JP4780095B2 - Method for producing curable resin composition - Google Patents

Description

  The present invention relates to a method for producing a curable resin composition, and more particularly to a method for producing a curable resin composition capable of forming a cured film having high transparency and low reflectance characteristics.

  Currently, with the development of multimedia, various developments have been seen in various display devices (display devices). Among various types of display devices, especially those that are used outdoors, especially for portable use, the improvement of visibility has become increasingly important, and there is a demand for easier viewing even in large display devices. This is a technical issue as it is.

Conventionally, as a means for improving the visibility of a display device, an antireflection film made of a low refractive index material is coated on the substrate of the display device, and as a method of forming the antireflection film, For example, a method of forming a thin film of a fluorine compound by vapor deposition is known.
However, in recent years, there has been a demand for a technique capable of forming an antireflection film on a large display device at a low cost centering on a liquid crystal display device. However, in the case of the vapor deposition method, it is difficult to form a high-efficiency and uniform antireflection film on a large-area substrate, and it is difficult to reduce the cost because a vacuum apparatus is required. is there.

  Under such circumstances, a method of forming an antireflection film by preparing a liquid composition by dissolving a fluorine-based polymer having a low refractive index in an organic solvent and applying it to the surface of a substrate has been studied. Yes. For example, Japanese Patent Application Laid-Open No. 61-40845 and Japanese Patent Publication No. 6-98703 propose that a fluorinated alkylsilane is applied to the surface of a substrate, and Japanese Patent Application Laid-Open No. 6-115023 discloses a specific structure. There has been proposed a method of applying a fluorine-based polymer having the following.

However, the conventional antireflection film made of a fluorine-based material is not sufficiently adhered to the base material, and has a problem that the antireflection film layer is peeled off particularly when it is repeatedly rubbed.
The present invention was made against the background described above, and its purpose is a cured film having high transparency, low refractive index, high adhesion to a substrate, and excellent scratch resistance. It is providing the manufacturing method of the curable resin composition which can form.

The method for producing a curable resin composition of the present invention includes a component (a) composed of a fluorine-containing olefin compound and a monomer comprising a monomer containing a hydroxyl group or an epoxy group, which is copolymerizable with the component (a). The structural unit derived from the component (a) is obtained by reacting the component (b) composed of the body compound, the component (c) composed of the azo group-containing polysiloxane compound, and the component (d) composed of the reactive emulsifier. 20 to 70 mol%, 10 to 70 mol% of structural units derived from component (b) (of which the proportion of those derived from monomers containing a hydroxyl group or an epoxy group is 1 to 20 mol%), The polysiloxane segment derived from the component (c) is contained in the main chain in an amount of 0.1 to 20 mol%, and the structural unit derived from the component (d) is contained in a proportion of 0.1 to 10 mol%, and the fluorine content 30% by weight or more , And the resulting a number average molecular weight terms of polystyrene of 5,000 or more, an olefin polymer having a hydroxyl group and / or epoxy group (A),
3 to 50 parts by weight of a crosslinkable compound comprising 100 parts by weight of the olefin polymer (A) and (B) a compound containing at least one of or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Is heated to 50 to 150 ° C. in the presence of an organic solvent to cause a reaction, whereby a solution of the curable resin composition is obtained.

  According to the method for producing a curable resin composition of the present invention, a curable resin composition that exhibits good thermosetting and forms a cured product having a low refractive index and excellent transparency to visible light is produced. . The curable resin composition obtained by the present invention can be advantageously used for the formation of an optical material such as an antireflection film and an optical fiber sheath material, and weather resistance is required by utilizing the high fluorine content. It can be suitably used as a coating material, a weather resistant film material, a coating material, etc. Moreover, since the cured film has excellent adhesion to the substrate, high scratch resistance, and imparts a good antireflection effect, it is extremely useful as an antireflection film and can be applied to various display devices. The visibility can be improved.

<Olefin polymer>
In the curable resin composition of the present invention, an olefin polymer having a polysiloxane segment in the main chain, a fluorine content of 30% by weight or more, and a number average molecular weight in terms of polystyrene of 5,000 or more (hereinafter, "Specific fluorine polymer") is contained as an essential component.
In the present invention, the specific fluoropolymer is an olefin polymer having a polysiloxane segment represented by the following general formula 1 in the main chain, and the ratio of the polysiloxane segment in the specific fluoropolymer is: Usually 0.1 to 10 mol%.

式中、Ｒ¹ およびＲ² は、同一でも異なってもよく、水素原子、アルキル基、ハロゲン化アルキル基またはアリール基を示す。

In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group.

Further, the specific fluorine-based polymer has a fluorine content of 30% by weight or more, preferably 40 to 60% by weight, and further has a number average molecular weight in terms of polystyrene obtained by gel permeation chromatography of 5000 or more, preferably Is from 10,000 to 500,000.
Here, the fluorine content is a value measured by the alizarin complexone method, and the number average molecular weight is a value when tetrahydrofuran is used as a developing solvent.

