JP2849240B2 - Active energy ray-curable oligomer for antifogging composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable oligomer used as a binder for a printing ink, a coating agent, a potting agent, a resist agent and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Energy saving, non-pollution, time reduction,
Instead of organic solvent solution type, aqueous solution type coating materials, thermosetting resins, moisture-curing resins, etc., they can be cured using active energy rays, especially ultraviolet rays or electron beams, for reasons such as production cost reduction. Solvent-type liquid resins have come to be used. This includes urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and the like.

[0003] In particular, urethane (meth) acrylate has been actively developed with excellent properties such as strength, elongation, and abrasion resistance. The urethane (meth) acrylate oligomer had a structure represented by the formula (2), which was polymerized using a diisocyanate compound, a glycol compound and a (meth) acrylate ester having one hydroxyl group. P ₄ -D- (P ₅ -D) n-P ₄ ... (2) n ≧ 1 D: Residue excluding isocyanate group of diisocyanate compound P ₄ : One hydroxyl group-containing (meth) Residue excluding hydroxyl group of acrylate ester P ₅ : Residue excluding hydroxyl group of glycol compound

In the general formula (2), the starting monomer for introducing D is a diisocyanate compound. Specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
Examples include isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.

[0005] In the general formula (2), the raw material monomer for introducing P ₄ is a hydroxyl group containing one group (meth) acrylate ester. Contains one hydroxyl group (meta)
Specific examples of acrylate esters include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and pentaerythritol tri (meth) acrylate.
There are acrylate, trimethylolpropane di (meth) acrylate and the like.

[0006] raw material monomer for introducing P ₅ is a glycol compound. Specific examples of the glycol compound include ethylene glycol, 1.4-butanediol, 1.6
-Aliphatic glycols such as hexanediol, alicyclic glycols such as dioxane glycol and spiro glycol, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polycarbonate diol, polyester polyol, polyether polyol, 1,2-polybutadiene glycol , 1,4-polybutadiene glycol and the like.

[0007]

These conventional active energy ray-curable urethane (meth) acrylate oligomers are used as active energy ray-curable binders for printing inks, various coating agents, potting agents, resist agents and the like. However, at that time, it was not possible to simultaneously satisfy the fast curing property, surface scratch resistance, low curing shrinkage property, bending strength and the like required at that time. That is, in the case of a conventional urethane (meth) acrylate containing two (meth) acryloyl groups, each of the two terminals has a crosslinkable (meth) acryloyl group at each end, and has low curing shrinkage and bending strength. Although it was possible to obtain a cured film having a certain quality, it was inferior in quick curing and surface scratch resistance. In addition, when three to six (meth) acryloyl groups are contained, a plurality of crosslinkable (meth) acryloyl groups are provided at both ends, so that quick curing property and surface strength are satisfied. However, hardening shrinkage is increased, and a harder and more brittle hardening material is obtained, which is inferior in bending resistance. Since these required properties are incompatible with each other, it was impossible to satisfy them at the same time with a conventional oligomer. In addition, it was difficult to obtain anti-fogging property for preventing fogging particularly in a cured film.

It is an object of the present invention to provide an active energy ray-curing type which has the properties of fast curing, surface scratch resistance, low curing shrinkage, bending strength, surface activity and the like, and has excellent antifogging properties. To provide oligomers.

[0009]

According to the present invention, there is provided a compound represented by the following general formula:
The present invention relates to an active energy ray-curable oligomer for an anti-fog composition represented by (1).

Embedded image

[P ₁ is a residue excluding a hydroxyl group of an alcohol compound having one hydroxyl group containing an acryloyl group or a methacryloyl group, and P ₂ is a residue not containing an acryloyl group or a methacryloyl group. Alcohol compound having a hydroxyl group of a monoalkoxy polyethylene glycol, a monoalkoxy polypropylene glycol, a monoalkoxypolybutylene glycol, a monoalkoxy ether of polyoxyethylene and a monoalkoxy ether of a block copolymer of polyethylene glycol-polypropylene glycol. a group given by removing hydroxyl groups of one or more alcohol compound selected from the group consisting residual P ₃ is a group given by removing hydroxyl groups of the polyol compound, T is, excluding the isocyanate groups of the triisocyanate compound In it, m is a number of repetitive units of 0 to 20. ]

[0011]

According to the active energy ray-curable oligomer of the present invention, a triisocyanate compound is used. Therefore, (m + 1) side chains containing a P ₂ group can be introduced into the oligomer. Moreover, as P ₂ , a residue excluding the hydroxyl group of an alcohol compound having one hydroxyl group, which does not contain an acryloyl group or a methacryloyl group, was used.

