JPH03115464A - Antifogging curable resin composition - Google Patents

Abstract

PURPOSE:To improve the antifogging properties and persistence thereof by compounding a curable resinous compd. and a reactive antifogging agent. CONSTITUTION:The title compsn. is prepd. by compounding: 100 pts.wt. curable resinous phosphazene compd. of formula I [wherein X and Y are each a polymerizable, curable group of formula II or III (wherein R<1> is 1-12C alkylene; and Z and Z' are each H or methyl) or a nonpolymerizable, curable group of formula IV or V {wherein M is -O-, -S-, or imino; R<2> is 1-18C linear or branched (halogenated) alkyl; R<3> is 1-4C linear or branched alkyl or halogen; and m is 0-5}, and at least one of X and Y is the polymerizable, curable group; p>=0, q>=0, and p+q=2; and m>=3]; 1-75 pts.wt. reactive antifogging agent (e.g. 2-glycoxyethyl methacrylate); and, if necessary, 0.1-10 pts.wt. polymn. initiator, and a polymn. accelerator, a solvent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an anti-fog curable resin composition, and more specifically, it has excellent anti-fog properties and its durability, and can be used, for example, in glasses, optical instruments, lenses, etc. The present invention relates to an anti-fog curable resin composition that can be suitably used in the field of manufacturing various anti-fog coatings and anti-fog molded products such as hard coat materials for various display boards and panels and transparent molded products.

[Prior Art and Problems to be Solved by the Invention] Curable resin compounds are used, for example, in hard coat materials for glasses, optical equipment, lenses, various display boards, panels, etc., packaging films and sheets for foods, etc., and agricultural films. It is widely used in various transparent molded products such as, and demand for it is expected to increase in the future.

However, in films, sheets, and other molded products that require such transparency, fogging occurs when the surface becomes covered with minute water droplets due to condensation of moisture in the air or adhesion of water vapor. Various serious problems have arisen, such as the contents becoming difficult to see and the transmission of light being significantly reduced, resulting in a significant loss of aesthetic appearance.

Therefore, how to prevent the occurrence of such clouding effectively and for a long period of time has become an important issue.

This clouding can be prevented by making the surface of the film easier to get wet with water, as described in ``Plastic Compounds'' Fundamentals and Applications (Taiseisha) 9280-281, and making the surface of the film easier to get wet with water. It is believed that this can be prevented by coalescing tiny water droplets that persist forever once they form on a surface, forming a uniform film over the entire surface.

Antistatic agents are known to be effective for such purposes, and are widely used as so-called antifogging agents (dripproofing agents, antifogging agents).

The aforementioned ``Plastic Compounds'' Fundamentals and Applications (Taiseisha) lists many examples of such antifogging agents.

Methods of using these antifogging agents include, for example, adding these antifogging agents to polymeric materials to make molded products such as films with antifogging properties, and adding antifogging agents to coating materials. And 1 each of films etc! There is a method of providing a film having antifogging properties on the surface of a molded article.

The latter method can be applied not only to various polymer molded products such as films but also to molded products made of other materials such as glass as a coating film that also serves as a protective film. It has attracted particular attention because it has the advantage of being able to be molded into layered films, multilayer films or sheets, and even molded articles of other shapes.

For example, relatively recently, attempts have been made to add the above-mentioned conventional antifogging agents to curable resin compounds to impart an antifogging effect to cured coatings.

However, a conventional curable resin composition obtained by adding an antifogging agent to a curable resin compound has a problem in that its antifogging effect cannot be sustained for a long period of time.

Generally, the antifogging effect has no practical meaning unless it lasts for a long period of time, as is clear from its use.

In other words, when formed into a cured coating film or molded product, it has a sufficient antifogging effect and can maintain the antifogging effect for a long period of time. There is a strong desire to develop an antifogging curable resin composition that can be easily formed into a film or molded into a molded article.

The present invention has been made in view of the above circumstances.

The purpose of the present invention is to solve the above-mentioned problems, to have sufficient anti-fog effect when made into a cured coating film or molded product, and to maintain the anti-fog effect for a long period of time. Another object of the present invention is to provide an antifogging curable resin composition whose curability is not inhibited and which can be easily formed into cured coatings or molded articles.

