JPH068337B2 - Novel urethane compound and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has the property of being cured by irradiation with ionizing radiation such as ultraviolet rays, electron beams, and γ rays, and not only for organic substances but also for pigments. It also has good leak adhesion suitability for inorganic powders such as, and inorganic substrates such as metal, glass, ceramics, etc., and also has excellent properties for mechanical strength such as yield point, break point, and elongation. The present invention relates to a novel urethane compound having a film-forming performance and a method for producing the same.

[Conventional technology]

Urethane compounds having a tough cured film forming ability are widely used for binders in various paints, adhesive compositions, coating material compositions, molding compositions for engineering plastics molded products, resists, and the like. For example, a thermosetting urethane having a cross-linking agent typified by an isocyanate compound having a polyvalent isocyanate group and a polymer having a polyvalent hydroxyl group or a polyvalent amino group to form a three-dimensional network structure by a chemical reaction, [In the formula, R ^a is hydrogen or a methyl group, R ^b is a lower alkylene, R ^c is an aliphatic or alicyclic divalent hydrocarbon,
A represents oxygen or -NH-, and p represents an integer of 2 to 50. ] The urethane compound represented by (Japanese Patent Publication No. 53-1
No. 12933), an organic polyisocyanate, and a formula [In the formula, R ^a is hydrogen or a methyl group, and R ^b is a carbon number of 2 to 5
Represents alkylene. An acrylic compound represented by], wherein _{^{R c (OC p H 2p)}} q OH [wherein ^{R c} is an alkyl group,
p and q represent integers] and an ionizing radiation curable urethane composed of a urethane compound (see Japanese Patent Publication No. 54-160494) which is a reaction product with a hydroxyl compound.

[Problems to be solved by the invention]

By the way, the thermosetting urethane described above requires a long time (for example, 10 to 24 hours at 60 ° C.) for the heating and curing process because of the three-dimensional network structure when the polyurethane is produced, that is, the crosslinking reaction of isocyanate is slow. That is, not only the production efficiency is poor, but, for example, when forming a coating film, blocking of the coating layer, deformation of the tape due to winding tightness, and the like are likely to occur, and there is an adverse effect on quality control.

Further, the other ionizing radiation curable urethane, when obtaining a coating film composed of polyurethane, at the stage where the coating layer of the coating agent for forming the coating film is irradiated with ionizing radiation to start curing, The coating layer undergoes a rapid volume shrinkage, and the resulting coating film is distorted, so that a coating film satisfying physical properties such as adhesive strength and processability cannot be obtained. Have

Furthermore, the conventional curable urethanes all have insufficient affinity for an inorganic substance, and are used as an adhesive between an inorganic substance and an organic substance, for example, when applied to an inorganic-organic composite. In this case, there is a drawback that the affinity performance for the inorganic component is low.

On the other hand, in the present invention, it is cured by irradiation of ionizing radiation, and yet exhibits sufficient affinity performance for both the inorganic component and the organic component, and yield value, rupture value, elongation, etc. It is possible to provide a novel urethane compound having a tough coating film forming ability having excellent mechanical properties and a method for producing the same.

[Means for Solving Problems] The novel urethane compound of the present invention has the general formula In the formula, R ¹ is a divalent hydrocarbon group having 6 to 20 carbon atoms, X
Is the formula X is the formula It is a urethane compound represented by.

In the urethane compound represented by the general formula [I], the portion represented by “X” has the same structure as described above. Polyester / urethane bond unit of 1 or more represented by The second urethane bonding unit represented by 1 or more is an assembly having as essential units, but the bonding state between different kinds of units in the “X” part is such that different kinds of units are alternately arranged, Units arranged in blocks,
Alternatively, the heterogeneous units may be arranged in a completely random state, and it is necessary that the total of all bonding units in the “X” portion is an integer of 10 or less, and preferably 2 to Within the range of 5. This is because in the urethane compound represented by the general formula [I], all units each having one or more of the above-mentioned polyester-urethane bond unit and second urethane bond unit in the portion represented by "X" are When the total exceeds 10, a (meth) acrylic acid ester group having a polymerizable unsaturated group at the terminal in the urethane compound represented by the general formula [I], that is, radical polymerizable represented by Q ¹ and Q ² . This is because the ratio of the compound component decreases, and the coating film formed by this urethane compound tends to be cured and deteriorated, and the yield point and the break point of the film tend to be remarkably lowered. In the case where the urethane compound represented by the general formula [I] does not have the “X” portion, the coating film formed by the urethane compound is extended. Without, so that exists a tendency to become brittle.

