JPH0517740A - Oligomer for antifogging composition - Google Patents

Abstract

PURPOSE:To provide the subject oligomer giving excellent antifogging properties, hardness, etc., to the surfaces of transparent products produced from glass, plastics, etc. CONSTITUTION:An oligomer of formula I {P1, P2 are the OH group-removed residual group of an alcohol compound having single OH group, either of the P1 and P2 containing an acryloyl or methacryloyl group; P3 is the OH group- removed residue of a polyol compound; one or more of P1-P3 contain a polyethylene oxide block [of formula II ((n) is 5-200)]; T is the isocyanate group-removed residue of a triisocyanate compound; (m) is a repeating unit number of 0-20}. The oligomer of formula I is produced e.g. by reacting (m/2 + 0.5) moles of a polyol compound with a reaction solution of (m + 1) moles (m>=1) of the triisocyanate compound with (m + 1) moles of an alcohol compound, and subsequently reacting the produced oligomer having isocyanate groups at the molecular ends with (m/2-0.5) moles of the remained polyol compound and 2 moles of the alcohol compound.

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 transparent products such as glass and plastic molded products.

[0002]

2. Description of the Related Art Generally, inorganic glass, polycarbonate resin, polymethylmethacrylate resin, polyvinyl chloride resin, cellulose ester resin, polystyrene resin,
Poly (diethylene glycol bisallyl carbonate)
Taking advantage of its excellent transparency, resins and other materials are used for window glass (glazing), helmet shields, ski goggles,
Widely used for underwater eyeglasses, eyeglass lenses, industrial protective eyeglasses, mirrors and the like. However, these plastic products have a serious problem that when the surface temperature becomes lower than the dew point temperature, moisture in the atmosphere becomes fine water droplets which condense on the surface and impair the visual field.

In order to solve this problem, various antifog processing methods have been proposed. For example, a surfactant is contained in the various resins, or a hydrophilic polymer or a mixture of a surfactant and a hydrophilic polymer is applied to the surface of the dew-condensable synthetic resin, or a film is attached. .

[0004]

The film thus obtained achieves the initial anti-fogging property, but the hydrophilic polymer swells or the surfactant flows out, and the hydrophilicity is lowered to prevent the anti-fogging property. However, there are drawbacks such as deterioration of properties and easy scratching due to poor hardness.

On the other hand, generally, in anti-fogging processing, a film of a substance having a high hydrophilicity, 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 into a water film as much as possible. There is a method of making the film into a shape and absorbing this moisture into the film. However, a highly hydrophilic substance has low strength when wet with water, and is easily broken when rubbed strongly, swells in water and loses planarity and becomes uneven, and is further eluted. . Although water resistance can be improved by adding a component that imparts a cross-linking structure to the coating composition to make it three-dimensional, the antifogging property is lowered on the contrary. As described above, hitherto, a coating 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 film excellent in antifogging property, surface scratch resistance (hardness), water resistance and durability on the surface of transparent products such as glass and plastic molded products. It is to be able to form.

[0007]

The present invention provides an oligomer for an antifogging composition represented by the following general formula. (P ₁ and P ₂ are residues except for the hydroxyl group of the alcohol compound having one hydroxyl group respectively, at least one of P ₁ and P ₂ contains an acryloyl group or a methacryloyl group, P ₃ is, It is a residue of a polyol compound excluding hydroxyl groups, and at least one of P ₁ , P ₂ and P ₃ contains a polyethylene oxide block — (CH ₂ CH ₂ 0) _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 repeating units of 0 to 20. ] It is related to.

[0008]

According to the oligomer for antifogging composition of the present invention,
Since a triisocyanate compound is used, it is possible to introduce (m + 1) side chains containing P ₂ groups into the oligomer.
Such a side chain is not found in the structure of an oligomer using a conventional diisocyanate compound.

