JP3186162B2 - Manufacturing method of resin material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a resin material having excellent heat resistance, solvent resistance and mechanical properties.

[0002]

2. Description of the Related Art In general, plastic materials are lightweight and have excellent impact resistance, workability and mass productivity.
Used in many applications. Various surface treatments have been attempted in order to further enhance the functionality of plastic materials having such characteristics.

[0003] For example, there are known many materials in which a cured film is provided on a thermoplastic resin such as polymethyl methacrylate or polycarbonate.

[0004]

However, materials using these thermoplastic resins have a problem that heat resistance, solvent resistance and mechanical properties are insufficient.

An object of the present invention is to solve these problems, and an object of the present invention is to provide a method for producing a resin material having excellent heat resistance, solvent resistance, and mechanical properties. Still another object is to provide a method for producing a resin material having excellent durability in these characteristics.

[0006]

The present invention has the following arrangement to achieve the above object.

"A method for producing a resin material, characterized by providing a cured film after bringing a three-dimensional crosslinked resin having a glass transition temperature of 130 ° C. or higher into contact with a solution containing an alkali." The original crosslinked resin can be used without particular limitation as long as it is a three-dimensional crosslinked resin having a glass transition temperature of 130 ° C or higher. However, a resin having a glass transition temperature of 150 ° C or higher has better heat resistance. More preferably used. Here, the glass transition temperature refers to the temperature at which a polymer changes from an amorphous glass state to a rubber state. In the transition region, various properties such as elastic modulus, expansion coefficient, heat content, refractive index, and dielectric constant are used. Changes. The glass transition temperature can be measured from changes in these properties,
Specifically, it can be evaluated by a known method such as differential scanning calorimetry (DSC) (for example, JIS K712).
1). In the case of measuring the glass transition temperature by differential scanning calorimetry, the glass transition temperature can be obtained by evaluating the three-dimensional resin itself or a product obtained by heat-treating the resin.

The mechanical properties of the three-dimensionally crosslinked resin are 200 kg / mm when the flexural modulus is used as an index.
² or more, and further preferably not 330 kg / mm ² or more.

The components of the three-dimensional crosslinked resin having a glass transition temperature of 130 ° C. or higher include, for example, polymethacrylic resins such as polymethacrylic acid and polycarboxyphenylmethacrylamide, and polystyrene resins such as poly (biphenyl) styrene. Representative polyolefin resins, representative polyether resins represented by poly (2,6-dimethyl-1,4-phenylene oxide), poly (oxycarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) ), A polyester resin typified by poly (oxy-2,2,4,4-tetramethyl-1,3-cyclobutyleneoxyterephthaloyl), poly (oxy-1,4)
-Phenylenesulfonyl-1,4-phenylene), poly (oxy-1,4-phenyleneisopropylidene-1,
Polysulfone-based resins such as 4-phenyleneoxy-1,4-phenylenesulfonyl-1,4-phenylene) and poly (iminoisophthaloylimino-4,4 ′)
Polyamide resin represented by -biphenylene), polysulfide resin represented by poly (thio-1,4-phenylenesulfonyl-1,4-phenylene), unsaturated polyester resin, epoxy resin, melamine resin,
Phenolic resins, diallyl phthalate resins, polyimide resins, polyphosphazene resins, and the like.Examples of these polymers include introducing a three-dimensional cross-linking structure into a three-dimensional cross-linking resin exhibiting the above thermal characteristics. It is possible to get. In particular, a polyolefin resin is preferable from the viewpoint of moldability, and a polyolefin copolymer obtained by polymerizing a composition containing a polyfunctional monomer having two or more unsaturated groups is more preferably used.

The above-mentioned polyolefin copolymer includes:
20 to 98% by weight of a monomer represented by the general formula (A), and 2 to 80% by weight of a polyfunctional monomer having two or more unsaturated groups.
A composition comprising a monomer represented by the general formula (A) and a polyfunctional monomer having two or more unsaturated groups having a total weight ratio of 30% by weight or more is polymerized. The copolymer obtained is preferably used.

