JP2816036B2 - Oligomers for antifogging compositions - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oligomer for an antifogging composition for forming an excellent antifogging film on the surface of a transparent product such as a glass or plastic molded product.

[0002]

2. Description of the Related Art In general, inorganic glass, polycarbonate resin, polymethyl methacrylate resin, polyvinyl chloride resin, cellulose ester resin, polystyrene resin,
Poly (diethylene glycol bisallyl carbonate)
Resins, etc., take advantage of their excellent transparency, window glass (glazing), helmet shield, ski goggles,
Widely used for underwater glasses, spectacle lenses, industrial protective glasses, mirrors and the like. However, these plastic products have a serious problem that when the surface temperature is lower than the dew point temperature, moisture in the atmosphere forms fine water droplets and condenses on the surface, impairing the visual field.

[0003] In order to solve this problem, various anti-fog processing methods have been proposed. For example, a surfactant is contained in the various resins, a hydrophilic polymer or a surfactant added thereto is applied to the surface of a dew-condensing synthetic resin, or a film is attached. .

[0004]

The coating thus obtained achieves the initial antifogging property, but swells the hydrophilic polymer or bleeds out the surfactant to reduce the hydrophilicity and thereby prevent the antifogging. However, there are drawbacks such as deterioration of the properties and inferior hardness, resulting in easy damage.

On the other hand, in general, in anti-fog processing, a film of a highly hydrophilic substance, that is, a substance having a small contact angle with water, is formed on the surface of a target plastic molded article, and condensed water droplets are formed as much as possible on the water film. And absorbing the moisture into the coating. However, a substance having high hydrophilicity has a low strength in a state of being wet with water, and easily breaks when rubbed strongly, or swells in water, loses planarity, becomes uneven, and further elutes . By adding a component that gives a crosslinked structure to the coating composition to make the composition three-dimensional, the water resistance can be improved, but in this case, the antifogging property is reduced. As described above, conventionally, a film satisfying all of the antifogging property, the surface scratch resistance (hardness), the water resistance, and the durability has not been obtained.

An object of the present invention is to provide an antifogging coating having excellent antifogging properties, surface scratch resistance (hardness), water resistance and durability on the surface of transparent products such as glass and plastic molded products. Is to be formed.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides an oligomer for an antifogging composition represented by the following general formula: (P ₁ and P ₂ are each a residue obtained by removing a hydroxyl group of an alcohol compound having one hydroxyl group, at least one of P ₁ and P ₂ contains an acryloyl group or a methacryloyl group, and P ₃ is A residue obtained by removing a hydroxyl group of a polyol compound, wherein at least one of P ₁ , P ₂ , and P ₃ contains a polyethylene oxide block — (CH ₂ CH ₂₀ ) _n — (n is 5 to 200; It is an integer.) T is a residue of the triisocyanate compound excluding the isocyanate group, and m is the number of 0 to 20 repeating units. ].

[0008]

According to the oligomer for an antifogging composition of the present invention,
Since a triisocyanate compound is used, (m + 1) side chains containing a P ₂ group can be introduced into the oligomer.
Such side chains were not found in the structure of the oligomer using the conventional diisocyanate compound.

On the premise of such a unique structure, the present inventors further incorporated a hydrophilic block-like molecular chain-(CH ₂ CH ₂ O) _n -and a hydrophobic block-like molecular chain into one molecule simultaneously, A nonionic surfactant effect was imparted to the molecular structure of the oligomer. This oligomer was emulsifying and dispersible or transparent and water-soluble.

[0010] At the same time, an acryloyl group or a methacryloyl group is a photoreactive group, since is contained in at least one of P ₁ and P _2, the multi-functional photoreactive groups are crosslinked structure Are formed densely, resulting in a dense three-dimensional crosslinked structure. Thereby, the film obtained by curing the antifogging composition containing the oligomer of the present invention becomes completely insoluble in water.