The method of the present invention for obtaining the novel urethane compound of the present invention represented by the above general formula [I] comprises a diisocyanate compound [A], a polyester compound [B] having hydroxyl groups at both ends, and two hydroxyl groups in the molecule. With a carboxylic acid compound [C] having A first step of obtaining a diisocyanate compound having an isocyanate group at both terminals represented by, a radically polymerizable compound consisting of the diisocyanate compound obtained in the first step and a (meth) acrylic acid ester having a hydroxyl group at the terminal [ D] while reacting while protecting the double bond in the radical polymerizable compound [D] to form a urethane bond between the isocyanate group of the diisocyanate compound and the hydroxyl group of the radical polymerizable compound, And the urethane compound obtained in the second step is reacted with glycidyl methacrylate or 2 (1-aziridinyl) ethyl methacrylate to obtain the urethane compound represented by the formula [I]. And a third step of obtaining a urethane compound which is a target compound.

The diisocyanate compound [A] used in the first step of the method of the present invention for obtaining the novel urethane compound is 1
Aliphatic and aromatic polyisocyanate compounds having two isocyanate groups in the molecule, for example,
Tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4'-diphenylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 1,3-bis ( Isocyanatomethyl) cyclohexane, trimethylhexamethylene diisocyanate and the like are used alone or in a mixture of two or more kinds.

Further, the polyester compound [B] whose both terminals are also composed of hydroxyl groups is a ring-opening polyester compound derived from a condensation product of a polybasic acid and a polyhydric alcohol and a cyclic ester compound, such as phthalic acid, Saturated polybasic acids such as isophthalic acid, terephthalic acid, adipic acid, succinic acid, sebacic acid, and unsaturated polybasic acids such as maleic acid, fumanic acid, itaconic acid, citraconic acid, ethylene glycol, diethylene glycol, 1 -Opening polymerization of polyester compounds as esterification reaction products with polyhydric alcohols such as 1,4-butanediol and 1,6-hexane glycol, and lactone compounds of ε-caprolactone, δ-valerolactone and their respective derivatives. A polyester compound or the like obtained by the above process and having a polymerization degree of 1 to 30 is used.

Further, as the carboxylic acid compound [C] which also has two hydroxyl groups in the molecule, for example, (CH ₂ OH) ₂ C (CH ₃ ) COOH or the like is used.

Examples of the radical-polymerizable compound [D] composed of a (meth) acrylic acid ester having a hydroxyl group at the terminal used in the second step of the method of the present invention include, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxy. Ethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, 4-hydroxycyclohexyl acrylate, 5-hydroxycyclooctyl acrylate, 5-hydroxycyclooctyl acrylate,
Radical polymerizable compounds having one polymerizable unsaturated group such as 2-hydroxy-3-phenyloxypropyl acrylate There are radically polymerizable compounds having two polymerizable unsaturated groups represented by.

In the method for producing the urethane compound of the present invention, the reaction between the hydroxyl group and the isocyanate group is a known method, that is, both reaction components of the compound having a hydroxyl group and the compound having an isocyanate group are mixed and the reaction is carried out at 40 to 100 ° A method of heating to C is available. As the solvent at the time of mixing, a monomer active to ionizing radiation can be used, but it is better to react in a solvent that is not reactive with an isocyanate group, or even if it is reacted in the absence of solvent. good. In addition, triethylamine, piperazine, triethanolamine, dibutyltin dilaurate, stannas octoate, stannas laurate, dioctyltin dilaurate and the like can be used in this reaction system for the purpose of promoting the reaction.

In addition, a radically polymerizable compound [D] composed of a (meth) acrylic acid ester having a hydroxyl group at the terminal and the first of the reaction
In the reaction system of the hydroxyl group and the isocyanate group between the diisocyanate prepolymer obtained in the step and the reaction system in the third step of the reaction, the acrylic acid ester group in the radically polymerizable compound [D] is protected. For this purpose, it is preferable to add a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, 2,6-di-t-butyl p-cresol or the like in an amount of about 10 to 1000 ppm.