On the premise of such a unique structure, the present inventor has further incorporated a hydrophilic block-like molecular chain-(CH ₂ CH ₂ O) _n --and a hydrophobic block-like molecular chain into one molecule at the same time, A nonionic surfactant effect was added to the molecular structure of the oligomer. The oligomer was emulsified and dispersible or transparent and water soluble.

At the same time, since an acryloyl group or a methacryloyl group which is a photoreactive group is contained in at least one of P ₁ and P ₂ , the polyfunctional photoreactive group has a crosslinked structure. Are densely formed, resulting in a dense three-dimensional crosslinked structure. As a result, the coating film obtained by curing the antifogging composition containing the oligomer of the present invention becomes completely insoluble in water.

Moreover, due to the effect of the hydrophilic block-like molecular chain (polyethylene oxide block) contained in the oligomer, the above-mentioned film after curing remains wettable to water. That is, the hydrophilic block-like molecular chain has the effect of spreading the vapor reaching the dew point in the form of a water film rather than in the form of water drops. By this action, the antifogging property of the coating film is maintained. Moreover, such a cured film has a small water absorption of 1% or less. Therefore, the strength of the film is less likely to decrease due to water absorption. Furthermore, due to the effect of hydrogen bonding between urethane bonding groups, it has abrasion resistance and the surface of the coating is not easily scratched. Thus, according to the present invention, it is possible to obtain a well-balanced cured coating that satisfies all of the antifogging property, the surface scratch resistance, the water resistance and the durability.

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

According to such an antifogging composition, the wettability related to the antifogging property, the balance between the hydrophobic group and the hydrophilic group related to the water resistance, the crosslink density, etc. can be adjusted, so that the excellent antifogging property is obtained. And wear resistance is obtained. Therefore, the obtained processed molded article exhibits good anti-fog property in a breath test, a steam test, etc., and further has a surface scratch resistance as shown in Examples described later. In particular, when a coating film of this composition is applied to a polycarbonate molded article, the surface hardness thereof is significantly improved and the water resistance is excellent, and even if it is immersed in running water for 10 hours, its antifogging property is hardly reduced. Thus, according to the composition utilizing the present invention, since it is possible to impart extremely excellent anti-fog property to the plastic molded product, motorcycle helmet shields, ski goggles, spectacle lenses which are required to have anti-fog property. It is useful for underwater spectacles, industrial spectacles, windows for various vehicles, windows for refrigerated vending machines, mirrors, and the like.

The oligomer of the present invention is a component for adjusting the wettability with respect to antifogging property, the balance between hydrophobic group and hydrophilic group with respect to water resistance, crosslink 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

If the above value is less than 0.25, the hydrophilicity is insufficient, and water droplets are likely to condense on the surface of the cured film of the composition to cause fogging. On the other hand, when the above value exceeds 0.75, the water swelling property of the main cured film becomes large, so that the smoothness of the film is lost, the surface scratchability is deteriorated, or the film is easily peeled from the substrate.

The raw material monomer for introducing P ₁ or P ₂ is a short-chain or long-chain alcohol compound containing one hydroxyl group. The alcohol compound of the short-chain or long chain containing one group a hydroxyl group, (1) not containing an acryloyl group and an 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
Containing alcohol, (3) an alcohol containing an acryloyl group and not containing an ethylene oxide chain (CH ₂ —CH ₂ —O) _n , (4) an acryloyl group containing and containing an ethylene oxide chain (CH ₂ —CH ₂ -O) an alcohol containing _n ,
There are four types of monomers.

Here, n represents the degree of polymerization of the polyethylene oxide chain (block). When the degree of polymerization n is less than 5, hydrophilicity is insufficient, and when it exceeds 200, crystallinity develops to become 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,
Examples include higher alcohols such as lauryl alcohol and stearyl alcohol, and cellsolves such as methylcellosolve and ethylcellosolve.

As a specific example of (2), a monoalkoxy polyethylene glycol having one hydroxyl group, such as methoxy polyethylene glycol, exoxy polyethylene glycol, phenoxy polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, Polyoxyethylene monoalkoxy ether, polyethylene glycol-polypropylene glycol block copolymer monoalkoxy ether,
Etc.