  The specific fluorine-based polymer in the present invention includes (a) a fluorine-containing olefin compound (hereinafter referred to as “component (a)”), (b) another monomer compound copolymerizable with the component (a) ( Hereinafter referred to as “component (b)”) and (c) an azo group-containing polysiloxane compound (hereinafter referred to as “component (c)”), and (d) a reactive emulsifier (hereinafter referred to as “(d)” as required. It can be obtained by reacting “component”).

Examples of the component (a) include compounds having at least one polymerizable unsaturated double bond and at least one fluorine atom. Specific examples thereof include (1) tetrafluoroethylene, Fluoroolefins such as hexafluoropropylene and 3,3,3-trifluoropropylene; (2) alkyl perfluoro vinyl ethers or alkoxyalkyl perfluoro vinyl ethers; (3) perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), Perfluoro (alkyl vinyl ethers) such as perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); (4) Perfluoro (alkoxyal) such as perfluoro (propoxypropyl vinyl ether) Vinyl ether) species; other can be exemplified. These compounds can be used alone or in combination of two or more.
Of these, hexafluoropropylene, perfluoroalkyl perfluorovinyl ether or perfluoroalkoxyalkyl perfluorovinyl ether is particularly preferable, and a combination thereof is preferably used.

  Specific examples of the component (b) copolymerizable with the component (a) include (1) methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n -Alkyl vinyl ethers or cycloalkyl vinyl ethers such as pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; (2) vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl esters such as vinyl acid vinyl, vinyl caproate, vinyl versatate, vinyl stearate; (3) methyl (meth) acrylate , Ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy) ethyl ( (Meth) acrylates such as (meth) acrylate; (4) carboxyl group-containing monomer compounds such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.

  The monomer compound of component (b) preferably has a functional group, and when such component (b) is used, the specific fluorine-based polymer has the functional group. A curable resin composition can be obtained. Here, the functional group is preferably a hydroxyl group or an epoxy group, and may have both.

Examples of the monomer compound containing a hydroxyl group include (1) 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl. Hydroxyl group-containing vinyl ethers such as vinyl ether and 6-hydroxyhexyl vinyl ether; (2) hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether; (3) allyl alcohol; 4) Hydroxyethyl (meth) acrylic acid ester;
Examples of the monomer compound containing an epoxy group include vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, glycidyl crotonic acid, and methyl glycidyl maleate.
These compounds can be used alone or in combination of two or more.

Among the above monomer compounds, alkyl vinyl ethers, cycloalkyl vinyl ethers, or carboxylic acid vinyl esters are preferably used from the viewpoint of increasing the yield in a polymerization reaction for obtaining a specific fluorine-based polymer. Is done.
On the other hand, from the point of increasing the fluorine content in a specific fluoropolymer, for example, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, etc. It is preferable to use a molecular weight monomer.
Furthermore, in order to increase the hardness of the thin film after curing of the curable resin composition and reduce the refractive index, a branched monomer such as isopropyl vinyl ether, tert-butyl vinyl ether, vinyl pivalate, or the like is used. It is effective.

The azo group-containing polysiloxane compound of component (c) is a compound having a polysiloxane segment represented by the general formula 1 while containing an azo group that is easily thermally decomposable represented by -N = N-, For example, it can be produced by the method described in JP-A-6-93100.
Specific examples of the component (c) include compounds represented by the following general formula 2.

式中、ｙ＝１０〜５００、ｚ＝１〜５０である。

In the formula, y = 10 to 500 and z = 1 to 50.

  Preferred combinations of the components (a), (b) and (c) are, for example, (1) fluoroolefin / alkyl vinyl ether / polydimethylsiloxane unit, (2) fluoroolefin / perfluoro (alkyl vinyl ether) / alkyl Vinyl ether / polydimethylsiloxane unit, (3) fluoroolefin / perfluoro (alkoxyalkyl) vinyl ether / alkyl vinyl ether / polydimethylsiloxane unit, (4) fluoroolefin / (perfluoroalkyl) vinyl ether / alkyl vinyl ether / polydimethylsiloxane unit, 5) Fluoroolefin / (perfluoroalkoxyalkyl) vinyl ether / alkyl vinyl ether / polydimethylsiloxane unit.

  In the specific fluoropolymer of the present invention, the structural unit derived from the component (a) is 20 to 70 mol%, preferably 25 to 65 mol%, more preferably 30 to 60 mol%. When the proportion of the structural monomer derived from the component (a) is less than 20 mol%, the fluorine content in the obtained specific fluorine-based copolymer tends to be excessive, and the cured product of the resulting curable resin composition has a refractive index. Is unlikely to be low enough. On the other hand, when the proportion of the structural unit derived from the component (a) exceeds 70 mol%, the solubility of the obtained specific fluoropolymer in an organic solvent is remarkably lowered, and the resulting curable resin composition is , Transparency and adhesion to the substrate are small.