[Means for Solving the 8 Problems] To achieve the above object, the present invention provides an anti-fog curable resin composition characterized by blending a curable resin compound and a reactive anti-fog agent. It is what it is.

Monocurable Resin Compound (1) In the present invention, the curable resin compound may be cured at room temperature, or by external physical and/or chemical curing such as irradiation with light such as ultraviolet rays, electron beams, or other radiation, or heating operation. Any material can be used as long as it can form a cured product such as a cured coating film by a chemical action.

Specifically, for example, curable phosphazene compounds, acrylic acids such as acrylic acid and methacrylic acid, acrylic esters such as methyl acrylate and methyl methacrylate,
Acrylamides, methacrylamides, acrylonitrile, other acrylic or methacrylic compounds,
Curable oligomers that can be obtained by low polymerization of various curable polymers such as curable olefins having vinyl groups, such as styrene, or one or more of these various curable monomers. and curable prepolymers.

Among these, the strength, abrasion resistance, transparency of the cured coating film,
In terms of durability etc. and good balance between these,
Particularly preferred are curable phosphazene compounds.

Note that these various curable resin compounds may be used alone or in combination of two or more as a mixture.

- Monocurable phosphazene compound - The curable phosphazene compound has, for example, the linear general formula (■): 廿-NP (X)p (Y)q-11. (I)
[However, in formula (1), X and Y are each a polymerizable curable group or a non-polymerizable curable group, and they may be the same or different, but at least one of them It is a polymerizable curable group, p and q are each a number of 0 or more, their total is 2, and n is an integer of 3 or more. ] Compounds represented by the following can be suitably used.

The polymerizable curable group in the general formula (I) can be cured not only at room temperature but also by external physical and/or chemical action such as irradiation with light such as ultraviolet rays or electron beams or other radiation, or heating operation. Any group having an unsaturated bond such as
) can be mentioned as preferable groups.

-01102C-Ten=CH2 ([1) [However, R1 in the formula (■) is a fullkylene group having 1 to 12 carbon atoms, and Z is a hydrogen atom or a methyl group. Moreover, Zo in formula (m) is a hydrogen atom or a methyl group. Note that Z and Zo may be the same group or atom, or may be different groups or atoms.] Note that R1 in the general formula (n) is a linear alkylene group; or may be an alkylene group having a branched chain; a preferable alkylene group is an ethylene group.

Specific examples of the group represented by the general formula (n) include 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxybutyl methacrylate, 6-hydroxy-3-methylhexyl methacrylate, to 5-hydroxy xyl methacrylate, 3-hydroxy-2-t-butylpropyl methacrylate, 3-hydroxy-2,2-dimethylhexyl methacrylate.

Residues obtained by removing hydrogen atoms from hydroxyl groups in methacrylates such as 3-hydroxy-2-methylethylpropyl methacrylate and 12-hydroxydodecyl methacrylate (hereinafter sometimes referred to as methacrylate residues), and 2 -Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxy-3-methylhexyl acrylate, to 5-hydroxy Among acrylates such as xyl acrylate, 3-hydroxy-2-t-butylpropyl acrylate, 3-hydroxy-2,2-dimethylhexyl acrylate, 3-hydroxy-2-methylethylpropyl acrylate and 12-hydroxydodecyl acrylate. Examples include residues obtained by removing a hydrogen atom from a hydroxyl group. Particularly preferred groups are 2-hydroxyethyl methacrylate residues and 2-hydroxyethyl acrylate residues. When comparing the various hydroxyalkyl methacrylate residues and hydroxyalkyl acrylate residues, hydroxyalkyl acrylate residues are preferable because of their higher crosslinking rate.

Specific examples of the group represented by the general formula (m) include an acrylamide group and a methacrylamide group.

On the other hand, as the non-polymerizable curable group, for example, the following general formulas (IV) and (V); (
-0-), sulfur atom (-3-) and imino group (-N
R2 in the formula (■) represents a linear or branched alkyl group having 1 to 18 carbon atoms or a halogen-substituted alkyl group, and R3 in the formula (V) represents a carbon number 1 to 4 linear or branched alkyl groups or halogen atoms, m in formula (V) represents an integer of O to 5, and R3 may be the same group or different Specific examples of the group represented by the general formula (IV) include:
For example, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, and octadecyloxy; methylthio, Alkylthio groups such as ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, and hexadecylthio; methylamino, ethylamino, propylamino, butylamino, pentylamino group, hexylamino group,
tomonoalkylamino groups such as octylamino, decylamino, dodecylamino, hexadecylamino, and octadecylamino groups, and at least one of these various flukoxy, alkylthio, and N-alkylamine groups. a haloalkyloxy group in which the H atom of the C-H group is substituted with a halogen atom,
Mention may be made of haloalkylthio groups and to(haloalkyl)amino groups.

