readily copolymerized with a vinyl monomer such as styrene, methyl methacrylate, acrylonitrile, vinyl acetate and vinyl chloride. It is useful as a monomer for UV curing or an amine curing adhesive.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a lactone-modified diketene (meth) having active methylene and lactone chains in the molecule.
Regarding acrylates. More specifically, it relates to a compound obtained by reacting a lactone-modified (meth) acrylate compound with diketene and the production thereof. Various paint resins, adhesives, inks, photographic light-sensitive materials, pigment dispersants, fiber treatments. The present invention relates to a lactone-modified diketene (meth) acrylate compound having a terminal acetylacetonate group consisting of a lactone in the molecule, which is useful as an agent, a rubber modifier, and the like.

[0002]

The following acetoacetoxyethyl (meth) acrylate is well known as a (meth) acrylate having an acetylacetonate group in the molecule.

[0003] The compound (III) is obtained from 2-hydroxyethyl methacrylate and diketene as described in JP-B-45-5819, and an acrylic polymer having an active proton is obtained by copolymerizing with butyl acrylate, acrylic acid and the like. It is known to be obtained. These polymers are disclosed in JP-B-45-5819 and JP-A-55-1.
As a light-sensitive material as described in JP-A-29346 and as a resist described in JP-A-61-275356, or JP-A-5-156225.
It is used as an adhesive in the publication.

Acetoacetoxyethyl (meth) acrylate (III) is also characterized by its excellent reactivity in pigment dispersants and inks. However, there are points to be improved in terms of flexibility, adhesion, compatibility, scratch resistance and the like.

On the other hand, recently, due to the problems of energy saving and resource saving, and diversification of applications, there has been a demand for higher performance and higher quality monomers and resins than ever before. As a light-sensitive material, various resins have been proposed such as a polymer that gives high sensitivity and stability, and a water-based paint, a high-solid paint, a UV curable paint, and the like for coating.

The (meth) acrylic polymer obtained by radically polymerizing acrylic acid, styrene and the like, including acetoacetyl (meth) acrylate, uses an amine compound as a curing agent, an adhesive for woodworking and a coating agent. To be done. However, it is difficult to relax the stress when the adhesive is cured, and as a result, the adhesion between the substrate and the coating film may be significantly impaired. Further, it is used in a coating field where weather resistance, chemical resistance, water resistance, stain resistance and high hardness are required in combination with a curing agent such as isocyanate and melamine. However, it is difficult to obtain a coating film having high flexibility with these (meth) acrylic polyol resins.

[0007]

The acetoacetyl (meth) acrylate monomer can be used in the above various fields because of its unique reactivity. However, when used as a (meth) acrylic monomer for coating,
There are still points to be improved in flexibility, adhesion, scratch resistance, resin compatibility and the like. Further, there is a demand for improvement in terms of stress relaxation during adhesion hardening.

Also, when it is used as an emulsion as a photographic light-sensitive material or a pigment dispersant, the adhesion to the pigment and the compatibility with other resins are insufficient.

[0009]

OBJECTS OF THE INVENTION The inventors of the present invention have made extensive studies as to develop a new compound capable of improving these drawbacks, and as a result, achieved the present invention.

[0010]

That is, the present invention is
"General formula (I) <In the general formula (I), R ₁ is H or CH ₃ , R ₂
Is a hydrocarbon having 1 to 10 carbon atoms, n is an integer of 1 to 20, X is a unit in which the following lactone compound is opened, Or a lactone-modified diketene (meth) acrylate compound represented by> representing a methyl group "and" general formula (II) A lactone-modified (meth) acrylate compound represented by the formula (I) and a diketene are reacted at 20 ° C to 140 ° C. <In the general formulas (I) and (II), R ₁ is H or CH ₃ , R ₂ is a hydrocarbon having 1 to 10 carbon atoms, and n is 1 to 2
Represents an integer of 0, X is a unit in which the following lactone compound is opened, Or a method for producing a lactone-modified diketene (meth) acrylate compound represented by> representing a methyl group.

When the lactone-modified diketene (meth) acrylate compound of the present invention is a (meth) acrylic copolymer, it has a lactone chain in its side chain, and the proportion of the lactone chain can be changed arbitrarily. It is possible to obtain a polymer having any flexibility, adhesion, and glass transition point, which is suitable for various applications. Furthermore, surprisingly, the reactivity of acetoacetic acid ester is higher than that of acetoacetyl (meth) acrylate (III).

