JPH08224534A - Laminate and its production - Google Patents

Abstract

PURPOSE: To obtain the hardness originally possessed by a hard coat soln. having any compsn. on a primer coating film and to obtain a laminate not damaged in its physical properties by applying a primer. CONSTITUTION: A laminate is produced by coating a base material with a primer to which a catalyst such as a metal salt of acetylacetone capable of curing hard coat is added to obtain a coating film and coating the coating film with a hard coat soln. composed of a silicone coating material to promote the curing of the hard coat film by the catalyst bled from the primer coating film.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a hard coat laminate provided on a plastic substrate or another substrate.

[0002]

2. Description of the Related Art Conventionally, the following methods have been used when a hard coating is applied to a plastic substrate or another substrate. In the case of a base material that easily obtains adhesion, for example, an acrylic plate or a CR-39 lens (one obtained by heat curing diethylene glycol bisallyl carbonate), the substrate is directly coated without using a primer. On the other hand, in the case of a substrate that is difficult to obtain adhesion, such as polycarbonate, polyester resin (PET), and some high refractive index lens substrates, the substrate is subjected to a special surface treatment (for example, oxygen plasma treatment), Direct coating on the substrate,
Alternatively, a hard coat is applied after treating the substrate with a primer. Further, a primer has been used also when it is desired to give the hard coat layer physical properties other than scratch resistance, such as weather resistance, impact resistance, and ultraviolet and infrared ray cut properties.

[0003]

When a primer is used in the method of forming a hard coat layer on a plastic substrate or other substrate of the above-mentioned conventional technique, the hard coat may not be cured on a special primer. For example, it is effective to use a primer made of urethane resin in order to improve the impact resistance of the lens, but on the coating film made of urethane resin, some commercially available hard coat thermosetting type lenses for lenses are used. In some silicon-based hard coats, curing is inhibited and sufficient hardness cannot be obtained.

[0004] Lens hard coat on the coating film made of urethane resin are partially commercially available (e.g., Crystal Court _R C-339 / Nippon er Earl Sea Corporation)
Except the above, thermosetting type silicon hard coats (for example, TS-56T / Tokuyama Corporation) do not have sufficient hardness because of inhibition of curing.

Therefore, the object of the present invention is to obtain the original hardness of the hard coat liquid of any composition on the primer coating film, and further to impair the physical properties obtained by coating the primer. It is to provide a laminated body and a manufacturing method thereof.

[0006]

The above objects of the present invention can be achieved by the following constitutions. That is, it is possible to cure the hard coat liquid applied on the base material through the primer layer, and yet to react with the primer component or to add a primer layer containing a catalyst that does not affect the characteristics of the primer. A laminate characterized by providing a hard coat layer on the primer layer, or a catalyst capable of curing the hard coat was added to the primer, and the primer was applied to a substrate to obtain a coating film. After that, a hard coat liquid is applied, and a method for producing a laminate in which curing of the hard coat film is accelerated by a catalyst exuding from the primer film.

Each coating film component will be described in detail below. (1) Primer (a) Blocked isocyanate component of urethane resin Hexamethylene diisocyanate, 1,3,3-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylene diisocyanate, hydrogenated xylylene diisocyanate, tri Polyisocyanates such as diisocyanate and modified products thereof (for example, trimers), isocyanurates, allophanates, burettes, carbodiimides, trimers of the above isocyanates, prepolymers, and those in which these isocyanate groups are blocked with a blocking agent. As the blocking agent, acetylacetone, 2,4-hexanedione,
Although 3,5-heptanedione or the like is used, β-diketone is preferable.

(B) Polyol component of urethane resin used as primer Various commercially available polyester polyols, polyether polyols or acrylic polyols, polycaprolactone, polycarbonate polyols such as Desmodur 1100 and polyethylene glycol manufactured by Sumitomo Bayer Co., Ltd. are used. To be In addition, a bromine-containing epoxy compound, for example, trade name Platherm E manufactured by Dainippon Ink and Chemicals
C-30, Fireguard FG3 manufactured by Teijin Chemicals Ltd.
600 etc. can also be used. The molar ratio of the block type polyisocyanate to the polyol is 0.3 to 2.0 in terms of molar ratio of isocyanate group to hydroxyl group, and 0.6 to 1.4 is particularly preferable. When the molar ratio is less than 0.3 or exceeds 2.0, the crosslink density of the cured film is too small and the impact resistance is not improved.