Note that examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition, R3 in the general formula (V) is a methyl group,
Mention may be made of ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 1-methylpropyl group, t-butyl group, fluorine atom, chlorine atom, bromine atom and iodine atom.

Specific examples of the compound represented by the general formula (V) include a phenol group, a phenylthio group, a phenylamino group,
and compounds in which 1 to 5 C-1 (H atoms of the bond) of the aromatic ring of these groups are substituted with a group selected from the substituents represented by R3 above.

The curable phosphazene compound represented by the general formula (I) is one in which n is an integer of 3 or more, preferably one in which n is 3 to 18, and particularly a cyclic compound in which n is 3 or 4, or a mixture thereof. suitable.

One Reactive Antifogging Agent The above-mentioned reactive antifogging agent may be any compound having one reactive group and having antifogging properties without any particular limitations.

Here, the term "reactive group" refers to not only reaction at room temperature but also physical and/or chemical action from the outside such as irradiation with light such as ultraviolet rays or electron beams or other radiation, or heating operation. It means a group that can react chemically, and specifically includes a group containing an acryloyl group or a methacryloyl group such as an acrylic group, a methacryl group, an acrylamide group, a methacrylamide group, a 1,2-epoxyethyl group,
2゜ Groups containing epoxy bonds such as 3-epoxyprobyl groups (glycidyl groups), reactive alkenyl groups or groups containing reactive alkenyl groups such as vinyl groups, allyl groups, 1-methylvinyl groups, vinylidene groups , conjugated polyene group,
A reactive alkynyl group or a group containing a reactive alkynyl group such as an ethynyl group or a 2-propynyl group, a formyl group,
Reactive acyl group or group containing a reactive acyl group such as acetyl group, benzoyl group, acetamino group, benzamide group, herroformyl group, thioformyl group, ketynyl group, carbamoyl group, isocyano group, incyanato group 1
Examples include an inthiocyanato group, an amidino group, a group containing a lactam bond, and a group containing a lactone bond.

Among these, particularly preferred groups include acrylic groups,
Examples include methacrylic group, vinyl group, and allyl group.

Here, having antifogging properties means a property that has a strong interaction with moisture and improves the wettability of the surface of the cured product when one composition is made into a cured product, and such antifogging properties In order to express this, it is necessary that the reactive antifogging agent has a polar group such as a hydroxyl group or a group having such a polar group.

The polar groups mentioned here are not limited to hydroxyl groups, but also cationic,
It may be anionic, nonionic or amphoteric.

In addition, as groups that exhibit antifogging properties, various hydroxyl group-containing groups obtained by abstracting one hydrogen atom or a small group such as a hydroxyl group from a glucoxyl group or other monosaccharide or polysaccharide molecule, such as the polysaccharide groups shown below. Various hydroxyl group-containing groups obtained by abstracting one hydrogen atom or hydroxyl group, preferably a hydrogen atom other than the hydrogen atom in the hydroxyl group, from a nonionic surfactant molecule such as a partial fatty acid ester of a hydrolic alcohol, [However, R4 is a hydrocarbon group having 2 to 18 carbon atoms. ] [However, R5 is a hydrocarbon group having 2 to 18 carbon atoms.

] For example, various residues, preferably hydroxyl group-containing residues, R6-0-( CH2CH20)
n H [However, R6 is a hydrocarbon group having 2 to 18 carbon atoms, and n is 8 to 15. ] R' -CH,2COO-(CH2CH20)n H[
However, R1 is a hydrocarbon group having 12 to 15 carbon atoms,
n is 3 to 3o. ] R8NH(CH2CH20)n H [where R8 is a hydrocarbon group having 2 to 18 carbon atoms,
n is 3-30. ] R9-CONH(CH2CH20) H[However, R9 is a hydrocarbon group having 2 to 18 carbon atoms, and m is 3 to
It is 30. [However, R10 is a hydrocarbon group having carbons a2 to 18, n is 3 to 30, and m is 3 to 30. ] [However, R
11 is a hydrocarbon group having 2 to 18 carbon atoms, and n is 3 to 3
It is 0. ] [However, RI2 is a hydrocarbon group having 2 to 1 carbon atoms, and n is 3 to 30.