[Operation of the present invention]

The novel urethane compound of the present invention represented by the general formula [I] has a (meth) acrylic acid ester group which is a radically polymerizable compound component represented by Q ¹ and Q ² in the compound, and "X". The expression where there is one in The presence of the polymerizable group represented by means that the urethane compound has good curing performance by irradiation with ionizing radiation, and the urethane bond and the ester bond which are also present in the component represented by X are different from each other. In addition to exhibiting good affinity for organic resins (particularly ester resins and urethane resins), these urethane bonds and ester bonds are highly advanced in the coating film formed by curing the above-mentioned urethane compounds. It is a factor which brings about the mechanical properties of (especially at the yield point and the breaking point).

The urethane compound of the present invention having the above-mentioned constitution is solely
Alternatively, it is a composition with other additives and compounding agents, and acts as an ionizing radiation-curable urethane compound or composition. For example, in the case of a composition with a reaction diluent, 100 parts by weight of the urethane compound is added. In contrast, the diluent is 1 to
A composition containing about 100 parts by weight is used. The reactive diluent in this case is, for example, a monomer having an ethylenically unsaturated bond in the molecule, for example, styrene-based monomers such as styrene and α-methylstyrene;
Methyl acrylate, 2-ethylhexyl acrylate, retoxyethyl acrylate, butoxyethyl acrylate,
Acrylic acid esters such as butyl acrylate, methoxybutyl acrylate, phenyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Methacrylic acid esters such as methoxyethyl methacrylate, ethoxyethyl methacrylate, phenyl methacrylate, and lauryl methacrylate; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; acrylic acid 2-
(N, N-dimethylamino) ethyl, methacrylic acid 2-
(N, N-dimethylamino) ethyl, (N, N-dimethylamino) methyl methacrylate, acrylic acid 2-
(N, N-dibenzylamino) ethyl, acrylic acid 2-
Substituted amino alcohol esters of unsaturated acids such as (N, N-diethylamino) propyl; N-methylcarbamoyloxyethyl acrylate, N-ethylcarbamoyloxyethyl acrylate, N-butylcarbamoyloxyethyl acrylate, N-phenyl Carbamoyloxyethyl acrylate, 2- (N-methylcarbamoyloxy)
Carbamoyloxyalkyl acrylates such as ethyl acrylate and 2-carbamoyloxypropyl acrylate; ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, triethylene It is possible to use one kind or a mixture of two or more kinds from polyfunctional compounds such as glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and ciethylene glycol dimethacrylate. .

The ionizing radiation-curable urethane comprising the novel urethane compound of the present invention or a composition containing the compound exhibits good affinity for both organic materials and inorganic materials, and has a strong cured film forming ability. Therefore, it can be widely used as a binder in various paints, an adhesive composition, a coating material composition, a molding composition for engineering plastics molded articles, a resist, and the like. For example, when used as a coating material composition to obtain a coating film, in the first step, a usual coating method for a substrate, that is, roll coating, gravure coating, fountain coating, curtain flow coating,
It is applied by a wire bar coating method or the like, and heating during this coating makes the coating even easier. In addition, it is preferable that a sensitizer is appropriately added and contained in the coating agent that is the above-mentioned composition for skin composite material. Then, in the second step performed, electron beams, α rays, β rays, γ are applied to the coating layer formed in the first step.
Although it is irradiated with ionizing radiation such as rays and ultraviolet rays, it is preferable to use an electron beam because of its high processing speed and high transparency. Cockloft-Walton type, Van de Graaff type, resonant transformer type, insulated core 50 to 1000 KeV, preferably 100 to 300 KeV emitted from various electron beam accelerators such as transformer type, linear type, dynamitron type and high frequency type.
It is preferable to use an electron beam having an energy in the range.

In addition, the method for producing a urethane compound of the present invention has an effect that a novel urethane compound having the above-mentioned effect can be obtained easily and surely.

〔Example〕

Hereinafter, specific configurations of the novel urethane compound and the method for producing the same of the present invention will be described based on examples.