(C) Water-dispersible urethane resin Witco Bond made by Witco, Asahi Denka Co., Ltd.
Trade name ADEKA BON TITER manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Splensol trade name by Dainippon Ink

(D) Various resins Various commercially available paint resins can be used. For example, acrylic resin Dainippon Ink Co., Ltd. trade name Acridic, Hitachi Chemical Co., Ltd. trade name Hitaroid polyester resin Hitachi Chemical Co., Ltd. trade name Polyset epoxy resin Dainippon Ink Co., Ltd. Trade name Epichlor melamine resin Trade name Melan manufactured by Hitachi Chemical Co., Ltd., Dainippon Ink Co., Ltd.
Trade name of Super Beckamine Amino resin Trade name of Simul Cyanamid Co., Ltd. Simul

Modified acrylic resin Urethane acrylate Sannopco Co., Ltd. trade name Photomer 6000, Shin-Nakamura Chemical Co., Ltd. NK oligo UA, Toagosei Co., Ltd. trade name, Aronix M epoxy acrylate San Nopco Co., Ltd. Trade name Photomer 3000, Trade name NK oligo EA polyester acrylate manufactured by Shin-Nakamura Chemical Co., Ltd. Trade name Photomer 5000 manufactured by San Nopco Co., Ltd. Trade name NK oligo PA manufactured by Shin Nakamura Chemical Co., Ltd., Acros Co., Ltd. Trade name of Actylan melamine acrylate Trade name of Shin Nakamura Chemical Co., Ltd. NK oligo MA amino acrylate Trade name of Setacure manufactured by ACROS Co., Ltd. is used.

(E) Primer curing catalyst When a thermosetting primer is used, it is not particularly necessary to cause a urethane reaction, but an organotin compound may be added. When using an acrylic primer, ammonium perchlorate or the like is suitable. A curing catalyst is not particularly required when using a room temperature dry type primer. When a photocurable primer is used, the following cationic photopolymerization initiator and radical photopolymerization initiator are used.

Cationic photopolymerization initiator of the formula (R ¹⁰ -C ₆ H ₄ ) _n X ⁺ MQ _h ^- wherein X is a radical selected from iodine (I), phosphorus (P) and sulfur (S), M is a metal or metalloid, Q is a halogen radical selected from fluorine (F), chlorine (Cl), bromine (Br), I, R ¹⁰ is hydrogen or a monovalent hydrocarbon group (having 1 to 12 carbon atoms), h is an integer of 4, 5 or 6, and n is an integer of 2 or 3. For example, MQ _h ^- is S
It is selected from bF ₆ ⁻ , AsF ₆ ⁻ , BF ₄ ⁻ and PF ₆ ⁻ . Specifically, the trade name IRGACURE ^R manufactured by Ciba Geigy
261 (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-), trade name CYRGACURE UVI-697 manufactured by Union Carbide Co.
04-4′-bis [di (β-hydroxyethoxy) phenylsulfonyl] phenylsulfide-bis-hexafluoroantimonate is preferred.

Radical photopolymerization initiator For example, benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxycyclo-2-methyl-
1-phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide,
2,2-diphenylethoxyacetophenone-3,
It is 3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone.

(2) Hard Coat As the hard coat layer of the laminate of the present invention, a thermosetting or photocuring type hard coat layer is used, and the hard coat layer is formed of a silicone coating or a UV curing resin coating. . The silicone paint can contain the following components as main components. Metal oxide fine particle dispersed sol, epoxy group-containing silicon compound or a partial hydrolyzate thereof, and a functional group having only one OH group or SH group in the molecule and further represented by the following structural formula in the molecular main chain -O-, -CO-O-, -S
-, -CO-S-, or -CS-S- containing one or more, and containing a compound soluble in water or a lower alcohol having 4 or less carbon atoms as a main component Metal oxide fine particle dispersed sol and alkyl A compound containing a compound containing a group-containing silicon compound or a partial hydrolyzate thereof as a main component Metal oxide fine particle dispersed sol, a silane and vinyl group having at least one or more functional groups, an allyl group, Mainly composed of a compound having a plurality of polymerizable functional groups of at least one of methacrylic group and epoxy group