Specific examples of (3) include (meth) acrylic acid esters containing one hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and polycaprolactone-modified ones. (Meth) acrylic acid ester and the like. Specific examples of (4) include polyethylene glycol mono (meth) acrylate and polyethylene glycol-polypropylene glycol block copolymer mono (meth) acrylate. Among these alcohol compounds, 1 type (s) or 2 or more types are used.

The raw material monomer for introducing P ₃ is a polyol compound (particularly a 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 its isomers, and bisphenol A. There is. Other polyol compounds include polytetramethylene glycol, polycaprolactone glycol, polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymers (pluronic nonionic glycol), and other polyol compounds having hydroxyl groups at both ends. is there. Among these polyol compounds, one kind or two or more kinds are used.

The raw material monomer for introducing T is a triisocyanate compound. As a concrete example,
There are trimer isocyanurates of diisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylene diisocyanate and hexamethylene diisocyanate. Further, there is an adduct of 1 mol of a triol compound such as trimethylolpropane and 3 mol of the above diisocyanate compound. From these triisocyanate compounds, 1
One kind or two or more kinds are used.

The value of the repeating unit m is 0 to 20. m
When the value exceeds 20, the oligomer becomes highly viscous and becomes difficult to dissolve in other monomers and oligomers.

When the oligomer of the present invention is produced, an alcohol compound is reacted with one end of the triisocyanate compound, which is the starting material for the application. T (NCO) ₃ + P ₂ OH → T (NHCOOP ₂ ) (NCO) ₂

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

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 together,
For example, if an equimolar number is added, a polymer having a large molecular weight will be produced. For this reason, it is preferable that the addition amount of the polyol compound is 1/2 equivalent or less of the triisocyanate compound, thereby preventing the formation of a polymer having a large molecular weight.

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

With such a production method, the molecular weight of the oligomer is not distributed to the larger one, and the viscosity of the coating solution in which the oligomer is dissolved does not excessively increase. Therefore, the moldability of such a coating liquid is improved, and mixing with other monomers and oligomers is facilitated.

An example of the above synthesis method will be shown. Triisocyanate: T (NCO) ₃ (m + 1) moles and (m + 1) moles of P ₂ OH are added and reacted to produce a diisocyanate compound T (NHCOOP ₂ ) (NC
O) ₂ is synthesized. Glycol P ₃ (OH) ₂ was added to this reaction solution.
(m / 2 + 0.5) mol is added to synthesize an oligomer having an isocyanate group at the end.

The remaining glycol P ₃ (OH) ₂ was added to this reaction solution.
The (m / 2-0.5) moles and, P ₁ (OH) 2 mol was added and reacted to obtain the oligomer of interest. Of course, in this case, m ≧ 1.

When m = 0, 1 mol of triisocyanate is used.
1 mol of P ₂ OH after reacting 2 mol of P ₁ OH with l
React or simultaneously react 3 mol of P ₁ OH and P ₂ OH in total.

When synthesizing the oligomer of the present invention, the 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 may be used.

Further, a catalyst for the urethanization reaction can be used if necessary. As such a catalyst, known Lewis bases such as triethylamine, triethanolamine, triethylenediamine, dibutyltin dilaurylate, dibutyltin diacetate and the like are used.

In addition to the above-mentioned oligomer, in order to improve the coating viscosity and the like, it is preferable to add an active energy ray-polymerizable monomer containing a hydroxyl group to the antifogging composition. The function of this monomer is a component for adjusting the viscosity of the composition, adjusting the crosslink density of the cured film, preventing warpage due to curing shrinkage, and the like, and the antifogging property of the urethane (meth) acrylate oligomer of the present invention. Use it to the extent that it does not harm. As such a monomer, a mono (meth) acrylate compound containing one or more hydroxyl groups, phosphoric acid groups or carboxyl groups,
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 phosphoric acid mono (meth) acrylate, ethylene oxide modified phenoxyphosphoric acid mono (meth) acrylate, ethylene oxide modified octoxylated phosphoric acid mono (meth) acrylate, Examples thereof include alkoxy acid phosphoric acid mono (meth) acrylate ester, ethylene oxide-modified phthalic acid mono (meth) acrylate, ethylene oxide-modified succinic acid mono (meth) acrylate, and the like.