The lactone compound which can be used is ε-
Cyclic lactones such as caprolactone, cyclooctanone lactone, β-methyl-valerolactone,
-Caprolactone is preferred. Further, instead of the lactone compound, oxycaproic acid which is a ring-opened product thereof can also be used.

For example, when ε-caprolactone is used as the lactone compound, z is 5, and R ^a and R ^b are H. When β-methyl-valerolactone is used as the lactone compound, z is 4, and R ^a and R ^b are both H.

This is because the acetoacetic acid ester group is separated from the main chain of the (meth) acrylic copolymer due to the lactone chain, so that the acetoacetic acid ester becomes easy to move, so that the acetoacetic acid ester can move with other curing agents. It is thought that this is because the reaction becomes easier.

On the other hand, acetoacetic acid is known to chelate with metals.

[0016]

[Chemical 1]

[Chemical 2] Regarding this chelation as well, it is considered that when the acetoacetic acid group is separated from the polymer main chain, the reactivity is similarly improved and the adhesion to the substrate such as a metal is improved.

[0017]

[Chemical 3] Further, it can be easily inferred that the lactone chain absorbs the stress at the time of curing when reacting with another curing agent, so that there is no distortion and the adhesiveness is maintained.

Further, by utilizing this metal chelating ability, for example, a (meth) acrylic polymer obtained by chelating copper, tin or a metal can be synthesized. Such a polymer utilizes the sustained metal release property, and as a coating agent, it can be applied to, for example, a ship bottom paint for the purpose of preventing the adhesion of microorganisms. Besides, it can be chelated with various metals such as aluminum, titanium, zirconium, iron, zinc and nickel. It is also possible to use such properties as a dispersant for metal pigments and the like.

Furthermore, a feature of this compound is that it is excellent in water resistance. Ordinary polyester polyols are susceptible to hydrolysis due to their ester bond, but exhibit the water resistance because of the most excellent polycaprolactone side chain among polyesters. Therefore, for example, acrylic acid, acrylic acid ester, and sodium bisulfite can be polymerized in water in the presence of an emulsifier to form an emulsion, which can be used as a photographic emulsifier or the like.

On the other hand, the active methylene of this acetoacetic acid ester reacts with melamine, isocyanate, aldehyde, amine and the like. Also, under basic conditions, double bond compound and M
ichael addition reaction.

[0021]

[Chemical 4]

[Chemical 5]

[Chemical 6] <Michael addition reaction> By utilizing these properties, it is also useful as a coating adhesive having a new curing mechanism.

In particular, it can be used for automobile paints, varnishes for woodworking, gravure erosion, etc. as well as the conventional reaction between melamine, isocyanate and polyol.

Further, it can be used together with an organic halide, a film property imparting polymer, a sensitizer and the like, and can be used for producing a photosensitive resin such as a printed wiring board and for precision machining of metal.

In general, UV cure can cure coatings, inks, etc. in a short time, is energy-saving, and has a great effect on productivity, and is useful for woodwork paints, offset printing illekes, and electronics-related resists. Is. However, due to the hardness of the coating film and the curing for a short time, the stress is not relaxed, and cracks or the like may be seen on the surface. From this point of view, the compound of the present invention solves these problems because of the unique properties of its lactone.

The lactone-modified (meth) acrylate, which is one of the starting materials used in the present invention, is a compound of the general formula (II). Specifically, for example, Praxel FM-1, FM-2 obtained by ring-opening polymerization of ε-caprolactone using 2-hydroxy (meth) acrylate as a ring-opening initiator.
FM-4, FA-1, FA-2 [Daicel Chemical Co., Ltd.
Manufactured by etc.] and Tone M100 and Tone M201 [U
CC company] and the like.

[0026] When n is 1, the FM is FM1 and when n is 2, FM is FM
It is 2.

[0027] When n is 1, the plaxel FA-1; when n is 2, F
It is A-2.

[0028] Furthermore, 1,4-butanediol monoacrylate ε-caprolactone adduct, hydroxypropyl (meth) acrylate ε-caprolactone adduct, and (meth) acrylic acid obtained by adding two or more molecules of ethylene oxide. Polyethylene glycol (meta)
Acrylates as well as ε-caprolactone adducts of polypropylene glycole (meth) acrylate can be mentioned.

The other starting material, diketene, is industrially manufactured on a large scale and is easily available. It is desirable to carry out the reaction at 20 to 140 ° C.