[0011]

Embedded image (In the formula, R ³ represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² each represent a substituent selected from hydrogen, a methyl group and an ethyl group.) R ¹ and R ² contained in the maleimide derivative compound represented by (A) may be the same or different.

When R ³ is a hydrocarbon group, specific examples include a methyl group, an ethyl group, a propyl group, an octyl group,
Linear alkyl group such as octadecyl group, branched alkyl group such as isopropyl group, sec-butyl group, tert-butyl group and isopentyl group; alicyclic hydrocarbon group such as cyclohexyl group and methylcyclohexyl group; phenyl group And aryl groups such as methylphenyl group, and aralkyl groups such as benzyl group and phenethyl group.

Further, R ¹ , R ² and R ³ are substituted with various substituents such as halogeno groups such as fluorine, chlorine and bromine, cyano groups, carboxyl groups, sulfonic acid groups, nitro groups, hydroxy groups and alkoxy groups. May be done.

Specific examples of the compound represented by the general formula (A) include N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, −
p-methylphenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenyl Maleimide, N
-O-chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide,
No-carboxyphenylmaleimide, Np-carboxyphenylmaleimide, Np-nitrophenylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-isopropylmaleimide and the like.

These monomers may be used alone or in combination with two or more.
It may be used as a mixture of more than one species. Among these maleimide compounds, alkylmaleimide and cycloalkylmaleimide are particularly preferred from the viewpoint of yellowing after the heat resistance test and weather resistance, and N-isopropylmaleimide and N-cyclohexylmaleimide are particularly preferred. Further, in view of the ease of preparing a monomer solution at the time of cast polymerization, and the fact that the above properties can be satisfied, N-alkylmaleimides such as N-isopropylmaleimide and N-cyclohexylmaleimide and N-cycloaliphatic alkylmaleimides are used. The combination is most preferred. The ratio of N-alkylmaleimide to N-alicyclic alkylmaleimide when used in combination should be appropriately determined experimentally depending on the type and amount of the polyfunctional monomer having two or more unsaturated groups. However, it is usually preferable to use 10 to 500 parts by weight of N-alicyclic maleimide with respect to 100 parts by weight of N-alkylmaleimide in order to exert the effect of the combined use.

Next, the polyfunctional monomer having two or more unsaturated groups will be described. That is, the polyfunctional monomer having two or more unsaturated groups is a monomer having two or more unsaturated functional groups copolymerizable with the maleimide, and the copolymerizable functional group includes a vinyl group, Methyl vinyl group,
An acryl group, a methacryl group and the like can be mentioned. Further, a monomer containing two or more different copolymerizable functional groups in one molecule is also included in the polyfunctional monomer in the present invention.

Preferred specific examples of the polyfunctional monomer having two or more unsaturated groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. , Glycerol (di / tri) (meta)
Acrylate, trimethylolpropane (di / tri)
Di-, tri-, tetra- (meth) acrylates of polyhydric alcohols such as (meth) acrylate and pentaerythritol (di / tri / tetra) (meth) acrylate;
Aromatic polyfunctional monomers such as p-divinylbenzene and o-divinylbenzene, esters such as vinyl (meth) acrylate and allyl (meth) acrylate, dienes such as butadiene, hexadiene and pentadiene, and dichlorophosphazene Examples of the raw material include a monomer having a phosphazene skeleton into which a polymerized polyfunctional group is introduced, and a polyfunctional monomer having a heteroatom cyclic skeleton such as triallyl diisocyanurate.

The above-mentioned polyolefin-based copolymer preferably contains the monomer represented by the aforementioned general formula (A) in an amount of 20 to 98% by weight. Properties such as high heat resistance, mechanical strength, and optical isotropy tend to be unsatisfactory. Also, 9
If it exceeds 8% by weight, the degree of cross-linking may be reduced, and the solvent resistance, low water absorption and the like may be insufficient. Further, the content of the monomer represented by the above general formula (A) is preferably 30 to 80% by weight, more preferably 40 to 60% by weight.