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 with hydroxyl group, etc. It is used to the 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 one or more hydroxyl group, phosphoric acid group or carboxyl group include triglycerol diacrylate, glycerol monoacrylate monomethacrylate, glycerol dimethacrylate, penta. 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 , Etc. epichlorohydrin-modified epoxy (meth) acrylate 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 groups, phosphoric acid groups or carboxyl groups can be used alone or in combination of two or more.

When ultraviolet rays are used as the active energy rays, it is necessary to add a photopolymerization initiator which has a function of generating radicals by the irradiation of ultraviolet rays and initiating 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 rays or cobalt γ rays.

Examples of the photopolymerization initiator include diethoxyacetophenone and 2-hydroxy-2-methyl-1-.
Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1
-One, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, acetophenone-based, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2- Benzoin compounds such as dimethoxy-2-phenylacetophenone, benzophenone, hydroxybenzophenone, 3,
Benzophenone series such as 3-dimethyl-4-methoxybenzophenone, thioxanthone series 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 the curability. The oligomer of the present invention is used as the main component of the antifogging composition. As described above, the antifogging composition is mixed with a polymerizable monomer containing a hydroxyl group to the extent that the antifogging property is not impaired, and the curability, surface scratch resistance, water resistance, etc. adjust. In addition to the above-mentioned polymerized monomer containing a hydroxyl group, a small proportion of other UV-curable monomers and oligomers may be added to this composition, and a leveling agent, a sensitizer and an interface may be added. If necessary, auxiliary agents such as an activator, a storage stabilizer, a heat stabilizer and a light stabilizer may be used in combination.

The antifogging composition is a liquid having a relatively low viscosity and can be applied without adding a solvent. This is extremely advantageous since a solvent drying process 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, n-butanol and the like, and cellsolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve are preferable.

The object of forming the film of the antifogging composition is a sheet of a transparent resin such as inorganic glass, polycarbonate resin, polymethylmethacrylate resin, polyvinyl chloride resin, cellulose ester resin, polyallyl diglycol carbonate resin, Examples include injection molded products and cast molded products.

In particular, the polycarbonate resin is excellent not only in transparency but also in impact resistance, so that it is often used for various face bodies and windows, and is most suitable as an object of the composition of the present invention. Further, antifogging property can be similarly imparted to glass and metals other than resin.

To form a film of the antifogging composition on the above molded article, any coating method is adopted. For example, spray method, dip method, flow coating method, roll coating method,
Any method such as bar coating method, curtain flow method, spin coating method and screen printing method may be used. If the thickness of the coating is too thin, the antifogging property becomes insufficient. Conversely, if the thickness is too large, peeling or embrittlement from the target substrate due to water swelling occurs and the water resistance decreases. 20 μm is preferable, and 10 to 20 μm is particularly preferable. Upon coating, if necessary, some pretreatment may be applied to the molded product and the coating to improve the adhesion, and it is also preferable to do so.

Immediately after coating or after setting for several minutes, a cured film is formed by irradiating with ultraviolet rays.
The ultraviolet irradiation device used is preferably a high-pressure mercury lamp that irradiates ultraviolet rays having a wavelength of 250 to 400 nm. The standard irradiation conditions are preferably a lamp output of 80 to 120 w / cm 2, a lamp distance of 5 to 30 cm, and a conveyor speed of 1 to 10 m / min. It can also be cured by active energy rays other than UV irradiation, such as electron beams.