In the specific fluoropolymer, the structural unit derived from the component (b) is 10 to 70 mol%, preferably 15 to 65 mol%, more preferably 30 to 60 mol%. When the proportion of the structural unit derived from the component (b) is less than 10 mol%, the specific fluoropolymer has poor solubility in an organic solvent, and when it exceeds 70 mol%, curing with the curable resin composition is performed. The object has deteriorated optical properties of transparency and low reflectance.
In addition, by using a monomer containing a hydroxyl group or an epoxy group as the component (b), the strength of the cured film can be improved when the resulting curable resin composition is used as a coating agent. preferable.
The ratio of the monomer containing a hydroxyl group or an epoxy group in all monomers is 0 to 20 mol%, preferably 1 to 20 mol%, more preferably 3 to 15 mol%. When this ratio exceeds 20 mol%, the cured product obtained from the curable resin composition has deteriorated optical characteristics, and the cured film becomes brittle when used as a coating agent.

  The azo group-containing polysiloxane (c) is itself a thermal radical generator, and has an action as a polymerization initiator in a polymerization reaction for obtaining a specific fluorine-based polymer. Can also be used together. The proportion of the structural unit derived from the component (c) in the specific fluoropolymer is such that the polysiloxane segment represented by the general formula 1 is 0.1 to 20 mol%, preferably 0.1 to 15 mol%, The ratio is preferably 0.1 to 10 mol%. When the proportion of the polysiloxane segment represented by the general formula 1 exceeds 20 mol%, the specific fluoropolymer obtained is inferior in transparency, and when used as a coating agent, the fluorinated polymer is repelled at the time of coating. Etc. are likely to occur.

In the present invention, in addition to the components (a) to (c), it is preferable to use a reactive emulsifier as a monomer component as the component (d). By using this (d) component, when using a specific fluorine-type polymer as a coating agent, favorable applicability | paintability and leveling property can be obtained.
As the reactive emulsifier, it is particularly preferable to use a nonionic reactive emulsifier. Specific examples of the nonionic reactive emulsifier include compounds represented by the following general formula 3.

式中、ｎ、ｍおよびｓは繰り返し単位を示し、ｎ＝１〜２０、ｍ＝０〜４、ｓ＝３〜５０であることが好ましい。

In the formula, n, m and s represent repeating units, and it is preferable that n = 1 to 20, m = 0 to 4, and s = 3 to 50.

  In the specific fluoropolymer, the proportion of the structural unit derived from the component (d) is usually 0 to 10 mol%, preferably 0.1 to 5 mol%. When this ratio exceeds 10 mol%, the resulting curable resin composition is tacky and difficult to handle, and moisture resistance decreases when used as a coating agent.

(D) The preferable combination in the case of containing a component is as follows. Here, the “functional group” is a hydroxyl group or an epoxy group.
(1) fluoroolefin / alkyl vinyl ether / functional group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier, (2) fluoroolefin / perfluoro (alkyl vinyl ether) / alkyl vinyl ether / functional group-containing vinyl ether / polydimethylsiloxane unit / Nonionic reactive emulsifier, (3) fluoroolefin / perfluoro (alkoxyalkyl) vinyl ether / alkyl vinyl ether / functional group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier, (4) fluoroolefin / (perfluoroalkyl) vinyl ether / Alkyl vinyl ether / functional group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier, (5) fluoroolefin / (perfluorocarbon Kokishiarukiru) vinyl ether / alkyl vinyl ether / functional group-containing vinyl ether / polydimethylsiloxane unit / nonionic reactive emulsifier.

  As a polymerization mode for producing a specific fluoropolymer in the present invention, any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or a solution polymerization method using a radical polymerization initiator can be used. As the polymerization operation, an appropriate one can be selected from batch operation, semi-continuous operation or continuous operation.

  Examples of radical polymerization initiators that can be used in combination with component (c) include (1) diacyl peroxides such as acetyl peroxide and benzoyl peroxide; (2) ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide. (3) Hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide; (4) Di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc. Dialkyl peroxides; (5) peroxyesters such as tert-butylperoxyacetate and tert-butylperoxypivalate; and (6) azo-based compounds such as azobisisobutyronitrile and azobisisovaleronitrile. Compounds like; (7) ammonium persulfate, sodium persulfate, persulfates such as potassium persulfate; Other can be exemplified.