On the other hand, the polyfunctional monomer having two or more unsaturated groups is preferably contained in the three-dimensional crosslinked polymer at a ratio of 2 to 80% by weight. If the content is less than 2% by weight, three-dimensional crosslinking may not proceed sufficiently, and heat resistance,
The solvent resistance and the like tend to decrease. 80% by weight
If the ratio exceeds the above, impact resistance and the like may be reduced, and the characteristics as a plastic may be reduced.

Further, in the above-mentioned polyolefin-based copolymer, improvement of mechanical strength, improvement of optical isotropy, improvement of refractive index, reduction of water absorption, improvement of dyeability, improvement of heat resistance, improvement of impact resistance, etc. For the purpose, various copolymerizable monomers are preferably used in combination. Examples of such a monomer that can be used in combination include an aromatic vinyl monomer, an olefin vinyl monomer, (meth) acrylic acid and its ester monomer, and a polycarboxylic anhydride. Specific examples of such an aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinyltoluene, chlorostyrene, bromostyrene, and the like. Usually, styrene, α-methylstyrene, p-methylstyrene, and the like are used from the viewpoints of performance and industrial availability. As other vinyl monomers, acrylonitrile, vinyl cyanide monomers such as methacrylonitrile, methyl methacrylate, methyl acrylate, cyclohexyl methacrylate, t-butyl methacrylate, benzyl methacrylate, acrylic Preferred specific examples include (meth) acrylic acid (ester) monomers such as acid and methacrylic acid, and maleic anhydride.

The total content of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups may be 30% by weight or more in the three-dimensional crosslinked resin. Preferably, it is more preferably at least 40% by weight. That is, when the content is less than 30% by weight, in the obtained polymer,
Transparency, heat resistance, chemical resistance, impact resistance, etc. are insufficient.

It is also useful to add various ultraviolet absorbers, antioxidants and antistatic agents to the three-dimensional crosslinked resin in the present invention for the purpose of improving light resistance, oxidation deterioration resistance and antistatic properties. In particular, it is preferable to copolymerize a monomer having an ultraviolet absorbing property or an antioxidant property, since these properties can be improved without lowering chemical resistance and heat resistance. Preferred examples of such a monomer include a benzophenone ultraviolet absorber having an unsaturated double bond, a phenylbenzoate ultraviolet absorber having an unsaturated double bond, and a (meth) acryl monomer having a hindered amino group as a substituent. Is mentioned. These copolymerized monomers are preferably used in the range of 0.5 to 20% by weight based on all monomers. When the amount is less than 0.5% by weight, the effect of addition is not recognized, and when it exceeds 20% by weight, heat resistance, mechanical strength, and the like tend to be reduced.

The method for polymerizing the three-dimensionally crosslinked resin of the present invention is not particularly limited, and it can be polymerized by a generally known method. When the transparent three-dimensional crosslinked resin is a polyolefin-based copolymer, polymerization can be performed by maintaining the above monomer mixture under a predetermined temperature condition in the presence or absence of a radical-generating initiator. Various methods such as bulk polymerization, solution polymerization, suspension polymerization, and cast polymerization can be used. The degree of polymerization of the three-dimensionally crosslinked resin of the present invention is not particularly limited, but the higher the degree of polymerization, the more preferable it is, and preferably 90% or more in consideration of post-processing such as solution coating such as a cured film and vacuum deposition.

There is no particular limitation on the molding method of the three-dimensional crosslinked resin of the present invention.
Cast polymerization methods are mentioned.