Each component will be described below. (A) Epoxy group-containing silicon compound or partial hydrolysis thereof (10 to 80% by weight based on the total solid content) The epoxy group-containing silicon compound or the epoxy group-containing silicon compound used for the partial hydrolysis thereof is represented by the following structural formula. Can be used. R ¹ R ² _a Si (OR ³ ) _3-a Here, R ¹ is a group containing an epoxy group having 2 to 12 carbon atoms, and R ² is an alkyl group, aryl group, or alkenyl having 1 to 6 carbon atoms. Group, halogenated alkyl group or halogenated aryl group, R ³ is hydrogen atom or carbon atom 1
The alkyl group, the acyl group, and the alkylacyl group a of 4 are 0, 1 or 2. The silane of the above structural formula is, for example, γ-glycidoxypropyltrimethoxysilane β-glycidoxypropyltrimethoxysilane γ-glycidoxypropyltriethoxysilane β-glycidoxypropyltriethoxysilane γ-glycidoxy Propylmethyldimethoxysilane γ-glycidoxypropylmethyldiethoxysilane β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

(B) Having only one OH group or SH group in the molecule that can be added to the hard coating solution, and further having in the main chain of the molecule functional groups represented by the following structural formulas —O— and —CO—
A compound that contains one or more of O-, -S-, -CO-S-, or -CS-S-, and is soluble in water or a lower alcohol having 4 or less carbon atoms (1 to 1 based on the total solid content). 45% by weight) can be represented by the following general formula. R ⁴ —X—R ⁵ YH Here, R ⁴ is a monovalent hydrocarbon group having at least one unsaturated group and may contain an oxygen atom or a sulfur atom. R ⁵ is a divalent hydrocarbon group having 2 or more carbon atoms and may contain an oxygen atom or a sulfur atom. Also,
X represents -O-, -CO-O-, -S-, -CO-S- or -CS-S-, and Y represents an oxygen atom or a sulfur atom.

The compound represented by the above general formula is, for example, 4-hydroxybutyl acrylate 4-hydroxybutyl methacrylate 4-hydroxyethyl acrylate 4-hydroxyethyl methacrylate diethylene glycol monoacrylate tetraethylene glycol monoacrylate polyethylene glycol monoacrylate tripropylene glycol mono. Acrylate polypropylene glycol monoacrylate diethylene glycol monomethacrylate tetraethylene glycol monomethacrylate polyethylene glycol monomethacrylate tripropylene glycol monomethacrylate polypropylene glycol monomethacrylate 4-hydroxybutyl allyl ether 4-hydroxybutyl vinyl ether di Tylene glycol monoallyl ether Triethylene glycol monovinyl ether Ethoxybutanol Methoxybutanol n-Butoxyethanol Triethylene glycol monoethyl ether Tetraethylene glycol monomethyl ether Polyethylene glycol monomethacrylate Poly (butanediol) monoacrylate Poly (butanediol) monomethacrylate 1,4 -Butanediol monovinyl ether 1,6-hexanedithiol monoacrylate 2-hydroxy-3-phenoxypropyl acrylate pentaerythritol triacrylate 2-hydroxybutyl acrylate 3-acryloyloxyglycerin monomethacrylate 2-hydroxy-1,3-dimethacryloxypropane 2-mercaptoethylthio Chill - methyl sulfide 2-mercapto-ethoxyethyl - methyl sulfide 1,6-hexanedithiol monomethyl ether 2-hydroxyethyl - butyl sulfide

(C) Other silicon compounds or partial hydrolysates thereof (0 to 60% by weight based on the total solid content) In the present invention, in addition to the silicon compounds of (a) or hydrolysates thereof, A silicon compound represented by the structural formula (1) or a partial hydrolyzate thereof can be added as a component of the hard coat. R ⁶ _d R ² _e Si (OR ³ ) _4-de R ² and R ³ are the same as those defined in the structural formula of the epoxy group-containing silicon compound of (2), and R ⁶ is an alkyl group having 1 to 4 carbon atoms. Group, halogenated alkyl group, 6 to 12 carbon atoms
Aryl group or halogenated aryl group, methacryloxyalkyl group having 5 to 8 carbon atoms, 2-1 to 2 carbon atoms
0 ureido alkylene group, aromatic ureido alkylene group, halogenated aromatic alkylene group, mercapto alkylene group d is 1, 2 or 3, and e is 0, 1 or 2, an organosilicon compound or a partial hydrolyzate thereof. Is.