[0047]

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

(Synthesis Example 1: m = 3) In a 1 liter reactor equipped with a stirrer and a reflux condenser, as a triisocyanate, "Mytec 215A" (manufactured by Mitsubishi Kasei Co., Ltd., trimethylolpropane) was used. Isocyanone diisocyanate 3 mol added isocyanate adduct, molecular weight 800, solid content 75
% Ethyl acetate solution) (56.89 g) was dissolved in 80 g of ethyl acetate in advance. While stirring, perform N ₂ gas replacement,
The temperature was raised to 50 ° C. and kept constant. Then (meta)
As the acryloyl group-containing alcohol, 2-hydroxyethyl acrylate (hereinafter abbreviated as HEA) 6.19 g,
As a urethane-forming catalyst, a solution prepared by dissolving 0.84 g of dibutyltin dilaurylate (hereinafter abbreviated as DBTDL) in 18 g of ethyl acetate was added, and the temperature was kept at 50 ° C. to react for 3 hours.

Next, as a glycol compound, "Newpol PE-68" (produced 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 temperature was kept at 50 ° C. and the reaction was carried out for 2 hours.

Furthermore, the remaining "PE-68" 117.3 g and "HE"
A solution of 3.09 g of “A” dissolved in 120.12 g of ethyl acetate was added, and the mixture was kept at 60 ° C. and reacted for 5 hours. 22 by IR measurement
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 put in a vacuum dryer, kept at 50 ° C., and decompressed by a vacuum pump to remove ethyl acetate, thereby obtaining a white solid oligomer. This oligomer is designated as oligomer A.

(Synthesis Example 2: m = 3) By the method shown in Synthesis Example 1, instead of "HEA" as an alcohol compound containing one hydroxyl group, "Plaxel A-5" (manufactured by Daicel Chemical Industries, Ltd., 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 called oligomer B.

(Synthesis example 3: an example of m = 3) [PE-68] was used as a glycol compound by the method shown in Synthesis example 1.
Instead of "New Pole PE-64" (made by NOF Corporation,
(Ethylene oxide-propylene oxide block copolymer, Mw2400, hereinafter abbreviated as "PE-64") except that the reaction was carried out in exactly the same manner as above, and the reaction solution was vacuum treated in the same manner to give a colorless and transparent product. A semi-solid oligomer of was obtained. This oligomer is referred to as an oligomer C.

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

Next, a solution of 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 the temperature was raised to 50 ° C. It was kept for 3 hours and reacted.
Next, as a glycol compound, a solution prepared by dissolving 234.7 g of “PE-68” in 234.7 g of ethyl acetate was added, and the temperature was kept at 50 ° C. to react for 2 hours.

Further, a solution prepared by dissolving 4.59 g of lauryl alcohol and the remaining 117.3 g of "PE-68" in 120.11 g of ethyl acetate was added, and the mixture was kept at 60 ° C. and reacted for 5 hours. It was confirmed by IR measurement that the characteristic absorption of NCO appearing at 2250 cm ^-1 had disappeared, the reaction was terminated, and the temperature was returned to 25 ° C. This reaction solution was put in a vacuum container, kept at 50 ° C., and decompressed by a vacuum pump to remove ethyl acetate, thereby obtaining a white solid oligomer. This oligomer is designated as oligomer D.

(Synthesis Example 5: Example of m = 3) By the method shown in Synthesis Example 4, as the alcohol containing one hydroxyl group, "HEA" and "HE" were used instead of lauryl alcohol.
Methoxypolyethylene glycol (molecular weight 2000) in place of "A", polytetramethylene glycol in place of "PE-68" as a glycol compound (manufactured by Mitsubishi Kasei,
"PTMG650", molecular weight 650, abbreviated as PTMG hereafter) was reacted in exactly the same manner as above, and the reaction solution was vacuum-treated in the same manner to obtain a white solid oligomer. This oligomer is referred to as oligomer E.

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

Next, as a (meth) acryloyl group-containing alcohol, "HEA" 4.87 g, and as a urethanization catalyst, a solution of 0.3 g of "DBTDL" dissolved in 14.16 g of ethyl acetate was added, and the temperature was kept at 50 ° C. The reaction was carried out for 3 hours. Next, as a glycol compound, a solution of 67.2 g of "PE-64" dissolved in 67.2 g of ethyl acetate was added, and the temperature was kept at 50 ° C.
The reaction was carried out for 2 hours.