The cured film in the present invention comprises an organic polymer as a main component, but the organic polymer is not particularly limited. Specific examples of the organic polymer include acrylic resins, silicone resins, polyurethane resins, epoxy resins, melamine resins, polyolefin resins, celluloses, polyvinyl alcohol resins, urea resins, nylon resins, polycarbonate resins, and the like. Is mentioned. These resins can be used alone or in combination of two or more, and can be three-dimensionally cross-linked using various curing agents, cross-linking agents and the like. Particularly for applications where surface hardness is important, it is preferable to use a curable resin. For example, a single resin or a composite resin such as an acrylic resin, a silicone resin, an epoxy resin, a polyurethane resin, and a melamine resin is preferably used. Is done. When various properties such as surface hardness, heat resistance, chemical resistance, and transparency are considered, it is preferable to use a silicone resin, and more preferably, an organosilicon compound represented by the following general formula (B) or Polymers obtained from the hydrolyzate can be mentioned.

[0026] ^{_{R 4 a R 5 b SiX 4}} -ab (B) ( wherein, R ⁴ is an organic group having 1 to 10 carbon atoms, R ⁵
Is selected from a hydrocarbon group having 1 to 6 carbon atoms and a halogenated hydrocarbon group, X is a hydrolyzable group, and a and b are 0 or 1. Examples of the organosilicon compound represented by the general formula (B) include methyl silicate, ethyl silicate, n-propyl silicate, iso-propyl silicate, n-butyl silicate, sec-butyl silicate, and t-butyl silicate.
Tetraalkoxysilanes such as butyl silicate, and hydrolysates thereof, further, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,
Vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ
-Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, N-β- (aminoethyl) -γ
-Aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane,
Chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β- Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β
-Glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ -Glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-
Glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ- Glycidoxybutyltriethoxysilane,
(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-
Trialkoxysilanes such as epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, triacyloxysilane, or triphenoxy Silanes or hydrolysates thereof and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-
Chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ- Aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyl Dimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane Silane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethylmethoxyethoxysilane, γ-glycid Xypropylmethyldiphenoxysilane, γ-glycidoxypropylmethyldiacetoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxy Silanes, dialkoxysilanes such as γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, diphenoxysilane or diacyloxysilanes or a hydrolyzate thereof Decomposition products are an example.

These organosilicon compounds may be used alone or in combination.
It is also possible to add more than one species. In particular, for the purpose of imparting dyeing properties, the use of an organosilicon compound containing an epoxy group or a glycidoxy group is suitable, and provides high added value.

These organosilicon compounds are preferably used after being hydrolyzed in order to lower the curing temperature and accelerate the curing. The hydrolysis is produced by adding pure water or an acidic aqueous solution of hydrochloric acid, acetic acid, sulfuric acid or the like, followed by stirring. Furthermore, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution.

It is preferable to add a fine particle inorganic oxide to the cured film for the purpose of improving scratch resistance and heat resistance. The fine particle inorganic oxides can be used alone or in combination of two or more. Although not particularly limited, a sol dispersed in a colloidal form is preferably used from the viewpoint of workability. Specific examples thereof include silica sol, titania sol, antimony oxide sol, and alumina sol.

The alkali in the present invention refers to an alkali metal hydroxide, an alkaline earth metal hydroxide, an organic alkali metal compound, and an organic base. These alkalis may be used alone or in combination of two or more. Used. In the present invention, a solution in which these alkalis are dissolved in water and / or an organic solvent is used, and preferably a solution having a pH of 10 or more, more preferably a pH of 12 or more is used.
Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide and the like. Specific examples of the alkaline earth metal hydroxide include calcium hydroxide, beryllium hydroxide, and magnesium hydroxide. Specific examples of the organic alkali metal compound include sodium methoxide, sodium ethoxide, potassium methoxide,
Potassium ethoxide, lithium methoxide, lithium ethoxide and the like can be mentioned. Specific examples of the organic base include aliphatic amines such as diethylamine and triethylamine, and aromatic amines such as aniline. Among these compounds, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, and the like are particularly preferably applied from the viewpoint of availability, economy, and the like.