At 140 ° C. or higher, lactone modification (meth)
The acrylate becomes unstable and gels easily. 20 ° C
In the following cases, the reaction is slow and economically disadvantageous. The reaction is advantageously carried out in the presence of a catalyst. For example, a tin compound is typical as the Lewis surface. Besides, Zn, Ti, N
i, Co, Al, Zr, etc. can be used.

Further, triethylamine, tri-n-butylamine and the like may be used as the tertiary amine. The reaction proceeds without using a solvent. However, an ester, an aromatic compound, a halogen compound, an aliphatic hydrocarbon or the like may be used depending on the application. However, solvents having active hydrogen such as alcohols and amines are not preferable. In order to carry out the reaction stably, it is desirable to coexist with a polymerization inhibitor. Commonly used phenolic compounds such as hydroquinone and hydroquinone monomethyl ether, sulfur compounds such as phenothiazine, nitroso compounds such as N-methylnitrosoaniline, and phosphorus compounds can be used alone or in combination.

The concentration depends on the reaction conditions, but is generally several pp
m-in the range of several thousand ppm. Furthermore, air or
This compound can be stably produced by circulating a mixture of nitrogen and oxygen in the reaction solution. However, the flow rate of air or N ₂ / O ₂ mixture needs to be in a range where organic substances in the gas phase do not form an explosive mixture.

The molar ratio of the diketene and the OH of the lactone-modified (meth) acrylate compound used may be selected at any ratio. Preferably the diketene to OH is 0.8-1.
It is twice the mole.

When a large amount of unreacted diketene remains at the end of the reaction, it can be decomposed and removed with water or an alkaline aqueous solution. Alternatively, the unreacted diketene can be distilled off with a thin film evaporator or the like.

[0035]

The lactone-modified diketene (meth) of the present invention
Acrylate compounds are styrene, methyl methacrylate,
Acrylonitrile, vinyl acetate, vinyl chloride, vinylpyrrolidone, butadiene, can be easily covalently combined with vinyl compounds such as isoprene, the above-mentioned coating agent,
The drawbacks of various materials such as adhesives, photographic materials, pigment dispersants, and photocurable resins can be compensated. Further, as a monomer, it can be used for various purposes such as a UV curing monomer and an amine curing adhesive.

Hereinafter, the present invention will be described in more detail with reference to examples, but these do not limit the present invention.

[Example-1: Acetoacetylation of lactone-modified methacrylate] In a 1000 ml flask equipped with a stirrer, reflux condenser, thermometer, dropping funnel and gas conduit, lactone-modified methacrylate [Praxel FM-
2: 514.7 g manufactured by Daicel Chemical Co., Ltd. and 126.8 g of diketene [manufactured by Daicel Chemical Co., Ltd.] were charged to the dropping funnel.

Next, 0.64 gr of dibutyltin dilaurate was added to the flask and stirring was started. Then, hydroquinone monomethyl ether was charged into a 0.3 gr flask. Heating was started in an oil bath so that the internal temperature was 85 to 95 ° C. Then, in about 1 hour, 12
6.8 gr of diketene was dropped into the flask.

After the dropping was completed, the internal temperature was kept at 90 ° C. for 12 hours, heating was stopped and the mixture was cooled to room temperature. When diketene in the reaction crude liquid was measured by gas chromatography,
It was 0.70%. Moreover, the hydroxyl value of the reaction product was 1.0 or less, and it was found that the reaction proceeded almost quantitatively.

Infrared analysis revealed that 1732 cm ¹
The absorption derived from acetylacetone is observed in [Fig. 1].

On the other hand, in FIG. 3, n = 0, 1, 2, ...
-It can be seen that the distribution is. In H-NMR, the following absorptions were observed, and in the compound of the formula (I), n = 2 as an average, R ¹ is CH ₃ , R ² is —CH ₂ CH ₂
It was confirmed that the − compound was produced [FIG. 2].

Δ (ppm) 1.3 to 1.45 Methylene (4H) 1.5 to 1.7 Methylene (8H) 1.95 Methyl (3H) 2.10 Methyl (3H) 2.2 to 2.4 Methylene (4H) 3.4 to 3.5 Methylene (1.9H) 4.0 to 4.18 Methylene (4H) 4.3 to 4.4 Methylene (4H) 5.6, 6.1 Methacryl proton (2H) 11.9 to 12.1 Ethanol proton of acetylacetone (0.1
H) On the other hand, in Chart-3, it is understood that n = 0, 1, 2, ... [Example-2: Acetoacetylation of lactone-modified acrylate] 151.1 g of lactone-modified acrylate [Placcel FA-2, manufactured by Daicel Chemical Industries, Ltd.] was used in place of the lactone-modified methacrylate.
40.9 g of diketene was used. Next, 0.02 gr of dibutyltin dilaurate was charged, and further 1 was added to the reactor.
The reaction was carried out in the same manner as in Example-1 by blowing in 0 ml / min of air.