At the same time, by introducing a (meth) acryloyl group at both ends (P ₁ ), performances such as fast curing property, surface scratch resistance, low curing shrinkage property, and bending strength are improved. At the same time, they were satisfied and succeeded in obtaining an active energy ray-curable urethane (meth) acrylate having a surfactant effect. This makes it particularly anti-fog,
We succeeded in introducing antistatic functionality.

In order to produce the above-mentioned oligomer, preferably, one end of a triisocyanate compound as a starting material is reacted with an alcohol compound containing no acryloyl group or methacryloyl group. T (NCO) ₃ + P ₂ OH → T (NHCOOP ₂ ) (NCO) ₂

[0014] Next, to the reaction product containing the diisocyanate compound, a polyol compound of 1/2 equivalent or less of the triisocyanate compound is added. T (NHCOOP ₂ ) (NCO) ₂ + P ₃ (OH) ₂ → T (NCO) (NHCOOP ₂ ) -NHCOO-P ₃ -OCONH-T (NCO) (NHCOOP ₂ )

At this stage, an oligomer having an isocyanate group terminal is synthesized. Where T (NHCOOP ₂ ) (NHCOOH) ₂
And P ₃ (OH) ₂ both have two reactive terminals, so that, for example, if they are added in equimolar numbers, a polymer having a large molecular weight will be produced. For this reason, in the present invention, the amount of the polyol compound to be added is set to be equal to or less than 1/2 equivalent of the triisocyanate compound, thereby preventing the formation of a polymer having a large molecular weight.

Then, an alcohol compound P ₁ OH having one hydroxyl group and a polyol compound P
₃ (OH) ₂ is added. Therefore, the polyol compound and the alcohol compound react competitively with the isocyanate terminal of the oligomer. At this time, when the alcohol compound binds to the isocyanate terminal, the chain reaction stops.

According to such a production method, the molecular weight in the oligomer is not distributed to the larger one, and the viscosity of the coating solution in which the oligomer is dissolved is not excessively increased. Accordingly, the moldability of such a coating solution is improved, and mixing with another monomer or oligomer becomes easy.

Preferably, at least one of P ₁ , P ₂ and P ₃ has a molecular weight of 500 or more and 3000 or less. P ₁ , P ₂ ,
If the molecular weight of P ₃ is all 500 or less, the coating after curing the coating solution containing the oligomers of the present invention becomes brittle. If it exceeds 3000, the reactivity during curing decreases.

In the general formula (1), the raw material monomer for introducing P ₂ is an alcohol containing no acryloyl group or methacryloyl group, and the raw material monomer for introducing P ₁ is acryloyl group or methacryloyl group. Is an alcohol containing groups.

In the present invention, in order to further improve the antifogging property, an alcohol containing no acryloyl group or methacryloyl group may be substituted with a monohydric alcohol such as methoxypolyethylene glycol, ethoxypolyethyleneglycol or phenoxypolyethyleneglycol. Monoalkoxypolybutylene glycol such as alkoxypolyethylene glycol, methoxypolypropyleneglycol, ethoxypolypropyleneglycol, phenoxypolypropyleneglycol, etc. containing one hydroxyl group; monoalkoxypolybutyleneglycol such as monoethoxypolybutyleneglycol, monobutoxypolybutyleneglycol, polyoxy Monoalkoxy ether of ethylene,
Monoalkoxy ether of a block copolymer of polyethylene glycol-polypropylene glycol.

Specific examples of the alcohol having an acryloyl group or a methacryloyl group include (meth) acrylic acid having one hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Esters, polycaprolactone-modified
(Meth) acrylic acid ester, polyethylene glycol mono (meth) acrylate, polyethylene glycol-
Mono- (meth) acrylate of a block copolymer of polypropylene glycol, and the like.

[0022] In the general formula (1), as the raw material monomer P ₃ (OH) ₂ for introducing P _3, but glycol compounds are preferred, it is also possible to use a polyol compound having three or more hydroxyl groups.

Examples of the glycol compound include hydrocarbon glycol compounds such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, dioxane glycol, and the like. And cyclic glycols such as spiro glycol.

Other polyol compounds include polytetramethylene glycol, polycaprolactone glycol, polycarbonate glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymer (pluronic nonionic glycol), polyester polyol, and hydroxyl group. There are polyol compounds having hydroxyl groups at both terminals, such as 1,2-polybutadiene, 1,4-polybutadiene, rubber-based glycols such as ethylene-propylene copolymers, bisphenol A, and cyclohexane dimethanol containing ethylene-propylene glycol at the terminals. One or more of these compounds are used as P ₃ (OH) ₂ .