] [However, R13 is a hydrocarbon group having 2 to 1 carbon atoms. ] and so on.

Among these, particularly preferred groups are residues of monosaccharides typified by glucoxy groups or 2-18 saccharides.

Among the reactive antifogging agents having the above-mentioned reactive groups and antifogging properties, particularly preferred examples include glucoxyalkyl methacrylates such as 2-glucoxyethyl methacrylate, 2-glucoxy Examples include glucoxyalkyl acrylates such as ethyl acrylate.

Here, there are various types of glucoxy groups, including various residues obtained by removing one hydrogen atom bonded to a carbon atom or an oxygen atom in a glucose molecule, and any of them may be used, but for example, 1 of the glucose molecules
Particularly preferred are residues obtained by abstracting the hydrogen atom from a hydroxyl group bonded to the carbon atom at the position.

The various reactive antifogging agents mentioned above may be used alone or in combination of two or more.

(1) Anti-fog curable resin composition (1) The anti-fog curable resin composition of the present invention can be obtained by blending the curable resin compound and the reactive anti-fog agent.

The mixing ratio of the curable resin compound and the reactive antifogging agent is not particularly limited and can be appropriately selected depending on the purpose of use, etc., but usually the curable resin compound used is 100% It is preferred that the amount of the reactive antifogging agent is in the range of 1 to 75 parts by weight, particularly 3 to 20 parts by weight.

When the blending ratio of this reactive antifogging agent is less than 1 part by weight,
A sufficient anti-fog effect cannot be obtained, and even if an anti-fog effect can be imparted by using other non-reactive anti-fogging agents (for example, the conventional anti-fogging agents mentioned above), it will not last long. It becomes difficult to maintain the antifogging effect over a period of time, and on the other hand, if the amount exceeds 75 parts by weight, the curability may decrease or the properties such as strength as a cured coating may become insufficient.

The antifogging curable resin composition of the present invention includes, in addition to the curable resin compound and the reactive antifogging agent, other components such as a polymerization initiator such as a thermal polymerization initiator, a photoinitiator, and a reef increasing agent;
It may contain a polymerization accelerator, a solvent, an additive, etc.

Examples of solvents to be added as desired include ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methanol, ethanol, propatool, impropyl alcohol, and butanol, and aromatic solvents such as benzene, toluene, xylene, and chlorobenzene. Solvents include various solvents such as ester solvents such as ethyl acetate and butyl acetate, haloalkane solvents such as dichloromethane and tetrachloroethane, amide solvents such as acetamide, I)MF, and DMSO.

In addition, these solvents should be selected appropriately depending on the purpose, and in some cases, one type of solvent may be used alone.
Two or more types may be used in combination as a mixed solvent or the like.

The optional additives include, for example, antioxidants, ultraviolet absorbers, lubricants, other reactive curable compounds, non-reactive antistatic agents or antifogging agents, weather resistance improvers, colorants, Examples include plasticizers and fillers.

Examples of the antioxidant include phenol substituted products,
Examples include organic phosphorous compounds, bisphenols, phosphorous esters, and aromatic amines.

Examples of the UV absorbers include benzophenone UV absorbers, benzoate UV absorbers, benzotriazole UV absorbers, and metal complex salt UV absorbers.

Examples of the lubricant include fatty acids, aliphatic alcohols, fatty acid esters, and metal soaps.

Reactively curable compounds having the above values include, for example, methyl acrylate, hydroxyethyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate and mixtures of tetraethylene glycol diacrylate and methacrylate, glycidyl acrylate, trimethylolpropane. tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate) , 2,2'-bis(acryloxyphenyl)propane, 2,2°-bis[
4-(3-methacryloxy)-2-hydroxypropoxyphenyl]propane, carboxylic vinyl esters (e.g. vinyl acetate, vinyl stearate, etc.), ethylenically unsaturated dicarboxylic acids (e.g. fumaric acid, maleic acid,
maleic anhydride, itaconic acid, itaconic anhydride, etc.), such as diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, triallylsialt,
Examples include allyl thread binders such as triallyl isocylate.