Example 1 A 4-necked flask (capacity 5) equipped with a stirrer, a thermometer, a condenser and a dropping funnel was charged with 522 g of toluene diisocyanate, 1.0 g of dibutyltin dilaurate and 134 g of dimethylolpropionic acid, and the mixture was cooled to room temperature
The mixture was stirred at 2 ° C for 1 hour. Then, a polyester solution of 500 g of polycaprolantone type polyester [molecular weight 500, manufactured by Daicel Co., Ltd.] and 300 g of MEK was added dropwise, and after completion of the addition, the mixture was stirred for 2 hours in a heated state at 40 to 50 ° C. to be added to the reaction solution. After confirming that the dispersed dimethylolpropionic acid had disappeared and a transparent solution had been obtained, 268 g of hydroxyethyl methacrylate containing 0.2 g of benzoquinone was added dropwise and heated at 50-60 ° C. Stir for 1 hour. Subsequently, 156 g of glycidyl methacrylate containing 0.1 g of benzoquinone was added dropwise while maintaining the heating state, and the mixture was further stirred for 2 hours.

Finally, 0.5 g of hydroquinone was added to obtain a transparent solution.

Result of IR spectrum of the material obtained by removing the MEK by distillation under reduced pressure from the resulting clear solution, the isocyanate groups and from 3,600 to 3,500 ^-1 carboxy group of 2330Cm ^-1 had completely disappeared. Further, in the result of gel permeation chromatography (GPC), unreacted toluene diisocyanate, hydroxyethyl methacrylate and glycidyl methacrylate were not detected at all, and a substantially single peak was shown.

The result of IR analysis is Had absorption.

From the above results, the obtained substance is represented by the chemical structural formula [I] It was confirmed that the compound was an arethane compound [i] corresponding to.

Example 2 In a four-necked flask of the same type as that used in Example 1, 522 g of toluene diisocyanate, 0.1 g of dibutyltin dilaurate and 134 g of dimethylolpropionic acid were added.
And MEK (300 g) were charged, and the mixture was stirred at room temperature (22 ° C) for 1 hour. Next, polycaprolactone-based polyester [molecular weight 500, manufactured by Daicel Corporation] 500 g and MEK
After dropping the polyester solution with 300 g, 4
After stirring for 2 hours in a heated state of 0 to 50 ° C, it was confirmed that dimethylolpropionic acid dispersed in the reaction solution disappeared and a transparent solution was obtained.
268 g of hydroxyethyl methacrylate containing is added dropwise, and the mixture is stirred for 1 hour in a heated state of 50 to 60 ° C. Subsequently, the benzoquinone 0.1 was added while maintaining the heating state.
143 g of 2- (1-aziridinyl) ethylmethacrylate containing g was added dropwise, and stirring was continued for another 2 hours.

Finally, 0.3 g of hydroquinone was added to obtain a transparent solution.

Result of IR spectra of the resulting clear solution of a material to remove the MEK by distillation under reduced pressure, the carboxy group of the isocyanate groups and 3600～3500Cm ^-1 of 2330Cm ^-1 had completely disappeared. Further, in the result of gel permeation chromatography (GPC), unreacted toluene diisocyanate, hydroxyethyl methacrylate, and 2- (1-aziridinyl) ethyl methacrylate were not detected at all, and a substantially single peak was shown.

The result of IR analysis is Had absorption.

From the above results, the obtained substance is represented by the chemical structural formula [I] It was confirmed to be a urethane compound [ii] corresponding to

Example 3 A 4-necked flask (capacity 5) equipped with a stirrer, a thermometer, a condenser and a dropping funnel was charged with 435 g of toluene diisocyanate, 1.5 g of dibutyltin dilaurate, 201 g of dimethylolpropionic acid and 200 g of MEK, and the mixture was cooled to room temperature (22 ° C.). Stirred under C) for 1 hour. Then
Ptyrene adipate polyester [Molecular weight 2500:
Nitsuporan 3027, manufactured by Nippon Polyurethane Co., Ltd.] 12
A polyester solution of 50 g and MEK 800 g was dropped,
After completion of the dropping, the mixture was stirred while maintaining a heating condition of 40 to 50 ° C., and after 2 hours, 134 g of hydroxyethyl methacrylate containing 0.2 g of benzoquinone was added dropwise and further 50 to 50
The mixture was stirred at 60 ° C. for 1 hour. After that, 1 g of glycidyl methacrylate containing 0.2 g of benzoquinone
After dropping 56 g and stirring for 2 hours, 0.4 g of hydroquinone was finally added to obtain a transparent solution.