Specific examples of the radical polymerization initiator include, for example, perfluoroethyl iodide, perfluoropropyl iodide, perfluorobutyl iodide, (perfluorobutyl) ethyl iodide, perfluorohexyl iodide, 2- ( Perfluorohexyl) ethyl iodide, perfluoroheptyl iodide, perfluorooctyl iodide, 2- (perfluorooctyl) ethyl iodide, perfluorodecyl iodide, 2- (perfluorodecyl) ethyl iodide, heptafluoro- 2-iodopropane, perfluoro-3-methylbutyl iodide, perfluoro-5-methylhexyl iodide, 2- (perfluoro-5-methylhexyl) ethyl iodide, perfluoro-7-methyloctyl iodide, -(Perfluoro-7-methyloctyl) ethyl iodide, perfluoro-9-methyldecyl iodide, 2- (perfluoro-9-methyldecyl) ethyl iodide, 2,2,3,3-tetrafluoropropyl iodide, 1H , 1H, 5H-octafluoropentyl iodide, 1H, 1H, 7H-dodecafluoroheptyl iodide, tetrafluoro-1,2-diiodoethane, octafluoro-1,4-diiodobutane, dodecafluoro-1,6-diiodohexane, etc. Mention may be made of iodine-containing fluorine compounds.
The iodine-containing fluorine compound can be used alone or in combination with the organic peroxide, azo compound or persulfate.

  The polymerization reaction for obtaining a specific fluoropolymer is preferably carried out in a solvent system using a solvent. Examples of preferable organic solvents include (1) esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, and cellosolve; (2) ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; (3) Cyclic ethers such as tetrahydrofuran and dioxane; (4) Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; (5) Aromatic hydrocarbons such as toluene and xylene; be able to. Further, if necessary, alcohols, aliphatic hydrocarbons and the like can be mixed and used.

Although the specific fluoropolymer obtained as described above may be able to use the reaction solution obtained by the polymerization reaction as it is as the curable resin composition, it may be appropriately used for the polymerization reaction solution. It is also free to perform post-processing.
As the post-treatment, for example, a polymerization reaction solution is added dropwise to an insolubilizing solvent for the specific fluoropolymer made of alcohol or the like, and a general purification method represented by a purification method for coagulating the specific fluoropolymer. A reprecipitation treatment can be performed, and then a solution of a specific fluoropolymer can be prepared by dissolving the obtained solid copolymer in a solvent.
Moreover, what removed the residual monomer from the polymerization reaction solution can also be used as a solution of a specific fluoropolymer as it is.

<Curable resin composition>
In practice, the curable resin composition of the present invention needs to have curability, and if the specific fluoropolymer itself does not have sufficient curability, a crosslinkable compound should be added. Thus, necessary curability can be imparted and curing characteristics can be improved.
When a crosslinkable compound is used, a mixture of the crosslinkable compound and a specific fluoropolymer is used as the curable resin composition, or all of the specific fluoropolymer and the crosslinkable compound are used. A reaction product obtained by reaction or a state in which only a part thereof is reacted can be used as the curable resin composition.

<Crosslinkable compound>
Examples of the crosslinkable compound include various amino compounds, various hydroxyl group-containing compounds such as pentaerythritol, polyphenol, and glycol, and others.

  The amino compound used as the crosslinkable compound is a total of two amino groups capable of reacting with a hydroxyl group or an epoxy group present in the fluoropolymer, for example, one or both of a hydroxyalkylamino group and an alkoxyalkylamino group. Specific examples of the compound contained above include melamine compounds, urea compounds, benzoguanamine compounds, glycoluril compounds, and the like.

Melamine compounds are generally known as compounds having a skeleton in which a nitrogen atom is bonded to a triazine ring, and specific examples include melamine, alkylated melamine, methylol melamine, alkoxylated methyl melamine, and the like. However, it is preferable to have one or both of a methylol group and an alkoxylated methyl group in one molecule in total. Specifically, methylolated melamine obtained by reacting melamine and formaldehyde under basic conditions, alkoxylated methylmelamine, or a derivative thereof is preferable, and good storage stability is obtained particularly for the curable resin composition. Alkoxylated methyl melamine is preferable in that it can be obtained and good reactivity can be obtained.
There are no particular limitations on the methylolated melamine and the alkoxylated methylmelamine used as the crosslinkable compound. For example, the methylolated melamine and the alkoxylated methylmelamine can be obtained by the method described in the document “Plastic Materials Course [8] Urea Melamine Resin” (Nikkan Kogyo Shimbun) Various resinous materials can also be used.

  Examples of urea compounds include polymethylolated urea and derivatives thereof, such as alkoxylated methylurea, methylolated uron having a uron ring, and alkoxylated methyluron. And various compounds described in the above documents can be used for compounds such as urea derivatives.

  The amount of the crosslinkable compound used relative to 100 parts by weight of the specific fluoropolymer is 70 parts by weight or less, preferably 3 to 50 parts by weight, and more preferably 5 to 30 parts by weight. If the amount of the crosslinkable compound used is too small, the durability of the thin film formed by the resulting curable resin composition may be insufficient, and if it exceeds 70 parts by weight, the specific fluoropolymer and In this reaction, it is difficult to avoid gelation, and the cured film does not have a low refractive index, and the cured product may become brittle.