Furthermore, the above-mentioned cured film remains wettable with water due to the effect of the hydrophilic block-like molecular chains (polyethylene oxide block) contained in the oligomer. That is, the hydrophilic block-like molecular chains have the effect of spreading the water vapor reaching the dew point into a water film rather than a water droplet. By this action, the antifogging property of the coating is maintained. Also, such cured coatings have a small water absorption of less than 1%. Therefore, a decrease in strength due to water absorption of the coating is small. Furthermore, due to the effect of hydrogen bonding between the urethane bonding groups, there is abrasion resistance and the surface of the coating is hardly damaged. As described above, according to the present invention, it is possible to obtain a well-balanced cured film which satisfies all of antifogging property, surface scratch resistance, water resistance and durability.

The antifogging composition containing the oligomer of the present invention does not require a solvent drying step after application to a transparent plastic sheet injection-molded article or the like, and it is exposed to ultraviolet light in the air or to an inert gas. And can be cured by an electron beam or γ-ray.

According to such an antifogging composition, it is possible to adjust the wettability with respect to antifogging properties, the balance between hydrophobic and hydrophilic groups with respect to water resistance, the crosslink density, and the like. And abrasion resistance are obtained. Therefore, the obtained molded article shows good antifogging property in a breath test, a steam test, and the like, and has a higher surface scratch resistance, as shown in Examples described later. In particular, when a film made of this composition is applied to a polycarbonate molded product, its surface hardness is greatly improved, and it is excellent in water resistance. Even if it is immersed in running water for 10 hours, its anti-fogging property hardly decreases. As described above, according to the composition using the present invention, an extremely excellent anti-fog property can be imparted to a plastic molded article, so that a motorcycle helmet shield, ski goggles, and spectacle lenses that require anti-fog property are required. It is useful for underwater glasses, industrial glasses, windows for various vehicles, windows and mirrors for refrigerated vending machines, and the like.

The oligomer of the present invention is a component for adjusting wettability with respect to anti-fogging property, balance between hydrophobic and hydrophilic groups with respect to water resistance, cross-link density, and the like.

In order to balance hydrophilicity and hydrophobicity,
The ratio of the total molecular weight of the polyethylene oxide block — (CH ₂ CH ₂ O) _n — to the total molecular weight of the oligomer is preferably in the following range. 0.25 ≦ (molecular weight of polyethylene oxide block / total molecular weight of oligomer) ≦ 0.75

Here, when the above value is less than 0.25, the hydrophilicity is insufficient, and water droplets are condensed on the surface of the cured composition film, so that clouding easily occurs. On the other hand, when the above value exceeds 0.75, the water-swelling property of the cured film becomes large, so that the smoothness of the film is lost, the surface is not easily scratched, or the film is easily peeled off from the substrate.

The raw material monomer for introducing a P ₁ or P ₂ is an alcohol compound of the short-chain or long chain containing one group a hydroxyl group. Examples of the short-chain or long-chain alcohol compounds containing one hydroxyl group include (1) an acryloyl group-free and ethylene oxide chain (CH ₂ -CH _2-
O) alcohols containing no _n, (2) not containing an acryloyl group and an ethylene oxide chain (CH ₂ -CH ₂ -O) _n
(3) an alcohol containing an acryloyl group and not containing an ethylene oxide chain (CH ₂ —CH ₂ —O) _n ; (4) an alcohol containing an acryloyl group and containing an ethylene oxide chain (CH ₂ —CH ₂ -O) an alcohol containing _n ,
There are four types of monomers.

Here, n indicates the degree of polymerization of the polyethylene oxide chain (block). When the degree of polymerization n is less than 5, the hydrophilicity is insufficient, and when it exceeds 200, crystallinity is developed to be a solid, or it is difficult to dissolve in a monomer described later.

Specific examples of (1) include lower alcohols such as methanol, ethanol and 1,3-propanol;
There are higher alcohols such as lauryl alcohol and stearyl alcohol, and cellsolves such as methylcellsolve and ethylcellsolve.