In the general formula (1), the starting monomer for introducing T is a triisocyanate compound. Specific examples thereof include 2,4-tolylene diisocyanate,
Of diisocyanates such as 6-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexanebis (methyl isocyanate), diphenylmethane-4,4'-diisocyanate and 4,4-methylenebis (cyclohexyl isocyanate) There are trimer isocyanurates. Further, there is an adduct of 1 mol of a triol compound such as trimethylolpropane or glycerin with 3 mol of the above diisocyanate compound. One or more of these triisocyanate compounds are used.

In the general formula (1), when m exceeds 20,
The coating liquid becomes high in viscosity and is hardly compatible with other monomers or oligomers.

One example of the active energy ray-curable oligomer of the present invention is shown below. Triisocyanate: T (NCO) ₃ (m + 1)
(M + 1) mole of P ₂ OH is added to the mole and reacted to synthesize a diisocyanate compound T (NHCOOP ₂ ) (NCO) ₂ . To this reaction mixture, (m / 2 + 0.5) mol of glycol P ₃ (OH) ₂ is added to synthesize an oligomer having a terminal isocyanate group.

The remaining glycol P ₃ (OH) ₂ is added to the reaction mixture.
(M / 2-0.5) mol and 2 mol of P ₁ (OH) are added and reacted to obtain the desired oligomer. Of course, in this case, m ≧ 1 must be satisfied.

When m = 0, 1 mol of triisocyanate
After reacting 2 mols of P ₁ OH with ₁ l, ₁ mol of P ₂ OH
The reaction is carried out, or a total of 3 mols of P ₁ OH and P ₂ OH are reacted simultaneously.

When synthesizing the oligomer of the present invention, a minimum necessary solvent can be used for adjusting the viscosity, controlling the molecular weight, and adjusting the compatibility of the raw materials. As the solvent, ethyl acetate,
Methyl ethyl ketone, toluene, benzene, dimethylformamide, dimethylsulfoxide, etc., alone or a mixture thereof.

The catalyst for the urethane-forming reaction can be used as needed. As such a catalyst, a known Lewis base such as triethylamine, triethanolamine, triethylenediamine, dibutyltin dilaurate, dibutyltin diacetate, or the like is used.

An active energy ray-polymerizable monomer can be added to the oligomer of the present invention to improve coating viscosity.

When an ultraviolet ray is used as the active energy ray, it is necessary to add a photopolymerization initiator which generates a radical by irradiating the ultraviolet ray and starts the polymerization of the (meth) acryloyl group. However, it is not particularly necessary for curing with active energy rays other than ultraviolet rays, for example, electron beams or cobalt γ rays.

As the photopolymerization initiator, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1
-One, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2- Benzoin based compounds such as dimethoxy-2-phenylacetophenone, benzophenone, hydroxybenzophenone, 3,
Benzophenones such as 3-dimethyl-4-methoxybenzophenone; thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and isopropylthioxanthone; 1-phenyl -1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl and the like.

The photopolymerization initiator is used alone or in combination of two or more. Further, a photopolymerization sensitizer may be used in combination with these photopolymerization initiators in order to adjust curability. When the oligomer of the present invention is cured, a small proportion of another UV-curable monomer or oligomer may be further blended, and a leveling agent, a colorant, a sensitizer, a surfactant, and a storage stabilizer may be used. If necessary, auxiliary agents such as a heat stabilizer and a light stabilizer may be used in combination.

[0036]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not particularly limited to the following examples.

(Synthesis Example) A solution prepared by dissolving 106.67 g of "Mitec 215 A" in 213 g of ethyl acetate as triisocyanate was placed in a reactor having an IL volume equipped with a stirrer and a reflux condenser. Perform N ₂ gas replacement while stirring, raise the temperature to 50 ° C,
Kept constant. Next, a solution prepared by dissolving 200 g of methoxypolyethylene glycol (molecular weight: 2,000), which is an alcohol containing no acryloyl group or methacryloyl group, and 0.53 g of DBTDL as a urethane-forming catalyst in 448 g of ethyl acetate was added. The temperature of the reaction solution was kept at 50 ° C., and the reaction was performed for 3 hours. Further, a solution prepared by dissolving 137.2 g of “Placcel FA-5” in 137.9 g of ethyl acetate was added, and the mixture was reacted at 60 ° C. for 5 hours.