For example, trimethylmethoxysilane triethylmethoxysilane trimethylethoxysilane triethylethoxysilane triphenylmethoxysilane diphenylmethylmethoxysilane phenyldimethylmethoxysilane phenyldimethylethoxysilane vinyldimethylmethoxysilane vinyldimethylethoxysilane γ-acryloxypropyldimethylmethoxysilane γ -Methacryloxypropyldimethylmethoxysilane γ-mercaptopropyldimethylmethoxysilane γ-mercaptopropyldimethylethoxysilane N-β (aminoethyl) γ-aminopropyldimethylmethoxysilane γ-aminopropyldimethylmethoxysilane γ-aminopropyldimethylethoxysilane γ -Glycidoxypropyl dimethylmethoxysilane γ Glycidoxypropyl dimethoxyethoxysilane β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane dimethyldimethoxysilane diethyldimethoxysilane dimethyldiethoxysilane diethyldiethoxysilane diphenyldimethoxysilane phenylmethyldimethoxysilane phenylmethyldiethoxysilane vinylmethyldimethoxy Silane Vinylmethyldiethoxysilane γ-acryloxypropylmethyldimethoxysilane γ-methacryloxypropyldimethyldimethoxysilane γ-mercaptopropylmethyldimethoxysilane γ-mercaptopropylmethyldiethoxysilane N-β (aminoethyl) γ-aminopropylmethyldimethoxy Silane γ-aminopropylmethyldimethoxysilane γ-Aminopropylmethyldi Ethoxysilane γ-glycidoxypropylmethyldimethoxysilane γ-glycidoxypropylmethoxydiethoxysilane β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane methyltrimethoxysilane ethyltrimethoxysilane methyltriethoxysilane ethyltriethoxy Silane Phenyltrimethoxysilane Phenyltriethoxysilane Vinyltrimethoxysilane Vinyltriethoxysilane

Vinyl (β-methoxyethoxy) silane γ-acryloxypropyltrimethoxysilane γ-methacryloxypropyltrimethoxysilane γ-mercaptopropyltrimethoxysilane γ-mercaptopropyltriethoxysilane N-β (aminoethyl) γ- Aminopropyltrimethoxysilane γ-aminopropyltrimethoxysilane γ-aminopropyltriethoxysilane γ-glycidoxypropyltrimethoxysilane β-glycidoxypropyltrimethoxysilane γ-glycidoxypropyltriethoxysilane β-glycid Xypropyltriethoxysilane β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane tetraethylorthosilicate tetramethylorthosilicate and the like.

(C) Alkyl group-containing silicon or its hydrolyzate (10 to 90% by weight based on the total solid content) As the alkyl group-containing silicon or its hydrolyzate, a compound having the following structural formula is used. You can R ⁹ _d R ⁹ _e Si (OR ³ ) _4-de Here, R ⁹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or an alkylacyl group, and all R ⁹ may be different, R ³ is the same as defined above. d is 1, 2 or 3, and e is 0, 1 or 2.
For example, trimethylmethoxysilane triethylmethoxysilane trimethylethoxysilane triethylethoxysilane dimethyldimethoxysilane diethyldimethoxysilane dimethyldiethoxysilane diethyldiethoxysilane methyltrimethoxysilane ethyltrimethoxysilane methyltriethoxysilane ethyltriethoxysilane tetraethylorthosilicate, tetramethyl Orthosilicate, etc.

(D) Silane having at least one or more functional groups R ⁷ _d R ² _e Si (OR ³ ) _4-d- e R ² and R ³ are the same as defined above, and R ⁷ is a carbon atom. Number 2
12, a group containing an epoxy group, an amino group, an acryl group, a mercapto group, a vinyl group, an NCO group, and a ureido group, d is 1, 2 or 3 and e is 0, 1 or 2, an organosilicon compound or a portion thereof. Hydrolyzate (1-50 parts by weight of total solids)