Specific examples of (2) include monoalkoxy polyethylene glycol containing one hydroxyl group such as methoxy polyethylene glycol, exoxy polyethylene glycol, phenoxy polyethylene glycol, polyoxyethylene lauryl ether and polyoxyethylene cetyl ether; Polyoxyethylene monoalkoxy ether, polyethylene glycol-polypropylene glycol block copolymer monoalkoxy ether,
Etc.

Specific examples of (3) include (meth) acrylic esters containing one hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and polycaprolactone-modified esters. (Meth) acrylates and the like. Specific examples of (4) include polyethylene glycol mono (meth) acrylate and mono (meth) acrylate of a block copolymer of polyethylene glycol-polypropylene glycol. One or more of these alcohol compounds are used.

The raw material monomer for introducing P ₃ is a polyol compound (especially glycol compound). Specific examples of the glycol compound include ethylene glycol,
Hydrocarbon glycol compounds such as 1,2-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and isomers thereof, bisphenol A, etc. There is. Other polyol compounds include polyol compounds having hydroxyl groups at both terminals such as polytetramethylene glycol, polycaprolactone glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymer (pluronic nonionic glycol), and the like. is there. One or more of these polyol compounds are used.

The starting monomer for introducing T is a triisocyanate compound. As a specific example,
There are trimer isocyanurates of diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylene diisocyanate, hexamethylene diisocyanate and the like. Further, there are adducts of 1 mol of a triol compound such as trimethylolpropane and 3 mol of the above diisocyanate compound. Among these triisocyanate compounds, 1
Seeds or two or more kinds are used.

The value of the repeating unit m is from 0 to 20. m
If it exceeds 20, the oligomer will have a high viscosity or will be less soluble in other monomers or oligomers.

In producing the oligomer of the present invention, an alcohol compound is reacted with one terminal of a triisocyanate compound which is a raw material for the application. T (NCO) ₃ + P ₂ OH → T (NHCOOP ₂ ) (NCO) ₂

Next, to the reaction product containing the diisocyanate compound is added a polyol compound which is not more than 1/2 equivalent of the triisocyanate compound. T (NHCOOP ₂ ) (NCO) ₂ + P ₃ (OH) ₂

At this stage, an oligomer having an isocyanate group terminal is synthesized. Where T (NHCOOP ₂ ) (NCO) ₂ and P
_{Since 3} (OH) ₂ has two reactive ends,
For example, when an equimolar number is added, a polymer having a large molecular weight is generated. For this reason, preferably, the amount of the polyol compound to be added is not more 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 (O
H) Add ₂ . 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.

An example of the above synthesis method will be described. Triisocyanates: the _{T (NCO) 3 (m +} 1) mol of P ₂ OH (m + 1) mol was added to react a diisocyanate compound T (NHCOOP ₂₎ (NC
O) Synthesize ₂ . Glycol P ₃ (OH) ₂ is added to this reaction solution.
(m / 2 + 0.5) mol is added to synthesize an oligomer whose terminal is an 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.

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

Further, a catalyst for the urethanation reaction can be used if necessary. As such a catalyst, a known Lewis base such as triethylamine, triethanolamine, triethylenediamine, dibutyltin dilaurate, dibutyltin diacetate, or the like is used.

In addition to the oligomer, it is preferable to add an active energy ray-polymerizable monomer having a hydroxyl group to the antifogging composition in order to improve coating viscosity and the like. The function of this monomer is to adjust the viscosity of the composition, adjust the crosslink density of the cured film, prevent warpage due to curing shrinkage, and the like. The antifogging property of the urethane (meth) acrylate oligomer of the present invention is described above. Use to the extent that does not harm. As such a monomer, a mono (meth) acrylate compound containing at least one hydroxyl group, phosphoric acid group or carboxyl group,
Examples include di- or tri (meth) acrylate compounds.