One or more of these various additives may be appropriately selected as necessary and used within a range that does not interfere with the purpose of the present invention.

In order to cure the antifogging curable resin composition of the present invention,
For example, heat curing methods using thermal polymerization, room temperature curing methods, photo curing methods that irradiate light such as ultraviolet rays, radiation curing methods that irradiate other radiations such as electron beams and gamma rays, or combinations of two or more of these methods. Various physical and/or chemical curing methods such as curing methods can be employed.

When employing a heat curing method, there are no particular restrictions on the heating temperature and heating time, and the optimum conditions may be set as appropriate.Furthermore, the heating conditions may be changed to effect curing in stages.

In addition, when adopting a curing method by thermal polymerization, 1 usually:
It is preferable to use a thermal polymerization initiator, and in some cases, a polymerization accelerator can be used in combination to further improve the curing rate.

The thermal polymerization initiator to be blended as desired may be appropriately selected depending on the type of curable resin compound and reactive antifogging agent used, but those that can be particularly preferably used include, for example: , peroxide-based compounds, amine-based compounds, or mixtures thereof.

Examples of the peroxide compounds include benzoyl peroxide, azobisisobutyronitrile, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butyl hydroperoxide, di-t-butyl Examples include peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, and the like.

In addition, examples of the amine compounds include N,N-jetanol-P-toluidine, dimethyl-P-)luidine,
P-toluidine, methylamine, t-butylamine, methylethylamine, diphenylamine, 4,4'-dinitrodiphenylamine, 0-nitroaniline, p-bromoaniline, 2,4.6-)ribromoaniline, and the like.

In addition, these may be used individually by 1 type, and may use 2 or more types together.

The amount of the polymerization initiator to be used is not particularly limited, but when using a curing method by thermal polymerization, the amount of the polymerization initiator is usually 100 parts by weight in total of the curable resin compound and the reactive antifogging agent. Approximately 11 to 10 parts by weight of O is sufficient.

Furthermore, the antifogging curable resin composition of the present invention can also be cured by irradiation with light or radiation.

When curing by light irradiation, ultraviolet rays can be particularly preferably used. In this case, it is preferable to use a photoinitiator or a sensitizer.

As the photoinitiator or sensitizer, various known ones can be used, but specific examples of particularly preferred ones include benzoin ethers such as isobutyl benzoin ether, isopropyl benzoin ether, and benzoin ethyl ether. Benzyl ketals such as 2,2-dimethoxy-2-phenylacetophenone and hydroxycyclohexylphenyl ketone;
Examples include 7cetophenone derivatives such as jetoxyacetophenone and 2-hydroxy-2-methyl-1-phenylpropan-1-one, and aromatic ketones such as benzophenone.

In addition, these may be used individually by 1 type, and may use 2 or more types together.

In the case of curing by irradiation with other radiation outside the scene, electron beams, gamma rays, etc. can be particularly preferably used.

Among the various curing methods mentioned above, ultraviolet curing methods can be particularly preferably used.

- Cured product of anti-fog curable resin composition and molded product thereof - The anti-fog curable resin composition of the present invention can be cured into a cured product and molded into various shapes having an anti-fog effect. Although it can be used as a product, it is usually used by coating a predetermined surface of a base material by coating, etc., and curing it using the various curing methods mentioned above to form a film such as a cured coating film. It can be suitably used.

There are no particular restrictions on the shape of the base material used here;
Various shapes can be mentioned, such as a film, a sheet, a block, a rod shape, and a vibrator shape. Which of the above shapes the base material should have is determined by its use.

In addition, the materials include various plastics such as polycarbonate, polyester, acrylic plastics, methacrylic plastics, polyolefin plastics such as polyethylene and polypropylene, metals, wood, papers, knitted fabrics, textiles, Various materials can be mentioned, such as non-woven fabrics.

Furthermore, these base materials may be those that have already been molded or may be raw materials that are in the process of being molded. For example, the antifogging curable resin composition of the present invention may be used in the molding process of the base material. It is also possible to arrange this on a predetermined surface of the base material by coating or the like, and then integrally mold this by, for example, laminating processing, etc., to finish it as a molded product having a desired shape and having an anti-fog cured coating film.