The concentration of the alkali in the alkaline solution is not particularly limited, but is preferably 1 to 50% by weight, more preferably 5 to 30%, from the viewpoints of shortening the processing time and the stability of the processing solution. It is used in the range of weight%.

In addition, a surfactant can be added to the alkali solution of the present invention for the purpose of improving the adhesion of the cured film or shortening the alkali treatment time. Agents, anionic surfactants and nonionic surfactants can be used alone or as a mixture of two or more. Specific examples of the cationic surfactant include octadecylamine acetate, tetradecylamine acetate, stearylamine acetate, octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, Examples include amine salts such as stearyl dimethyl ammonium chloride and tetradecyl dimethyl benzyl ammonium chloride, and amines such as oxyethylene dodecyl amine. Specific examples of the anionic surfactant include sulfonates such as sodium dodecylbenzenesulfonate, sodium lauroylmethyltaurate, and sodium dioctylsulfosuccinate; sulfates such as sodium lauryl sulfate, ammonium lauryl sulfate, and triethanolamine lauryl sulfate; And the like. Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene derivatives such as polyoxyethylene nonyl phenyl ether, and polyoxyethylene derivatives. Oxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan Esters such as sesquioleate and sorbitan monolaurate.

The surfactant is appropriately selected depending on the composition and properties of the three-dimensional crosslinked resin, but a cationic surfactant is preferably used from the viewpoint of stability in an alkaline solution and the effect of treatment. The content of the surfactant in the alkaline solution,
Although it should be determined experimentally, usually 0.01% by weight to 20% by weight is applied, but 0.1% by weight to 10% by weight is preferably applied from the viewpoint of processing effect and stability.

The organic solvent in the present invention is an organic compound which is liquid at normal temperature or at an alkali treatment temperature. Specific examples of the organic solvent include aliphatic compounds such as pentane and hexane, aliphatic halogen compounds such as dichloromethane and dichloroethane, methanol, ethanol, propanol, phenol, phenethyl alcohol, benzyl alcohol, and 2-methoxyethanol. Polyhydric alcohols such as polyhydric alcohols, ethylene glycol, diethylene glycol, and triethylene glycol;
Ketones such as acetone and methyl ethyl ketone; aldehydes such as propionaldehyde; esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether and diisopropyl ether; and aromatic hydrocarbon compounds such as benzene and toluene. . Water may be added to a solution containing an alkali and an organic solvent. The type and concentration of the organic solvent should be determined by experiments, but it is preferable to use the organic solvent at a concentration of 0.1 to 100% by weight of the total solvent.

In the present invention, the cured coating is provided after the three-dimensional crosslinked resin is brought into contact with a solution containing an alkali.
The contact method is not particularly limited, and an immersion method, a shower method, or the like is appropriately selected and used.

The treatment time is determined experimentally, but is preferably from 1 minute to 100 hours, more preferably from 1 minute to 5 hours. The treatment temperature is determined experimentally in consideration of the composition and properties of the three-dimensional crosslinked resin, but is preferably 5C to 95C, more preferably 50C to 90C. The alkali treatment can be performed in combination with ultrasonic treatment to enhance the treatment effect.

The resin material obtained by the present invention is excellent in transparency, heat resistance, light resistance, weather resistance, impact resistance, glazing, chemical resistance, optical isotropy, etc. Various displays such as lenses, camera lenses, video camera lenses, goggle lenses, contact lenses, and other optical lenses, as well as substrates for liquid crystal displays, light guide plates for liquid crystal displays, substrates for electrochromics, and substrates for electroluminescence. The substrate material is applied to windows such as front, side, rear, and roof of automobiles and aircrafts, and to optical disc substrates because of its excellent optical isotropy. In particular, when a transparent conductive film such as ITO is formed on the resin material of the present invention, the conductivity is maintained even at a high temperature, so that it can be used as a heat-resistant transparent conductive film substrate. It is preferably used for liquid crystal displays and the like.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

(A) Evaluation of properties of three-dimensional crosslinked resin The total light transmittance was measured based on ASTM D-648, and the solvent resistance was determined by rubbing the surface with gauze impregnated with acetone. The change was evaluated visually. The bending test was performed based on JIS K-7203. Glass transition temperature is measured by Mettler TA
It measured using 3000 (measured by 2nd run).