The IR spectrum of the substance obtained by removing MEK from the obtained transparent solution by vacuum distillation showed that the isocyanate group at 2330 cm ^-1 had disappeared. In addition, according to the result of gel permeation chromatography (GPC),
Unreacted toluene diisocyanate, hydroxyethyl methacrylate and glycidyl methacrylate were not detected at all, and a single peak was shown.

In addition, the result of IR analysis is Had absorption.

From the above results, the obtained substance is represented by the chemical structural formula [I] It was confirmed that the compound was a urethane compound [iii] corresponding to

Example 4 A 4-necked flask (capacity 5) equipped with a stirrer, a thermometer, a condenser and a dropping funnel was charged with 375 g of xylene diisocyanate, 1.0 g of dibutyltin dilaurate, 168 g of dimethylolpropionic acid and 300 g of MEK, and the mixture was cooled to room temperature (22 °). The mixture was stirred under C) for 2 hours. Next, butylene adipate polyester [Molecular weight 25
00: Nippon Poland 3027, Nippon Polyurethane Co., Ltd.
[Production] A polyester solution of 625 g and MEK 300 g was dropped, and after completion of the dropping, the mixture was stirred at a temperature of 40 to 50 ° C. for 2 hours, and the dimethylolpropionic acid dispersed in the reaction solution disappeared to give a transparent solution. After confirming that
58 g of hydroxyethyl acrylate containing 0.1 g of benzoquinone was added dropwise, and the mixture was stirred for 1 hour while heated at 50-60 ° C. After that, 108 g of 2 (1-aziridinyl) ethyl methacrylate containing 0.1 g of benzoquinone was added dropwise while maintaining the heating state, and the mixture was stirred for 1 hour.

Finally, 0.3 g of hydroquinone was added to obtain a transparent solution.

The IR spectrum of the substance obtained by removing MEK from the obtained transparent solution by vacuum distillation showed that the isocyanate group at 2330 cm ^-1 had disappeared. In addition, according to the result of gel permeation chromatography (GPC),
Unreacted xylene diisocyanate, hydroxyethyl methacrylate, and 2 (1-aziridinyl) ethyl methacrylate were not detected at all, and a single peak was shown.

The result of IR analysis is Had absorption.

From the above results, the obtained substance is represented by the chemical structural formula [I] It was confirmed that the urethane compound [iv] corresponds to

Experiment 1 Each of the urethane compounds after removal of the solvent obtained in each of the above Examples was hot-melt coated on a releasable surface of another release paper, dried and then electron beam irradiation apparatus [ESI: Electro Curtain CB200 / 50/30], acceleration voltage 175
After irradiation with KV and an irradiation dose of 10 Mrad, the coating film was cured and then peeled off from the release paper to obtain a film having a thickness of 50 μm.

The measured values of yield point, breaking point and elongation of the obtained film are shown in Table 1.

[Effect of the invention] The novel urethane compound of the present invention has good curing performance by irradiation with ionizing radiation, has a good affinity not only for organic substances but also for inorganic substances, and has a yield point and a breaking point. It has a tough coating film forming ability that exhibits excellent mechanical properties such as, and is used as a binder for various paints, adhesive composition, coating material composition, molding composition for engineering plastics molded products. It is a useful material that can be applied to an extremely wide range of applications such as products and resists.

Further, the method for producing a urethane compound of the present invention reliably and easily obtains the novel urethane compound having the above characteristics.

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Claims (2)

[Claims] 1. A general formula A new urethane compound represented by. 2. A diisocyanate compound [A], a polyester compound [B] having hydroxyl groups at both ends, and a carboxylic acid compound [C] having two hydroxyl groups in the molecule are reacted to give a compound of the formula A first step of obtaining a diisocyanate compound having an isocyanate group at both terminals represented by, a radically polymerizable compound consisting of the diisocyanate compound obtained in the first step and a (meth) acrylic acid ester having a hydroxyl group at the terminal [ D] while reacting while protecting the double bond in the radical polymerizable compound [D] to form a urethane bond between the isocyanate group of the diisocyanate compound and the hydroxyl group of the radical polymerizable compound, And a urethane compound obtained in the second step is reacted with glycidyl methacrylate or 2 (1-aziridinyl) ethyl methacrylate to obtain a urethane compound represented by the general formula: And a third step for obtaining the urethane compound represented by.