Examples of the mono (meth) acrylate compound containing at least one hydroxyl group, phosphoric acid group or carboxyl group include 2-hydroxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
Hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, glycerol (meth) acrylate, caprolactone-modified (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol -Polypropylene glycol block copolymer mono (meth) acrylate,
Ethylene oxide-modified phthalic acid monoacrylate,
Ethylene oxide-propylene oxide modified phthalic acid monomethacrylate, epichlorohydrin modified butyl acrylate, epichlorohydrin modified diethylene glycol methacrylate, epichlorohydrin modified ethylene glycol dimethacrylate, epichlorohydrin modified ethylene glycol diacrylate, 3-
Chloro-2-hydroxypropyl methacrylate, 2
-Hydroxy-3-methacryloxypropyltrimethylammonium chloride, ethylene oxide-modified phosphate mono (meth) acrylate, ethylene oxide-modified phenoxylated phosphate mono (meth) acrylate, ethylene oxide-modified octoxylated phosphate mono (meth) acrylate, Examples include alkoxy acidic phosphoric acid mono (meth) acrylate ester, ethylene oxide-modified phthalic acid mono (meth) acrylate, and ethylene oxide-modified succinic acid mono (meth) acrylate.

The di- or tri (meth) acrylate compound containing at least one hydroxyl group, phosphoric acid group or carboxyl group is a component for adjusting the crosslink density, water absorption, wettability by the hydroxyl group, etc. It is used to such an extent that the antifogging property of the oligomer of the present invention is not impaired.

Examples of the di- or tri (meth) acrylate compound containing at least one hydroxyl group, phosphoric acid group or carboxyl group include triglycerol diacrylate, glycerol monoacrylate monomethacrylate, glycerol dimethacrylate, and pentane. Erythritol triacrylate, dipentaerythritol monohydroxypentaacrylate, epichlorohydrin-modified glycerol triacrylate, epichlorohydrin-modified 1,6-hexanediol diacrylate, epichlorohydrin-modified propylene glycol diacrylate, epichlorohydrin-modified trimethylolpropane triacrylate, epichlorohydrin-modified phthalic acid diacrylate Epoxy (meth) acrylate relay modified with epichlorohydrin S, ethylene oxide-modified phosphoric acid di (meth) acrylate, ethylene oxide-modified phosphoric acid tri (meth) acrylate, butane carboxylic acid di {(meth) acryloyloxy ethyl} ester, and the like. These di- or tri (meth) acrylate compounds containing one or more hydroxyl, phosphoric or carboxyl groups can be used alone or in combination of two or more.

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.

One or more photopolymerization initiators are used in combination. Further, a photopolymerization sensitizer may be used in combination with these photopolymerization initiators in order to adjust curability. The oligomer of the present invention is used as a main component of the antifogging composition. As described above, the antifogging composition is mixed with a polymerizable monomer having a hydroxyl group to such an extent that the antifogging property is not impaired, and the curability, surface scratch resistance, water resistance, etc. adjust. The composition may contain, in addition to the hydroxyl group-containing polymerizable monomer, a further small proportion of another UV-curable monomer or oligomer, and may further contain a leveling agent, a sensitizer, and an interface. Auxiliary agents such as an activator, a storage stabilizer, a heat stabilizer and a light stabilizer may be used in combination as needed.

The antifogging composition is a liquid having a relatively low viscosity, and can be applied without adding a solvent. This is extremely advantageous because a solvent drying step is not particularly required in the processing line. However, a solvent may be added for the purpose of further adjusting the film thickness and improving the specularity. At this time, as the solvent used, alcohols such as ethanol, isopropanol and n-butanol, and cellsolves such as methylcellsolve, ethylcellsolve and butylcellsolve are preferable.

The object of forming a film of the antifogging composition is a sheet of a transparent resin such as an inorganic glass, a polycarbonate resin, a polymethyl methacrylate resin, a polyvinyl chloride resin, a cellulose ester resin, and a polyallyl diglycol carbonate resin. Injection molded products, cast molded products and the like can be mentioned.

In particular, polycarbonate resins are excellent in not only transparency but also impact resistance, and therefore are often used for various face bodies and windows, and are most suitable as the object of the composition of the present invention. Also, glass and metal other than resin can be similarly provided with anti-fogging properties.