(B) Evaluation of contact angle As a contact angle meter, "FACE CO" manufactured by Kyowa Interface Science Co., Ltd. was used.
Using NTACT ANGLEMETER CA-D ", the static contact angle of water (hereinafter abbreviated as contact angle) on the surface of the alkali-treated three-dimensional crosslinked resin was measured at room temperature.

(C) Evaluation of Adhesiveness of the Cured Coating A cellophane adhesive tape (trade name “Cellotape”, manufactured by Nichiban Co., Ltd.) was put on the surface of the coating with a steel knife, and 100 pieces of a metal pattern reaching a substrate of 1 mm were put on the coating with a steel knife. Paste strongly,
The film was rapidly peeled in the 90 ° direction, and the presence or absence of peeling of the coating film was examined.

Example 1 (1) Preparation of three-dimensional crosslinked resin 26.5 g of isopropylmaleimide, 18.5 of styrene
g, 5.0 g of divinylbenzene and 0.05 g of azobisisobutyronitrile were mixed and dissolved, and cast and molded by cast polymerization. Cast polymerization was performed as follows.

2 of a size of 150 mm × 150 mm and a thickness of 5 mm
The outer peripheral portions of the two glass plates were adhered with a soft vinyl chloride gasket, and assembled so that the distance between the two glass plates was 2 mm. The above monomer mixture was poured into the assembled glass plate, and polymerized at 70 ° C. for 8 hours, at 100 ° C. for 1 hour, and further at 160 ° C. for 1 hour.
Cast plate (I)).

The glass transition temperature of this casting plate (I) is 18
The temperature was 0 ° C., and the total light transmittance was 90%. The flexural modulus was 398 kg / mm ² , the flexural strength was 9 kg / mm ² , and the solvent resistance was good.

(2) Preparation of coating composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate In a reactor equipped with a rotor, 95.3 g of γ-glycidoxypropyltrimethoxysilane was placed. Charge, maintain the liquid temperature at 10 ° C., and stir with a magnetic stirrer for 0.01
21.8 g of a specified aqueous hydrochloric acid solution was gradually added dropwise. After dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

(B) Preparation of paint The above silane hydrolyzate was added to 216 g of methanol, 216 g of dimethylformamide, and 0.5 part of a silicone surfactant.
g, bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 827), 67.5 g, and mixed. Further, colloidal antimony pentoxide sol (manufactured by Nissan Chemical Co., Inc., trade name: antimony sol A-2550, average) After adding 270 g of a particle diameter of 50 mμ) and 13.5 g of aluminum acetylacetonate and sufficiently stirring, a coating composition was obtained.

(3) Preparation of Alkali Treatment Solution 100 g of sodium hydroxide was dissolved in 300 g of water, and 1.2 g of an alkylammonium-type cationic surfactant (Cation BB, dodecyltrimethylammonium chloride (trade name, manufactured by NOF Corporation) was added. Was added to prepare an alkali treatment solution. (4) Alkali treatment of resin The alkali treatment liquid prepared in the above (3) was heated to 80 ° C. After the casting plate (I) obtained in (1) was immersed in the heated alkali treatment solution for 10 minutes, the plate was washed with hot water at 50 ° C. for 10 minutes, dried, and treated. )). Table 1 shows the contact angles of the obtained treated plates (I).
Shown in