As a method for coating the base material, a coating method can usually be suitably employed, but other coating methods such as casting and dipping methods can also be used. Examples of the coating method include a bar coater method, a roll coater method, a gravure coater method, a spray method, and a brush coating method. These coating methods may be used alone or in appropriate combinations.

In addition, the cured coating film formed by the antifogging curable resin composition according to the present invention is not necessarily limited to being formed by a coating method, and may be a cured coating formed using another method.

The cured coating film (film) and molded cured product of the antifogging curable resin composition of the present invention obtained as described above have high antifogging properties, and the antifogging effect remains for a long period of time. It has extremely long lasting anti-fog properties.

Further, the above-mentioned antifogging cured coating film (film) and molded cured product generally have excellent properties such as mechanical strength.

In particular, the antifogging cured coating (film) and molded cured product obtained using the above-mentioned curable phosphazene compound as a curable resin compound have excellent antifogging properties and long-term sustainability.
It also has excellent surface hardness, mechanical strength, wear resistance, transparency, and durability.

Furthermore, the antifogging curable resin composition of the present invention can be used to form a cured coating film (film) that maintains the antifogging effect 4 for a sufficiently long period of time even when applied once. Of course, it is possible to further improve the anti-fog effect, its durability, and other properties as a film by applying two or three coats if necessary, but usually one coat is sufficient. Obtainable.

That is, by using the antifogging curable resin composition of the present invention, it is possible to easily impart excellent antifogging function that lasts for a long time to various molded products, and it can also be used by itself. Various anti-fog molded products having excellent anti-fog properties and durability can be easily obtained.

The excellent anti-fog properties of the curable anti-fog resin composition of the present invention, especially its long-term durability, are due to the addition of a specific anti-fog agent called a reactive anti-fog agent to the curable resin compound. It is expressed by blending.

The reason for such excellent anti-fog properties is as follows.
Although it is not always clear, conventional antifogging agents (non-reactive antifogging agents) do not cause virtually any chemical reaction with the curable resin compound during curing, whereas the antifogging curable resin composition of the present invention In products, the reactive antifogging agent that is blended easily reacts with the curable resin compound during curing, or some of the reactive antifogging agents polymerize with each other to form a polymer, creating a strong chemical in the cured product. This is thought to be because the antifogging agent is integrated and extremely stabilized by bonding, and therefore, even during long-term use, the antifogging agent will not be lost due to leakage or the like, and the antifogging agent will function effectively for a long period of time.

Moreover, the reason why the antifogging curable resin composition of the present invention has excellent curability is thought to be because the compounded reactive antifogging agent itself also has polymerization curability.

Furthermore, the cured product such as a cured coating film obtained using the antifogging curable resin composition of the present invention is excellent in strength such as surface hardness, but this also has a reactive antifogging compound blended as described above. This is thought to be due to the fact that the agents are integrated by strong chemical bonds and are polymerized. In particular, in the case of conventional non-reactive anti-fogging agents, the strength of the cured product decreases significantly when the amount of the non-reactive anti-fogging agents is increased, whereas the reactive anti-fogging agents used in the present invention are themselves curable. Therefore, even if the blending ratio is significantly increased, the strength etc. of the cured product can be sufficiently maintained.

In this way, since the blending ratio of the antifogging agent (reactive antifogging agent) can be freely increased, the antifogging properties can be significantly improved.

From the above, the antifogging curable resin composition of the present invention can be used, for example, in glasses, optical equipment, lenses, various windows, etc.
Various display boards, panels, decorative laminates 1. Anti-fog properties of various sheets and films, including packaging films for food products, films for going out of business, and other molded products. Anti-fog properties of hard coat materials and various anti-fog parts. It can be suitably used as a molded article in a wide range of fields where antifogging properties, particularly long-term sustainability, are required.

[Examples] Next, the present invention will be explained in more detail by showing Examples, Reference Examples, and Comparative Examples of the present invention, but the present invention is not limited to these Examples.