For example, vinyldimethylmethoxysilane vinyldimethylethoxysilane γ-acryloxypropyldimethylmethoxysilane γ-methacryloxypropyldimethylmethoxysilane γ-mercaptopropyldimethylmethoxysilane γ-mercaptopropyldimethylethoxysilane N-β (aminoethyl) γ-aminopropyldimethylmethoxysilane γ-aminopropyldimethylmethoxysilane γ-aminopropyldimethylethoxysilane γ-glycidoxypropyldimethylmethoxysilane γ-glycidoxypropyldimethoxyethoxysilane β- (3.4-epoxycyclohexyl) ethyl Dimethylmethoxysilane Vinylmethyldimethoxysilane Vinylmethyldiethoxysilane γ-acryloxypropylmethyldimethoxysilane γ Methacryloxypropyl dimethyldimethoxysilane γ-mercaptopropylmethyldimethoxysilane γ-mercaptopropylmethyldiethoxysilane N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane γ-aminopropylmethyldimethoxysilane γ-aminopropylmethyldiethoxysilane γ-glycidoxypropylmethyldimethoxysilane γ-glycidoxypropylmethoxydiethoxysilane β- (3.4-epoxycyclohexyl) ethylmethyldimethoxysilane vinyltrimethoxysilane vinyltriethoxysilane vinyl (β-methoxyethoxy) silane γ -Acryloxypropyltrimethoxysilane γ-methacryloxypropyltrimethoxysilane γ-mercaptopropyltrimethoxysilane γ-mercaptopro Lutriethoxysilane N-β (aminoethyl) γ-aminopropyltrimethoxysilane γ-aminopropyltrimethoxysilane γ-aminopropyltriethoxysilane γ-glycidoxypropyltrimethoxysilane β-glycidoxypropyltrimethoxysilane γ -Glycidoxypropyltriethoxysilane β-glycidoxypropyltriethoxysilane β- (3.4-epoxycyclohexyl) ethyltrimethoxysilane.

(E) Compound having a plurality of polymerizable functional groups of at least any one of vinyl group, allyl group, methacryl group and epoxy group (5 to 90% by weight of total solid content) Used. Glycidyl ether Trimethylolpropane triglycidyl ether Ethylene glycol diglycidyl ether Tripropylene glycol diglycidyl ether 1,6-hexanediol diglycidyl ether Bisphenol A diglycidyl ether Glycidyl methacrylate allyl ether 1,1,2,2, -Tetraallyloxyethane Triallyl cyanurate Diethylene glycol diallyl ether Maleic acid diallyl ether Adipate diallyl ether Diethylene glycol bisallyl carbonate Allyl glycidyl ether Vinyl ether Diethylene glycol divinyl ether Triethylene glycol divinyl ether Tetraethylene glycol divinyl ether Dipropylene glycol Divinyl ether Tryp Propylene glycol divinyl ether 1,4-divinyloxybutane 1,6-hexanediol divinyl ether-cyclohexane dimethanol divinyl ether

Acrylate, methacrylate trimethylolpropane triacrylate trimethylolpropane triethoxytriacrylate trimethylolpropane trimethacrylate di-trimethylolpropane tetraacrylate pentaerythritol monohydroxytriacrylate pentaerythritol tetraacrylate dipentaerythritol (monohydroxy) pentaacrylate 1,6-hexanediol diacrylate 1,4-butanediol diacrylate ethylene glycol diacrylate diethylene glycol diacrylate tetraethylene glycol diacrylate tripropylene glycol diacrylate neopentyl glycol diacrylate poly (butanediol) diacrylate polyethyi Len glycol diacrylate Polypropylene glycol diacrylate 1,6-hexanediol dimethacrylate 1,4-butanediol dimethacrylate Ethylene glycol dimethacrylate Diethylene glycol dimethacrylate Tetraethylene glycol dimethacrylate Tripropylene glycol dimethacrylate Neopentyl glycol dimethacrylate Poly (butanediol ) Dimethacrylate Polyethylene glycol dimethacrylate Polypropylene glycol dimethacrylate Bisphenol A diacrylate

(F) Metal fine particle dispersed sol (10 to 70% by weight based on the total solid content) Colloidal metal fine particles can be used based on the total solid content in the hard coating solution. Metal components are Si, Ti, C
e, Fe, Sn, Zr, Al, W, Sb, Ta, La,
At least one kind of metal oxide fine particles selected from In, composite oxide fine particles, a mixture of single metal oxide fine particles or a mixture of single metal oxide fine particles and composite metal oxide fine particles is dispersed in water or another solvent. It is a sol.