The diketene in the crude reaction liquid was measured by gas chromatography and found to be 0.50%. Also,
The hydroxyl value of the reaction product was 1.0 or less, indicating that the reaction proceeded almost quantitatively.

Infrared analysis showed that 1732 cm ¹
Absorption derived from acetylacetone is observed in [Fig. 4]. Further, from the GPC chart [FIG. 6], it is found that the present compound has a distribution of n = 0, 1, 2, ...

In H-NMR, the following absorptions were observed, and a compound in which R ¹ was H and R ² was —CH ₂ CH ₂ — in the compound (I) having n = 2 as an average. It was confirmed [Fig. 5].

Δ (ppm) 1.4 methylene (2H) 1.6 methylene (8H) 2.2-2.4 methyl (3H) 3.3-3.4 methylene (1.9H) 4.0-4. 2 Methylene (4H) 4.2 to 4.4 Methylene (4H) 5.6 to 6.5 Methacryl proton (3H) 11.9 to 12.1 Acetoneacetone enol proton (0.1
H) [Example-3: Acetoacetylation of lactone-modified methacrylate] Praxel F instead of Praxel FM-2
122.0 g of M-1 [manufactured by Daicel Chemical Industries, Ltd.] and 42.0 g of diketene were used. Next, 0.01 gr of dibutyltin dilaurate was charged, and further 10 ml was charged in the reactor.
Air was blown in at a flow rate of / min to carry out the reaction in the same manner as in Example-1.

The diketene in the reaction crude liquid was measured by gas chromatography to be 0.50%. Also,
The hydroxyl value of the reaction product was 1.0 or less, indicating that the reaction proceeded almost quantitatively.

The reaction crude liquid has a viscosity of 25 cp / 25 ° C. and an APHA value of 30.
Met.

[Example-4: Acetoacetylation of lactone-modified acrylate] In place of Praxel FA-2, 115.0 g of Praxel FA-1 [manufactured by Daicel Kagaku KK] was used and 37.9 g of diketene was used. Next, 0.01 gr of dibutyltin dilaurate was charged, and 10 ml / min of air was blown into the reactor to carry out the reaction in the same manner as in Example-1.

The diketene in the reaction crude liquid was measured by gas chromatography to be 0.03%. Also,
The hydroxyl value of the reaction product was 1.0 or less, indicating that the reaction proceeded almost quantitatively.

The reaction crude liquid has a viscosity of 28 cp / 25 ° C. and an APHA value of 20.
Met. (Below margin)

[Brief description of drawings]

FIG. 1 is an IR spectrum chart of the lactone-modified diketene methacrylate compound obtained in Example 1.

FIG. 2 is the same ¹ H-NMR spectrum chart.

FIG. 3 is the same GPC spectrum chart.

FIG. 4 is an IR spectrum chart of the lactone-modified diketene acrylate compound obtained in Example 2.

FIG. 5 is the same ¹ H-NMR spectrum chart.

FIG. 6 is the same GPC spectrum chart.

[Explanation of symbols]

None (the margin below)

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (4)

[Claims] 1. The general formula (I) <In the general formula (I), R ₁ is H or CH ₃ , R ₂
Is a hydrocarbon having 1 to 10 carbon atoms, n is an integer of 1 to 20, X is a unit in which the following lactone compound is opened, Or a lactone-modified diketene (meth) acrylate compound represented by> representing a methyl group. 2. General formula (II) A lactone-modified (meth) acrylate compound represented by the formula (I) and a diketene are reacted at 20 ° C to 140 ° C. <In the general formulas (I) and (II), R ₁ is H or CH ₃ , R ₂ is a hydrocarbon having 1 to 10 carbon atoms, and n is 1 to 2
Represents an integer of 0, X is a unit in which the following lactone compound is opened, Or a lactone-modified diketene (meth) acrylate compound represented by &gt; 3. The method for producing a lactone-modified diketene (meth) acrylate compound according to claim 2, wherein the reaction is carried out in the presence of a Lewis acid. 4. The method for producing a lactone-modified diketene (meth) acrylate compound according to claim 2, wherein the reaction is carried out in the presence of an amine compound.