(Reference example) Production of phosphazene compound [Synthesis of +, 1,3,3,5.5-hexa(methacryloylethylenedioxy)cyclotriphosphazene] Attach a thermometer, stirring device, dropping funnel and condenser 58.0 g of hexachlorocyclotriphosphazene (hereinafter abbreviated as 3PNG) in one flask.
(0,167 mol), 50 mJL of toluene, and 158 g (2.0 mol) of pyridine were charged, and stirring was started in a nitrogen stream. Next, 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) 14. 3g
(1.1 mol) was slowly added dropwise from the dropping funnel. After the reaction was carried out in a hot water bath at a temperature of 60° C. for 8 hours with stirring, the precipitated solid (mainly pyridine hydrochloride) was removed by filtration.

Thereafter, the filtrate was washed with water, dried using Glauber's salt, and the solvent was removed by vacuum distillation to obtain a yellow viscous liquid, 1,1,3,3,5,5-hexa(methacryloyl). ethylenedioxy)cyclotriphosphazene [hereinafter referred to as
This is simply called a curable phosphazene compound. ] 1
38 g was obtained. The yield was 91%.

(Example 1) Preparation example of pace coaching material 10 g of the curable phosphazene compound obtained in the above reference example
, 5 g of methyl ethyl ketone, 6 g of isopropyl alcohol
g and 0-5 g of benzophenone were mixed to prepare a base coating material.

0.5 g of 2-glucoxyethyl methacrylate (hereinafter sometimes abbreviated as GEM) was added to the base coating material prepared as above, and coating material A was added.
And so. This was coated on polycarbonate using a bar coater and irradiated with ultraviolet rays at 600 J/cm2 to form a cured coating film.

The obtained cured coating film sample with substrate was placed in a constant temperature and humidity bath at a temperature of 15°C and a humidity of 20%, and after 30 minutes, the temperature was 25°C.
The sample was taken out in an environment with a humidity of 60%, and the surface condition was visually observed (hereinafter, this will be referred to as Test 1).

Furthermore, after leaving the sample in running water (tap water) for two months, it was taken out and its surface was wiped with a cloth, and the same test as above was conducted on this sample, and the surface condition was visually observed (hereinafter referred to as ``tap water''). (referred to as Test 2).

In addition, the surface hardness and light transmittance of the sample were measured.

The results of these tests are shown in Table 1.

(Comparative example 1) The base coating material prepared in Example 1.

Example 1 was carried out in the same manner as in Example 1, except that 2-glucoxyethyl methacrylate (GEM) was used as it was without adding it to form a cured coating film.

The test results are shown in Table 1.

(Comparative Examples 2 to 4) In place of 2-glucoxyethyl methacrylate (OEM), Ichihara's antifogging agent [partial fatty acid ester of polyhydric alcohol (a) for Comparative Example 2, and for Comparative Example 3 Example 1 was repeated except that 0.5 g of ethylene oxide adduct of fatty acid (b) was added for Comparative Example 4, and 0.5 g of ethylene oxide adduct of alkylphenol (C) was added for Comparative Example 4.

The test results for each sample obtained are shown in Table 1.

1st Test 10XOOO Test 20 X XXX Surface Hardness 9 8+41517 Total Light Transmittance 92 92 89 88 83
Antifogging agent GEM: 2-glycoxyethyl methacrylate (a)
, (b) and (c), see text.

Evaluation symbols for Test 1 and Test 2: O: No clouding, X: Cloudy Surface hardness Wear axis: C9-10, Number of revolutions: 100. Weight: 40
0 g [Effects of the Invention] According to the present invention, it has a sufficient anti-fogging effect, can maintain the anti-fogging effect for a long period of time, and has excellent curability, making it suitable for cured coatings and cured molded products. It is possible to provide an antifogging curable resin composition having advantages such as ease of film formation and molding. In particular, when used as a cured coating material, it is possible to obtain a cured coating III (film) which has a high antifogging effect even with one application and is extremely advantageous in practice, such as lasting for a long period of time.

Therefore, the antifogging curable resin composition of the present invention has extremely high utility value in the field of manufacturing a wide range of antifogging molded products that require antifogging properties, especially long-term sustainability.

Claims (2)

[Claims] (1) An anti-fog curable resin composition comprising a curable resin compound and a reactive anti-fog agent. (2) The antifogging curable resin composition according to claim 1, wherein the curable resin compound is a curable phosphazene compound.