As the metal oxide fine particle sol, a sol composed of single metal oxide fine particles, composite metal oxide fine particles, a mixture of single metal oxide fine particles, or a mixture of single metal oxide fine particles and composite metal oxide fine particles is used. The average particle size of the metal oxide fine particles is preferably 1 to 100 nm. Particles having an average particle size of less than 1 nm cannot be substantially manufactured,
If it exceeds 100 nm, the transparency of the coating film is lowered. Colloidal silica is the most typical example. The following compounds can be used as the SiO ₂ dispersed sol. Average particle size 20 nm, solid content 40%, water dispersion sol manufactured by Nissan Kagaku Co., Ltd., trade name Snowtex O-40, average particle size 20 nm, solid content 30%, isopropyl alcohol dispersion sol manufactured by Nissan Kagaku Co., Ltd., trademark Name IPA-S
T, average particle size 20 nm, solid content 30%, prepoxyethanol dispersion sol manufactured by Nalco, trade name Nalco105
7, an average particle size of 10 to 20 nm, a solid content of 30%, an aqueous dispersion sol manufactured by Catalyst Kasei Co., Ltd., trade name Cataloid SA.

By subjecting the metal oxide fine particles or composite metal oxide fine particles used in the metal oxide fine particle sol to a surface treatment with an organic silicon compound, the reactivity and affinity with the matrix are improved. As the organosilicon compound for surface treatment of the metal oxide fine particles, R ₃ SiX (R is an alkyl group,
A monofunctional silane represented by a phenyl group, a vinyl group, a methacryloxy group, a mercapto group, an amino group, an organic group having an epoxy group, and X is a hydrolyzable group, for example,

Trimethylmethoxysilane Triethylmethoxysilane Trimethylethoxysilane Triethylethoxysilane Triphenylmethoxysilane Diphenylmethylmethoxysilane Phenyldimethylmethoxysilane Phenyldimethylethoxysilane Vinyldimethylmethoxysilane Vinyldimethylethoxysilane γ-acryloxypropyldimethylmethoxysilane γ-methacryl Roxypropyldimethylmethoxysilane γ-mercaptopropyldimethylmethoxysilane γ-mercaptopropyldimethylethoxysilane N-β (aminoethyl) γ-aminopropyldimethylmethoxysilane γ-aminopropyldimethylmethoxysilane γ-aminopropyldimethylethoxysilane γ-glyce Cydoxypropyl dimethylmethoxysilane γ-glycy Propyl dimethoxy silane beta-(3,4-epoxycyclohexyl) ethyl dimethyl silane

Alternatively, a bifunctional silane represented by R ₂ SiX ₂ , for example, dimethyldimethoxysilane diethyldimethoxysilane diethyldiethoxysilane diethyldiethoxysilane diphenyldimethoxysilane phenylmethyldimethoxysilane phenylmethyldiethoxysilane vinylmethyldimethoxysilane vinyl Methyldiethoxysilane γ-acryloxypropylmethyldimethoxysilane γ-methacryloxypropyldimethyldimethoxysilane γ-mercaptopropylmethyldimethoxysilane γ-mercaptopropylmethyldiethoxysilane N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane γ -Aminopropylmethyldimethoxysilane γ-aminopropylmethyldiethoxysilane γ-glycidoxypropylmethyldi Methoxysilane γ-glycidoxypropyl methoxydiethoxysilane β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane

Alternatively, trifunctional silane represented by RSiX ₃ , for example, methyltrimethoxysilane ethyltrimethoxysilane methyltriethoxysilane ethyltriethoxysilane phenyltrimethoxysilane phenyltriethoxysilane vinyltrimethoxysilane vinyltriethoxysilane vinyl (Β-Methoxyethoxy) silane γ-acryloxypropyltrimethoxysilane γ-methacryloxypropyltrimethoxysilane γ-mercaptopropyltrimethoxysilane γ-mercaptopropyltriethoxysilane N-β (aminoethyl) γ-aminopropyltrimethoxy Silane γ-aminopropyltrimethoxysilane γ-aminopropyltriethoxysilane γ-glycidoxypropyltrimethoxysilane β-glycidoxypropyltri Tokishishiran γ- glycidoxypropyl triethoxysilane beta-glycidoxypropyl triethoxysilane beta-(3,4-epoxycyclohexyl) ethyl trimethoxysilane.

Further, a tetrafunctional silane represented by SiX ₄ , for example, tetraethyl orthosilicate tetramethyl orthosilicate can be used.