In order to form a film of the antifogging composition on the above-mentioned molded article, any coating method is employed. For example, spraying, dipping, flow coating, roll coating,
Any method such as a bar coating method, a curtain flow method, a spin coating method, and a screen printing method may be used. If the thickness of the coating is too thin, the anti-fogging property becomes insufficient.On the contrary, if it is too thick, peeling or embrittlement from the target substrate due to water swelling occurs and water resistance decreases, so It is preferably 20 μm, particularly preferably 10 to 20 μm. Upon painting, some pretreatment can be applied to improve the adhesion between the molded article and the coating, if necessary, and this is also preferable.

Immediately after coating or when set for several minutes, a cured film is formed by irradiating ultraviolet rays.
A high-pressure mercury lamp or the like that irradiates ultraviolet rays having a wavelength of 250 to 400 nm is suitable for the ultraviolet irradiation apparatus used. The standard irradiation conditions are preferably a lamp output of 80 to 120 w / cm, a lamp distance of 5 to 30 cm, and a conveyor speed of about 1 to 10 m / min. Further, it can be cured by an active energy ray other than ultraviolet irradiation, for example, an electron beam.

[0047]

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 1: Example of m = 3) In a 1-liter reactor equipped with a stirrer and a reflux condenser, "Mytec 215A" (trimethylolpropane, manufactured by Mitsubishi Kasei Corporation) was used as a triisocyanate. 3 mol of isophorone diisocyanate isocyanate adduct, molecular weight 800, solid content 75
% Ethyl acetate solution) was previously dissolved in 80 g of ethyl acetate. Perform N ₂ gas replacement while stirring,
The temperature was raised to 50 ° C. and kept constant. Next, (meta)
6.19 g of 2-hydroxyethyl acrylate (hereinafter abbreviated as HEA) as an acryloyl group-containing alcohol;
As a urethanization catalyst, a solution prepared by dissolving 0.84 g of dibutyltin dilaurate (hereinafter abbreviated as DBTDL) in 18 g of ethyl acetate was added, and the mixture was reacted at a temperature of 50 ° C. for 3 hours.

Next, as a glycol compound, "Newpol PE-68" (manufactured by NOF Corporation, ethylene oxide-
A solution prepared by dissolving 234.7 g of propylene oxide block copolymer, Mw8800 (hereinafter abbreviated as “PE-68”) in 234.7 g of ethyl acetate was added, and the mixture was reacted at a temperature of 50 ° C. for 2 hours.

Further, 117.3 g of the remaining “PE-68” and “HE
A solution of 3.09 g of "A" in 120.12 g of ethyl acetate was added, and the mixture was reacted at 60 ° C. for 5 hours. By IR measurement, 22
After confirming that the characteristic absorption of NCO appearing at 50 cm ^-1 had disappeared, the reaction was terminated, and the temperature was returned to 25 ° C. The reaction solution was placed in a vacuum dryer, kept at 50 ° C., and depressurized with a vacuum pump to remove ethyl acetate, thereby obtaining a white solid oligomer. This oligomer is designated as oligomer A.

(Synthesis Example 2: Example of m = 3) In the method shown in Synthesis Example 1, "Placcel A-5" (manufactured by Daicel Chemical Industries, Ltd., instead of "HEA") was used as the alcohol compound having one hydroxyl group. The reaction was carried out in exactly the same manner except that polymerization was carried out using a hydroxy group-containing caprolactone-modified acrylate, molecular weight 686), and the reaction solution was vacuum-dried in the same manner to obtain a white solid oligomer. This oligomer is referred to as oligomer B.

(Synthesis Example 3: Example where m = 3) According to the method shown in Synthesis Example 1, “PE-68” was used as a glycol compound.
Instead of "New Pole PE-64" (made by NOF Corporation,
(Ethylene oxide-propylene oxide block copolymer, Mw2400, hereinafter abbreviated as "PE-64"). Was obtained as a semi-solid oligomer. This oligomer is referred to as oligomer C.

(Synthesis Example 4: Example of m = 3) In a 1-liter reactor equipped with a stirrer and a reflux condenser, 56.89 g of "Mitec 215A" was previously dissolved as triisocyanate in 80 g of ethyl acetate. The solution was charged. The N ₂ gas was replaced while stirring, and the temperature was raised to 50 ° C. and kept constant.