The reaction between the specific fluoropolymer and the crosslinkable compound can be achieved by, for example, adding the crosslinkable compound to a solution of an organic solvent in which the specific fluoropolymer is dissolved, and heating and stirring the reaction system for an appropriate time. It can be done while making it. The heating temperature for this reaction is in the range of 30-150 ° C, preferably in the range of 50-120 ° C. When the heating temperature is 30 ° C or lower, the progress of the reaction is extremely slow, and when the heating temperature is 150 ° C or higher, in addition to the intended reaction, a crosslinking reaction occurs due to the reaction between methylol groups and alkoxylated methyl groups in the crosslinkable compound, resulting in a gel Since it produces | generates, it is not preferable.
The progress of the reaction is quantitatively confirmed by quantifying methylol groups or alkoxylated methyl groups by infrared spectroscopic analysis, etc., or by recovering the dissolved polymer by reprecipitation method and measuring the increase amount. It can be performed.

Moreover, it is preferable to use the same organic solvent, for example, the same organic solvent used in manufacture of a specific fluoropolymer for reaction of a specific fluoropolymer and a crosslinkable compound.
In the present invention, the reaction solution obtained by the specific fluoropolymer and the crosslinkable compound thus obtained can be used as it is as the solution of the curable resin composition, and various additives can be used as necessary. It can also be used after blending.

<Additives>
The curable resin composition of the present invention includes, for example, various polymers having a hydroxyl group for the purpose of improving the coating properties of the curable resin composition and the properties of the thin film after curing, and imparting photosensitivity to the coating film. Various additives such as stabilizers such as anti-aging agents and ultraviolet absorbers, thermal acid generators, photosensitive acid generators, surfactants, solvents, polymerization inhibitors, etc. Can be contained.
In particular, for the purpose of improving the hardness and durability of the formed cured film, it is preferable to add a thermal acid generator or a photoacid generator, particularly without reducing the transparency after curing of the curable resin composition, In addition, it is preferable to select and use one that dissolves uniformly in the solution.

<Polymer having hydroxyl group>
Examples of the polymer having a hydroxyl group that can be blended in the curable resin composition of the present invention include a polymer obtained by copolymerizing a hydroxyl group-containing copolymerizable monomer such as hydroxyethyl (meth) acrylate, a novolac resin, or the like. Examples of the resol resin include resins having a known phenol skeleton.

<Coloring agents such as pigments or dyes>
Examples of colorants that can be blended in the curable resin composition of the present invention include (1) extender pigments such as alumina white, clay, barium carbonate, barium sulfate; (2) zinc white, lead white, yellow lead Inorganic pigments such as red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black; (3) organics such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green Pigments; (4) basic dyes such as magenta and rhodamine; (5) direct dyes such as direct scarlet and direct orange; (6) acidic dyes such as roserine and methanyl yellow; and the like.

<Stabilizers such as anti-aging agents and UV absorbers>
A well-known thing can be used as an anti-aging agent and ultraviolet absorber which can be mix | blended with the curable resin composition of this invention.
Specific examples of the antioxidant include, for example, di-tert-butylphenol, pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone mono Propyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl- 4-hydroxyphenyl) -3-phenylpropane, diphenylamines, phenylenediamines, phenothiazine, mercaptobenzimidazole and the like.

  Specific examples of ultraviolet absorbers include, for example, salicylic acid ultraviolet absorbers represented by phenyl salicylate, benzophenone ultraviolet absorbers such as dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, benzotriazole ultraviolet absorbers, cyano Ultraviolet absorbers used as additives for various plastics such as acrylate ultraviolet absorbers can be used.

<Heat acid generator>
The thermal acid generator that can be blended in the curable resin composition of the present invention improves the heating conditions to be milder when the coating film of the curable resin composition is heated and cured. It is a substance that can.
Specific examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid and maleic acid, and various aromatic carboxylic acids such as benzoic acid and phthalic acid. Examples thereof include acids and salts thereof, alkylbenzene sulfonic acids and ammonium salts thereof, various metal salts, phosphoric acid esters of organic acids and the like.
The use ratio of the thermal acid generator is 0 to 10 parts by weight, preferably 0.1 to 5 parts by weight, with respect to 100 parts by weight of the specific fluoropolymer in the curable resin composition. When this ratio is excessive, the storage stability of the curable composition is deteriorated, which is not preferable.