(5) Coating and curing of coating agent The coating composition prepared in (2) is dip-coated on the treated plate (I) obtained in (4) at a pulling rate of 20 cm / min. Then, preliminary curing was performed at 100 ° C. for 10 minutes, and further, heating was performed at 110 ° C. for 4 hours to form a cured film on the processing plate (I). Table 1 shows the adhesion of the cured film.
Shown in

Example 2 In the preparation of the alkali treatment liquid of Example 1, an alkylammonium type cationic surfactant was used as a sulfonic acid type anionic surfactant (trade name: Rapisol B-8, manufactured by NOF CORPORATION).
0, sodium dioctylsulfosuccinate), except that the treated plate (hereinafter referred to as treated plate (I
I)). Table 1 shows the contact angle of the obtained treated plate (II).

On the treated plate (II) obtained, a cured film was provided in the same manner as in Example 1. Table 1 shows the adhesiveness of the cured film.

Example 3 In the preparation of the alkali treatment solution of Example 1, an alkylammonium-type cationic surfactant was used as an ether-type nonionic surfactant (trade name: Nonion S-220, manufactured by NOF Corporation).
Except for replacing with polyoxyethylene stearyl ether, a treated plate (hereinafter referred to as treated plate (III
)). Table 1 shows the contact angles of the obtained treated plates (III).

A cured film was provided on the treated plate (III) in the same manner as in Example 1. Table 1 shows the adhesiveness of the cured film.

[0053] Example 4 Example alkylammonium type in the preparation of the alkaline processing liquid 1 Cationic surfactants benzyl ammonium type cationic surfactant (manufactured by NOF Corporation, trade name cation F ₂ -20R, alkyl dimethyl benzyl ammonium chloride A processing plate (hereinafter, referred to as a processing plate (IV)) was prepared in the same manner as in Example 1 except for changing to (1). Table 1 shows the contact angles of the obtained treated plates (IV).

A cured film was provided on the treated plate (IV) in the same manner as in Example 1. Table 1 shows the adhesiveness of the cured film.

Example 5 A treated plate (hereinafter referred to as treated plate (V)) was prepared in the same manner as in Example 1 except that an alkylammonium-type cationic surfactant was not added in the preparation of the alkaline treatment solution of Example 1. did. Table 1 shows the contact angles of the obtained treated plates (V).

A cured coating was provided on the treated plate (V) in the same manner as in Example 1. Table 1 shows the adhesiveness of the cured film.

Example 6 A mixture comprising 50% by weight of isopropylmaleimide and 50% by weight of cyclohexylmaleimide in the preparation of the casting plate (I) of Example 1 26.5.
A transparent casting plate (hereinafter referred to as casting plate (II)) was obtained in the same manner as in Example 1 except that g was replaced with g.

The glass transition temperature of this casting plate (II) is 19
The temperature was 0 ° C., and the total light transmittance was 90%. The flexural modulus was 400 kg / mm ² and the flexural strength was 8 kg / mm ² , and the solvent resistance was also good.

The obtained casting plate (II) was subjected to an alkali treatment in the same manner as in Example 1 to prepare a treated plate (VI). Table 1 shows the contact angles of the obtained treated plates (VI).

A cured film was provided on the treated plate (VI) in the same manner as in Example 1. Table 1 shows the adhesiveness of the cured film.

Comparative Example 1 The contact angle of the casting plate (I) produced in Example 1 (without alkali treatment) was examined. Table 1 shows the results.

Further, a cured film was provided on the above-mentioned casting plate (I) in the same manner as in Example 1, and the adhesion was evaluated. Table 1 shows the results.

Comparative Example 2 The contact angle of the casting plate (II) produced in Example 6 (without alkali treatment) was examined. Table 1 shows the results.

Further, a cured film was provided on the above-mentioned casting plate (II) in the same manner as in Example 1, and the adhesion was evaluated. Table 1 shows the results.