Next, a solution prepared by dissolving 6.19 g of “HEA” as a long-chain alcohol compound containing one hydroxyl group and 0.84 g of “DBTDL” as a urethanization catalyst in 27 g of ethyl acetate was added. And reacted for 3 hours.
Next, a solution in which 234.7 g of “PE-68” was dissolved in 234.7 g of ethyl acetate was added as a glycol compound, and the mixture was reacted at a temperature of 50 ° C. for 2 hours.

Further, a solution prepared by dissolving 4.59 g of lauryl alcohol and 117.3 g of the remaining “PE-68” in 120.11 g of ethyl acetate was added, and the mixture was reacted at 60 ° C. for 5 hours. It was confirmed by IR measurement that the characteristic absorption of NCO at 2250 cm ^-1 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. This oligomer is referred to as oligomer D.

(Synthesis Example 5: Example in which m = 3) In the method shown in Synthesis Example 4, “HEA” and “HE” were used as alcohols having one hydroxyl group instead of lauryl alcohol.
A) is replaced by methoxypolyethylene glycol (molecular weight: 2000), and as a glycol compound, polytetramethylene glycol (manufactured by Mitsubishi Kasei,
The reaction was carried out in exactly the same manner except that polymerization was carried out using "PTMG650" (molecular weight: 650; hereinafter abbreviated as PTMG), and the reaction solution was vacuum-treated in the same manner to obtain a white solid oligomer. This oligomer is designated as oligomer E.

(Synthesis Example 6: Example of m = 20) In a 1-liter reactor equipped with a stirrer and a reflux condenser, 44.8 g of "Mitec 215A" was previously dissolved as a triisocyanate in 63 g of ethyl acetate. The solution was charged. The N ₂ gas was replaced while stirring, and the temperature was raised to 50 ° C. and kept constant.

Next, a solution prepared by dissolving 4.87 g of "HEA" as an alcohol having a (meth) acryloyl group and 0.3 g of "DBTDL" as a urethanization catalyst in 14.16 g of ethyl acetate was added. The reaction was performed for 3 hours. Next, as a glycol compound, a solution prepared by dissolving 67.2 g of “PE-64” in 67.2 g of ethyl acetate was added, and the temperature was maintained at 50 ° C.
The reaction was performed for 2 hours.

Further, 33.6 g of the remaining "PE-64" and "HE
A) A solution of 0.47 g in 34.97 g of ethyl acetate was added.
The reaction was maintained at 60 ° C. for 5 hours. 2250cm by IR measurement
^After confirming that the characteristic absorption of NCO at ^-1 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. This oligomer is designated as oligomer F. Table 1 shows the oligomer materials of each synthesis example.

[0060]

[Table 1]

Example 1 100 parts by weight of the urethane acrylate oligomer A of Synthesis Example 1, "Aronix M-305"
50 parts by weight (pentaerythritol triacrylate, manufactured by Toa Gosei Chemical Co., Ltd.), "Light ester BP-4EA"
50 parts by weight of (diacrylate of ethylene oxide-modified bisphenol A) and 5 parts by weight of "Darocur 1173" were mixed to obtain a colorless and transparent solventless photosensitive solution. This photosensitive solution was applied to a polycarbonate film having a thickness of 50 μm and adjusted to a thickness of 7 μm using an applicator, and cured by an ultraviolet irradiation device. The UV irradiator is “ORM-2077A” (manufactured by Oak Manufacturing Co., Ltd.) (High pressure mercury lamp 80W / cm * 3
Lamp base, lamp distance 15 cm) was used. UV integrated light quantity is 50
0 mJ / cm ² .