<Photosensitive acid generator>
The photosensitive acid generator that can be blended in the curable resin composition of the present invention imparts photosensitivity to the coating film of the curable resin composition and, for example, irradiates the coating film with light or the like. It is a substance that makes it possible to photocur.
Examples of the photosensitive acid generator include (1) various onium salts such as iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt; (2) β-ketoester, β-sulfonylsulfone and these Sulfone compounds such as α-diazo compounds of (3); sulfonic acid esters such as alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates; (4) sulfonimide compounds represented by the following general formula 4 (5) Diazomethane compounds represented by the following general formula 5;

式中、Ｘはアルキレン基、アリレーン基、アルコキシレン基等の２価の基を示し、Ｒ³ はアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価に基を示す。

In the formula, X represents a divalent group such as an alkylene group, an arylene group, or an alkoxylen group, and R ³ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

式中、Ｒ⁴ およびＲ⁵ は、互いに同一でも異なってもよく、アルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。

In the formula, R ⁴ and R ⁵ may be the same as or different from each other, and represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group, or a halogen-substituted aryl group.

The photosensitive acid generator can be used alone or in combination of two or more, and can also be used in combination with the thermal acid generator.
The usage-amount of a photosensitive acid generator is 0-20 weight part with respect to 100 weight part of sclerosing | hardenable specific fluoropolymers in curable resin composition, Preferably it is 0.1-10 weight part. When this ratio is excessive, the strength of the cured film becomes inferior and the transparency is also lowered, which is not preferable.

<Polymerization inhibitor>
Examples of the thermal polymerization inhibitor that can be incorporated into the curable resin composition of the present invention include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n -Butylphenol, phenol, hydroquinone monopropyl ether, 4,4 '-[1- [4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and the like.
The thermal polymerization inhibitor is preferably used in an amount of 5 parts by weight or less based on 100 parts by weight of the curable resin composition.

<Surfactant>
In the curable resin composition of the present invention, a surfactant can be blended for the purpose of improving the applicability of the curable resin composition. As this surfactant, known ones can be used. Specifically, for example, various anionic surfactants, cationic surfactants, and nonionic surfactants can be used. In order to make the film have excellent strength and good optical properties, it is preferable to use a fluorosurfactant.
The use ratio of the surfactant is preferably 5 parts by weight or less with respect to 100 parts by weight of the curable resin composition.

<Solvent>
Although the curable resin composition of the present invention contains a solvent as an essential component, the curable resin composition is usually a solvent used in the production of a specific fluorine-based polymer, or a specific fluorine-based resin. It is obtained as a solution in the solvent used for the reaction between the polymer and the crosslinkable compound, and therefore contains the solvent as it is. Further, for the purpose of improving the applicability of the curable resin composition and other purposes, a solvent can be separately added and blended.
Preferable solvents contained in the curable resin composition of the present invention include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and esters such as ethyl acetate and butyl acetate.
Furthermore, in the solution of the curable resin composition of the present invention, a solvent that cannot dissolve the specific fluoropolymer, for example, a poor solvent such as water, alcohols, ethers, etc., the specific fluoropolymer is deposited. It can be used in combination as long as it is not. Thereby, the solution of the specific fluorine-based polymer may have good storage stability and preferable coating properties. Examples of such a poor solvent include ethyl alcohol, isopropyl alcohol, tert-butyl alcohol, and the like.

<Formation method of coating film>
The curable resin composition of the present invention can be applied to various substrates in the form of a solution, and by curing the obtained coating film, for example, excellent antireflection when the substrate is a transparent substrate A film is formed.
Specific examples of the transparent substrate include various transparent plastic plates such as inorganic glass, polycarbonate resin, acrylic resin, styryl resin, arylate resin, norbornane resin, and films.
As a coating method, a known coating method can be used, and various methods such as a dip method, a coater method, and a printing method can be applied.

In order to cure the coating film of the curable resin composition formed by coating to form a cured film having excellent optical properties and durability, it is particularly preferable to give a heat history by heating. Of course, even when left at room temperature, the curing reaction proceeds with the passage of time, and the desired cured film is formed. However, in practice, heating and curing are effective in reducing the required time. is there.
Moreover, the curing reaction can be further promoted by adding a thermal acid generator as a curing catalyst. The curing catalyst is not particularly limited, and the above-mentioned various acids and salts used as curing agents for general urea resins, melamine resins, and the like can be used, and ammonium salts are particularly preferably used. it can.
The heating conditions for the curing reaction can be selected as appropriate, but the heating temperature needs to be equal to or lower than the heat resistant limit temperature of the substrate to be coated.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following description, “parts” and “%” indicate parts by weight and% by weight, respectively, unless otherwise specified.
Production Example 1
<Production of specific fluoropolymer>
A stainless steel autoclave with a magnetic stirrer with an internal volume of 2.0 liters was sufficiently replaced with nitrogen gas, 500 g of solvent ethyl acetate, 53.2 g of (a) component perfluoro (propyl vinyl ether) (FPVE), and (b) of component (b) 48.7 g of ethyl vinyl ether (EVE) and 26.4 g of hydroxybutyl vinyl ether (HBVE), 20.0 g of “ADEKA rear soap NE-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) as a nonionic reactive emulsifier of component (d), As the azo group-containing polydimethylsiloxane of component (c), 3.0 g of “VPS-1001” (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.0 g of polymerization initiator lauroyl peroxide (LPO) were charged, and dry ice-methanol After cooling to −50 ° C. with a system cryogen, oxygen in the system was removed again with nitrogen gas.