[0065] Example 7 40 g of sodium hydroxide was dissolved in 360 g of methanol to prepare an alkali treatment solution. A treated plate (hereinafter referred to as treated plate (VI
I)). Table 2 shows the contact angles of the obtained treated plates (VII).

A cured film was provided on the treated plate (VII) in the same manner as in Example 1. Table 2 shows the adhesiveness of the cured film.

Example 8 160 g of sodium hydroxide was dissolved in 180 g of water, and 60 g of methanol was added to prepare an alkali treatment solution. A treated plate (hereinafter, referred to as treated plate (VIII)) was prepared in the same manner as in Example 7, except that the alkali treatment liquid was used in the alkali treatment of the resin. The obtained treated plate (VIII)
Are shown in Table 2.

A cured film was provided on the obtained treated plate (VIII) in the same manner as in Example 7. Table 2 shows the adhesiveness of the cured film.

Example 9 An alkali treatment solution was prepared by dissolving 100 g of sodium hydroxide in 300 g of water and adding 20 g of benzyl alcohol. A treated plate (hereinafter, referred to as treated plate (IX)) was prepared in the same manner as in Example 7, except that the alkaline treatment was performed at 90 ° C. using this alkaline treatment liquid. Table 2 shows the contact angles of the obtained treated plates (IX).

A cured coating was provided on the treated plate (IX) in the same manner as in Example 7. Table 2 shows the adhesiveness of the cured film.

Example 10 28% sodium methoxide
A treated plate (hereinafter referred to as treated plate (X)) was prepared in the same manner as in Example 7, except that a methanol solution (trade name: sodium methylate, manufactured by Wako Pure Chemical Industries, Ltd.) was used. Table 2 shows the contact angles of the obtained treated plates (X).

A cured film was provided on the treated plate (X) in the same manner as in Example 7. Table 2 shows the adhesiveness of the cured film.

Example 11 Using the casting plate (II) obtained in Example 6, alkali treatment was carried out in the same manner as in Example 7, to produce a treated plate (hereinafter referred to as treated plate (XI)). Table 2 shows the contact angles of the obtained treated plates (XI).

A cured film was provided on the obtained processing plate (XI) in the same manner as in Example 7. Table 2 shows the adhesiveness of the cured film.

[0075]

[0076]

According to the present invention, a resin material having a cured film having excellent heat resistance, solvent resistance and mechanical properties can be produced. Further, the resin material obtained according to the present invention is excellent in the adhesiveness between the three-dimensional crosslinked resin and the cured film, and thus is excellent in the durability of the above effects. Further, in the present invention, continuous processing is possible, and by a simple operation, surface treatment can be performed without being affected by the shape of the article, and a resin material having a cured film excellent in the above characteristics can be efficiently produced. Obtainable.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08J 7/04

Claims (5)

(57) [Claims] 1. A method for producing a resin material, comprising: bringing a three-dimensional crosslinked resin having a glass transition temperature of 130 ° C. or higher into contact with a solution containing an alkali and then providing a cured film. 2. The method according to claim 1, wherein the alkali-containing solution is an aqueous alkali solution. 3. The method according to claim 1, wherein the solution containing an alkali is a solution containing an alkali and an organic solvent.
A method for producing the resin material described above. 4. The method according to claim 2, wherein the aqueous alkali solution is a solution containing a surfactant. 5. The three-dimensional crosslinked resin contains 20 to 98% by weight of a monomer represented by the general formula (A) and 2 to 80% by weight of a polyfunctional monomer having two or more unsaturated groups. And polymerizing a composition in which the total weight ratio of the monomer represented by the general formula (A) and the polyfunctional monomer having two or more unsaturated groups is 30% by weight or more. The method for producing a resin material according to claim 1, wherein the resin material is a copolymer comprising: Embedded image (In the formula, R ³ represents a substituent selected from hydrogen and a hydrocarbon group having 1 to 20 carbon atoms. R ¹ and R ² each represent a substituent selected from hydrogen, a methyl group and an ethyl group.)