Using the surface-treated film thus obtained, a breath test, a direct steam test, a rubbing test, a water resistance test, and a durability test were performed under the following conditions. The results are shown in the table. Breath test: At room temperature, a sample is stuck to the side (outside) of a beaker containing ice water, and the test is performed by blowing on the surface of the beaker with the coating surface facing outward. Direct steam test ─── Place the sample on a 40 ° C water bath and test by applying direct steam. Rubbing test (1) Using a rubbing tester manufactured by Ohira Rika Kogyo Co., Ltd., rubbing 100 times back and forth with a load of 1 kg using a wet felt as an abrasive, and then directly carry out a steam test. Water resistance test ① After soaking in water for 1 hour, perform a direct steam test. Durability test ① Attached to the mirror in the bathroom of the Hayakawa Rubber employee dormitory in Minamitejo-cho, Fukuyama City, and tested for one month.

Examples 2 to 8 As shown in Example 1, the urethane acrylate oligomers A to F obtained in Synthesis Examples 1 to 6 each contained a mono (meth) acrylate compound containing at least one hydroxyl group, And a photopolymerization initiator and a di- or tri (meth) acrylate compound containing at least one of the following were blended to obtain a solventless photosensitive solution. Then, in the same manner as in Example 1, each photosensitive liquid was cured to obtain a surface-treated film. Subsequently, each surface-treated film was subjected to a breath test, a direct steam test, a rubbing test, a water resistance test, and a durability test. The results are shown in the table.

The abbreviations in the table are as follows. PETA: pentaerythritol triacrylate,
"Aronix M-305" BP-4EA: "Light ester BP-4EA" HEMA: 2-hydroxyethyl methacrylate D-1173: "Darocur 1173"

[0065]

[Table 2]

[0066]

[Table 3]

(Comparative Examples 1 to 5) Commercially available urethane acrylate oligomers 1 and 2 were compared with the mono (meth)
An acrylate compound, a di- or tri (meth) acrylate compound and a photopolymerization initiator were blended, and a breath test, a direct steam test, a rubbing test, a water resistance test, and a durability test were performed in the same manner as in Example 1. Table 4 shows the results.

The urethane acrylate oligomers 1 and 2 are as follows. Oligomer 1: "Aronix M-1200" manufactured by Toa Gosei Co., Ltd., bifunctional non-yellowing type urethane acrylate oligomer Oligomer 2: "Shinko 3000B" manufactured by Nippon Gohsei Co., Ltd. light ester 9EG-A "manufactured by Kyoeisha Yushi Co., _{Ltd.: H 2 C = CH-COO} - (CH 2 CH 2 O) 9 -COCH = CH 2

[0069]

[Table 4]

[0070]

As is apparent from the above examples, when the antifogging composition containing the oligomer of the present invention as a main component is prepared, the surface of the transparent product has antifogging properties and surface scratch resistance. A film excellent in all properties, water resistance and durability can be formed.

Continued on the front page (58) Fields surveyed (Int.Cl. ⁶ , DB name) C09K 3/18 C08F 299/06 C08G 18/83 C09D 5/00 C09D 175/08 WPI / L (QUESTEL)

Claims (2)

(57) [Claims] An oligomer for an antifogging composition represented by the following general formula: (P ₁ and P ₂ are each a residue obtained by removing a hydroxyl group of an alcohol compound having one hydroxyl group, at least one of P ₁ and P ₂ contains an acryloyl group or a methacryloyl group, and P ₃ is A residue obtained by removing a hydroxyl group of a polyol compound, wherein at least one of P ₁ , P ₂ , and P ₃ contains a polyethylene oxide block — (CH ₂ CH ₂₀ ) _n — (n is 5 to 200; It is an integer.) T is a residue of the triisocyanate compound excluding the isocyanate group, and m is the number of 0 to 20 repeating units. ] 2. The antifogging composition according to claim 1, wherein at least one of P ₁ , P ₂ and P ₃ has an ethylene oxide-propylene oxide block copolymer portion represented by the following general formula. Oligomers. -(CH ₂ CH ₂ 0) _a- [CH ₂ CH (CH ₃ ) O] _b- (CH ₂ CH ₂ O) _c- [a is an integer of 5 to 200, b is an integer of 5 to 400, c is It is an integer of 5-200. ]