Next, 120 g of component (a) hexafluoropropylene (HFP) was charged, and the temperature was raised. The pressure when the temperature in the autoclave reached 60 ° C. was 6.1 kgf / cm ² . Thereafter, the reaction was continued at 60 ° C. with stirring for 20 hours, and when the pressure dropped to 2.5 kgf / cm ² , the autoclave was cooled with water to stop the reaction. After the reaction product reached room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 221 g of a fluorinated copolymer A1. Table 1 shows the monomer charge, yield, polymerization addition rate, and solid content concentration for obtaining the fluorine-based copolymer A1.

When the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography using a 0.5% solution prepared by dissolving this fluorocopolymer A1 in tetrahydrofuran (THF), it was 55000.
Further, the glass transition temperature (Tg) by differential thermal analysis (DSC), the fluorine content by alizarin complexone method, and the hydroxyl value by acetylation using acetic anhydride were measured. In addition, both 1H-NMR and 13C-NMR NMR analysis and elemental analysis were performed, and the inorganic silica content was measured from the fluorine content, the hydroxyl value, and the remaining weight after firing at 600 ° C. The ratio of each monomer component constituting the polymer A1 was determined. The results are shown in Table 2.

Production Examples 2-7, Comparative Production Examples 1 and 2
Fluoropolymers A2 to A7 and comparative copolymers B1 and B2 were prepared in the same manner as in Example 1 except that the type and amount of each monomer were changed as shown in Table 1. . Table 2 shows the ratio and physical properties of each monomer component constituting these copolymers.

Example 1
<Production of crosslinked polymer>
As shown in Table 3, 100 g of the specific fluoropolymer A1 obtained in Production Example 1 was mixed with 30 g of the crosslinkable compound methoxylated methylmelamine “Cymel 303” (manufactured by Mitsui Cytec Co., Ltd.) as a solvent methyl isobutyl. It was dissolved in 900 g of ketone (MIBK) and reacted at 100 ° C. with stirring for 5 hours. After the reaction, the reaction mixture was cooled to room temperature to obtain a solution of a crosslinked polymer that was a reaction product of a specific fluorine-based polymer and a crosslinking compound.
Subsequently, this solution was gradually added to a large excess of cold methanol with stirring to precipitate a crosslinked polymer. Furthermore, after the obtained crosslinked polymer was dissolved in MIBK, a precipitation treatment was performed using cold methanol.
The obtained crosslinked polymer was dried by vacuum drying. A chart of the infrared absorption spectrum of the crosslinked polymer after drying is shown in FIG.

<Preparation of curable resin composition solution>
As shown in Table 3, a curable resin composition solution was prepared by adding 100 g of the above-mentioned crosslinked polymer and 2 g of p-toluenesulfonic acid as a curing catalyst to 900 g of MIBK and dissolving them. This solution had a solid content concentration of 10% and a viscosity of 30 cps or less.

<Formation and evaluation of cured film of curable resin composition>
Measurement of Refractive Index The above curable resin composition solution was applied onto a silicon wafer by a spin coater so that the thickness after drying was about 0.1 μm, and the resulting coating film was measured using an ellipsometer with an ellipsometer. The refractive index (n _D ²⁵ ) at 0 ° C. was measured.

Measurement of transmittance / reflectance After forming a coating film by the casting method using the above curable resin composition solution, it is cured by heating at 120 ° C. for 1 hour using a press, and cured to a thickness of 200 μm. A membrane was formed. About this cured film (this is called "sample 1"), the light transmittance in wavelength 340-700nm was measured. Further, the pencil hardness was measured according to JIS K5400.
Further, the curable resin composition solution is diluted with butanol to prepare a varnish having a solid content concentration of 4%, and this varnish is pulled up to a transparent polycarbonate plate having a thickness of 3 mm by a dip coating method at a speed of 100 mm / min. The coated film thus obtained was heated at 120 ° C. for 1 hour to form a cured film. The thickness of the cured film measured with an ellipsometer was 1140 angstroms.
Using a spectrophotometer “U-3410 type” (manufactured by Hitachi, Ltd.) with an integrating sphere having a diameter of 60 mm, the polycarbonate plate (this is referred to as “Sample 2”) on which this cured film is formed is used. The rate and reflectivity were measured.