Furthermore, 33.6 g of the remaining "PE-64" and "HE
A) 0.47 g of a solution of ethyl acetate in 34.97 g was added,
The mixture was kept at 60 ° C. and reacted for 5 hours. 2250cm by IR measurement
^It was confirmed that the characteristic absorption of NCO appearing in ^-1 had disappeared, the reaction was terminated, and the temperature was returned to 25 ° C. This reaction solution was put in a vacuum container, kept at 50 ° C., and decompressed by a vacuum pump to remove ethyl acetate, thereby obtaining a white solid oligomer. This oligomer is designated as an oligomer F. Table 1 shows the material of the oligomer of each synthesis example.

[0060]

[Table 1]

(Example 1) 100 parts by weight of urethane acrylate oligomer A of Synthesis Example 1, "Aronix M-305"
"(Toa Gosei Kagaku, pentaerythritol triacrylate) 50 parts by weight," 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 transparent solvent-free photosensitive solution. This photosensitive solution was applied to a polycarbonate film having a thickness of 50 μm using an applicator to adjust the thickness to 7 μm, and cured by an ultraviolet irradiation device. The UV irradiation device is "ORM-2077A" (high pressure mercury lamp 80W / cm * 3, manufactured by Oak Manufacturing Co., Ltd.).
A lamp base and a lamp distance of 15 cm) were used. UV integrated light intensity is 50
It is 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 conducted under the following conditions. The results are shown in the table. Breath test --- At room temperature, attach the sample to the side (outer side) of a beaker containing ice water, and with the coating film side facing outward, breathe and test. Direct steam test ─── Place the sample on a water bath at 40 ℃ and apply steam directly to test. Rubbing test --- Using a rubbing tester manufactured by Ohira Rika Kogyo Co., Ltd., using water-containing felt as an abrasive, rubbing 100 times back and forth under a load of 1 kg, and then directly performing a steam test. Water resistance test --- After soaking in water for 1 hour, perform a direct steam test. Durability test ──── Affixed to the mirror in the bathroom of the Hayakawa Rubber employee dormitory in Minamiteki-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 are mono (meth) acrylate compounds containing one or more hydroxyl groups, and hydroxyl groups. A di- or tri (meth) acrylate compound containing at least one of the above and a photopolymerization initiator were blended to obtain a solventless photosensitive liquid. Then, in the same manner as in Example 1, each photosensitive solution was cured to obtain a surface-treated film. Next, 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.

However, 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 Mono (meth) shown in Table 4 against commercially available urethane acrylate oligomers 1 and 2
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 conducted in the same manner as in Example 1. The results are shown in Table 4.

However, the urethane acrylate oligomers 1 and 2 are as follows. Oligomer 1: "Aronix M-1200" manufactured by Toa Gosei Co., Ltd., bifunctional non-yellowing urethane acrylate oligomer 2: "Shikou 3000B" manufactured by Nippon Synthetic Chemical Co., Ltd., bifunctional non-yellowing urethane acrylate oligomer 9EG-A: " 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 is prepared by using the oligomer of the present invention as a main component, the transparent product surface has antifogging property and surface scratch resistance. It is possible to form a film having excellent properties, water resistance and durability.

Claims (2)

[Claims] 1. An oligomer for an antifogging composition represented by the following general formula. (P ₁ and P ₂ are residues except for the hydroxyl group of the alcohol compound having one hydroxyl group respectively, at least one of P ₁ and P ₂ contains an acryloyl group or a methacryloyl group, P ₃ is, It is a residue of a polyol compound excluding the hydroxyl group, and at least one of P ₁ , P ₂ and P ₃ contains a polyethylene oxide block — (CH ₂ CH ₂ 0) _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 repeating units of 0 to 20. ] 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 moiety represented by the following general formula. Oligomer. _{- (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 to 200. ]