According to IR measurement, NCO appearing at 2250 cm ^-1
After confirming that the characteristic absorption of the group had disappeared, the reaction was terminated, and the temperature was returned to 25 ° C. This reaction solution was placed in a vacuum vessel, kept at 50 ° C., and depressurized with a vacuum pump to remove ethyl acetate, thereby obtaining a white solid oligomer. Table 1 summarizes the components of this oligomer.

[0039]

[Table 1]

The following experiment was conducted using the oligomer according to the above synthesis example. (Example 1) 100 parts by weight of a urethane acrylate oligomer of a synthesis example,
Pentaerythritol triacrylate (PETA) 1
0 parts by weight, 10 parts by weight of di (acryloyltetraethylene glycol) adduct of bisphenol A (BP-4EA), 2-hydroxyethyl methacrylate (HEM)
A) 10 parts by weight, "Darocur 1173" (manufactured by Merck,
2-hydroxy-2-methyl-1-phenylpropane-
1-one) and 6.5 parts by weight were mixed to obtain a colorless and transparent solventless photosensitive solution. This photosensitive solution is applied to a polycarbonate film having a thickness of 50 μm by using an applicator.
It was adjusted to a thickness and cured by an ultraviolet irradiation device. The UV irradiation device is "ORM-2077A" manufactured by Oak Manufacturing Co., Ltd.
(High pressure mercury lamp 80 w / cm, 3 lamps, lamp distance 15 cm) was used. The integrated amount of ultraviolet light is 100 mJ / cm ² .

Using the surface-treated film thus obtained, under the following conditions, curability, surface scratching property, curing shrinkage property, bending property and anti-fog property were observed. Table 2 shows the results.

The evaluation method of each evaluation item is as follows. Curability: Determined by the presence or absence of surface finger tack on the cured film. 〇 means no tack, × means tack remains. Surface scratching property: Using a rubbing tester manufactured by Taihei Rika Kogyo Co., Ltd., using felt as an abrasive, with a load of 1 kg
0 reciprocation, and then the degree of surface damage was visually observed. Curing shrinkage: 2 g of the photosensitive solution was potted on a 100 × 30 × 1 m / m 2 polycarbonate film, irradiated with ultraviolet rays, and the degree of warping after curing was observed. Bendability: Performed in accordance with JIS-K-5400 (bending resistance). (Diameter of mandrel: 8 m / m) Anti-fogging property: The sample was placed on a water bath at 40 ° C., and steam was directly applied to the coated surface for 1 hour to observe the occurrence of fogging.

[0043]

[Table 2]

[Comparative Example] The urethane acrylate oligomer 1, which is currently commercially available
To 2 was added a photopolymerization initiator shown in Table 3 to prepare a photosensitive solution. The curability, surface scratching property, curing shrinkage property, bending property and antifogging property of this photosensitive liquid were measured in the same manner as in Example 1. Table 3 shows the measurement results.

The urethane acrylate oligomers 1 and 2 are as follows. Oligomer 1: "Aronix M-1200" (manufactured by Toa Gosei Chemical Co., Ltd., bifunctional, non-yellowing type urethane acrylate oligomer) Oligomer 2: "Shikko 1700 B" (Nippon Synthetic Chemical Co., Ltd.)
Manufactured, bifunctional, non-yellowing type urethane acrylate oligomer)

[0046]

[Table 3]

As is clear from Table 2, the urethane acrylate oligomer according to the embodiment of the present invention simultaneously improves various properties such as fast curing property, surface scratch resistance, low curing shrinkage property and bending strength. Can be simultaneously excellent in anti-fog properties.

[Brief description of the drawings]

FIG. 1 is a diagram showing a gel permeation chromatograph of an oligomer according to an example of the present invention.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 18/67 C08G 18/72 C08F 299/06 C09K 3/18

Claims (1)

(57) [Claims] 1. An active energy ray-curable oligomer for an anti-fog composition represented by the following general formula (1). Embedded image [P ₁ is a residue containing an acryloyl group or a methacryloyl group, excluding a hydroxyl group of an alcohol compound having one hydroxyl group, and P ₂ is a single hydroxyl group containing no acryloyl group or methacryloyl group. An alcohol compound having the formula:
At least one alcohol compound selected from the group consisting of monoalkoxy polyethylene glycol, monoalkoxy polypropylene glycol, monoalkoxy polybutylene glycol, monoalkoxy ether of polyoxyethylene, and monoalkoxy ether of block copolymer of polyethylene glycol-polypropylene glycol P ₃ is a residue of the polyol compound excluding the hydroxyl group, T is a residue of the triisocyanate compound excluding the isocyanate group, and m is a repeating group of 0 to 20. The number of units. ]