Scratch resistance test Further , for the sample 2, the scratch resistance test was performed in order to evaluate the adhesion of the cured film to the substrate and the strength of the cured film. That is, the surface of the cured film was repeatedly rubbed 25 times under the condition of a load of 1 kg / cm ² using Kimwipe (manufactured by Jujo Kimberley), and the presence or absence of scratches on the surface of the cured film was visually confirmed. And, it was evaluated as “◯” when no peeling of the cured film or occurrence of scratches was observed, and “×” when the cured film was partially peeled or streaky scratched on the surface of the cured film. did.

Examples 2-9 and Comparative Examples 1-2
In Example 1, a crosslinked polymer was produced in the same manner as in Example 1 except that the specific fluorine-based polymer and the crosslinkable compound were changed to those shown in Table 3, and the obtained crosslinked polymer was converted to Table 3. The curable resin composition was manufactured by adding the curing catalyst shown in the above. And the coating film formed using these curable resin compositions was heated at 120 degreeC for 60 minute (s), the cured film was formed, and various physical properties were measured about this. The results are shown in Table 4.
In Table 3, the amount of the curing catalyst indicates an addition amount (g) with respect to 100 g of the curable resin composition.

The abbreviations in the table indicate the following.
(A) Component HFP: Hexafluoropropylene,
CTFE: chlorotrifluoroethylene,
FPVE: Perfluoro (propyl vinyl ether)

(B) Component EVE: ethyl vinyl ether,
iso-BVE: isobutyl vinyl ether,
CHVE: cyclohexyl vinyl ether,
VAc: vinyl acetate,
VPi: vinyl pivalate,
VeoVa10: vinyl versatate,
HBVE: hydroxybutyl vinyl ether,
GVE: Glycidyl vinyl ether

(C) Component VPS-0501: azo group-containing polydimethyl represented by the above general formula 2, y = 60-80, z = 6-8, number average molecular weight 30000-40000, polysiloxane segment molecular weight about 5000 Siloxane (manufactured by Wako Pure Chemical Industries),
VPS-1001: azo group-containing polydimethylsiloxane represented by the above general formula 2, y = 120 to 150, z = 7 to 10, number average molecular weight 70000 to 90000, polysiloxane segment molecular weight about 5000 (Wako Pure Chemical Industries, Ltd.) Yakuhin Kogyo Co., Ltd.)

(D) Component NE-10: Nonionic reactive emulsifier “NE-10” (manufactured by Asahi Denka Kogyo Co., Ltd.) represented by the above general formula 3, wherein n = 9, m = 1, and s = 10.
NE-30: Nonionic reactive emulsifier “NE-30” (manufactured by Asahi Denka Kogyo Co., Ltd.) represented by the above general formula 3, wherein n = 9, m = 1, and s = 30

(Crosslinkable compound)
Cymel 303: a compound represented by the following formula 6 self-condensed to an average of 1.7 mer,
Cymel 238: a compound represented by the following formula 7 self-condensed to an average of 1.6 mer,
Cymel 1170: A compound represented by the following formula 8 self-condensed into an average 1.5-mer,
My Coat 106: A compound represented by the following formula 9 self-condensed to an average of 1.7 mer

From the results of Table 4, according to the curable resin composition according to the examples, it has a low refractive index, high light transmittance, high strength, low reflectance, and high adhesion to the substrate. It is clear that a film can be formed.
On the other hand, when the structural unit by the component (c) is not contained, even if they have the same average molecular weight, the scratch resistance is insufficient or the reflectance is high.

2 is a chart showing an infrared absorption spectrum of a cured film obtained from the curable resin composition in Example 1. FIG.

Claims (1)

Component (a) composed of a fluorine-containing olefin compound, Component (b) composed of a monomer compound containing a monomer containing a hydroxyl group or an epoxy group, copolymerizable with component (a), and an azo group By reacting the component (c) composed of the polysiloxane compound and the component (d) composed of the reactive emulsifier, the structural unit derived from the component (a) is derived from 20 to 70 mol% and derived from the component (b). 10 to 70 mol% of the structural unit (of which the proportion derived from the monomer containing a hydroxyl group or an epoxy group is 1 to 20 mol%), and the polysiloxane segment derived from the component (c) is a main chain. It contains 0.1 to 20 mol% of structural units derived from component (d) in a proportion of 0.1 to 10 mol%, the fluorine content is 30% by weight or more, and the number average in terms of polystyrene A is molecular weight of 5,000 or more, resulting olefin polymer having a hydroxyl group and / or epoxy group (A),
3 to 50 parts by weight of a crosslinkable compound comprising 100 parts by weight of the olefin polymer (A) and (B) a compound containing at least one of or both of a hydroxyalkylamino group and an alkoxyalkylamino group. A method for producing a curable resin composition, characterized in that a solution of the curable resin composition is obtained by heating to 50 to 150 ° C. in the presence of an organic solvent.

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