Further, as the metal-dispersed sol other than colloidal silica, the following can be specifically used. The metal oxide sol composed of CeO ₂ has a solid content of 15%, the water-dispersed sol manufactured by Taki Chemical Co., Ltd., the trade name Needral U-15, and the metal oxide sol composed of Sb ₂ O ₅ has a solid content of 15%. 30% methanol dispersion sol manufactured by Nissan Chemical Industries, Ltd., trade name San colloid _R AMT-130,
The composite metal oxide sol composed of TiO ₂ —Fe ₂ O ₃ —SiO ₂ has a solid content of 30%, a methanol dispersion sol manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name Optraque 1130F-.
As a mixed metal oxide sol composed of 2 (A-8) and TiO ₂ —CeO ₂ —SiO ₂ , solid content of 30%, methanol dispersion sol manufactured by Catalysts & Chemicals Industry Co., Ltd., trade name OPTRAK 1130A-2 ( A-8), a mixed metal oxide sol comprising SnO ₂ —WO ₃ having a solid content of 30%, a methanol dispersion sol manufactured by Nissan Kagaku Co., Ltd., trade name Sun Colloid H
The metal oxide sol consisting of IS-30M and Al ₂ O ₃ has a solid content of 10% and is a water-dispersed sol manufactured by Nissan Chemical Co., Ltd.
Trade name Alumina sol-200

(G) Other components added to the hard coat In addition to the above (a) to (g), the hard coat of the present invention comprises
The following functional compounds can be added. These compounds are components capable of reacting with silanol groups after hydrolysis, and may assist the preparation of physical properties such as dyeability, heat resistance, water resistance, antistatic property, improvement of surface hardness, or catalytic action. . A, unsaturated dibasic acid Itaconic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid B, cyclic dibasic acid of unsaturated dibasic acid Succinic anhydride, glutaric anhydride, trimellitic anhydride,
Pyromellitic anhydride, phthalic anhydride, maleic anhydride C, unsaturated dibasic acid imide compounds Succinimide, glutaric acid imide, phthalic acid imide,
Maleic acid imide

D, saturated polycarboxylic acid adipic acid, suberic acid E, saturated polycarboxylic acid cyclic anhydride F, saturated polycarboxylic acid imide compound G, aminos and organic carboxylic acids, cyclic ethers, ketones , Adducts with aldehydes, hydroquinone, etc., or condensates, H, urea and its formaldehyde adducts I, alkyl-substituted methylolated melamine

Compounds having two or more J, OH or SH groups 1,4-butanediol, 1,6-hexanediol,
1,9-nonanediol, 1,10-decanediol,
Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, tripropylene glycol, polypropylene glycol, trimethylolpropane, neopentyl glycol, catechol,
Resorcinol, alkylene glycol, polyvinyl alcohol K, compound having two or more epoxy groups Glycidyl ether L of the above polyhydric alcohol, dicyandiamide, hydrazide, thiourea, guanidine, ethyleneimine sulfonamide and derivatives thereof

In addition, an acidic or alkaline compound can be added to adjust the pH. The above compound may or may not have a functional group.
For example, acrylic acid, acrylic acid dimer, acetic acid, itaconic acid, ammonium perchlorate, aminoethyl acrylate, dimethylbenzylamine and the like.

Further, the following monofunctional compounds may be added to adjust the physical properties. For example, acrylic group,
A polymerizable compound having a glycidyl group, an allyl group, and a vinyl group, 2-hydroxyethyl acrylate 2-hydroxyethyl methacrylate 4-hydroxybutyl acrylate 4-hydroxybutyl methacrylate tetrahydrofurfuryl acrylate tetrahydrofurfuryl methacrylate methyl acrylate methyl methacrylate ethyl Acrylate ethyl methacrylate propyl acrylate propyl methacrylate n-butyl glycidyl ether phenyl glycidyl ether allyl alcohol allyl cinnamate allyl cyclohexane phenyl allyl ether vinyl acetate 4-hydroxybutyl vinyl ether dodecyl vinyl ether propenyl ether propylene carbonate.

Further, a compound having ultraviolet ray resistance and ultraviolet ray absorption performance and having a polymerizable functional group may be added. Specifically, RUVA-93 from Otsuka Chemical Co., Ltd.
However, the following materials may be added in addition to the above. For infrared absorption, a commercially available compound having infrared absorption performance, for example, infrared absorption agent kayas manufactured by Nippon Kayaku Co., Ltd.
Use the orb series. Further, for ultraviolet absorption resistance, a benzophenone or benzotriazole-based compound having an ultraviolet absorption property, for example, an ultraviolet absorber TINUVIN series manufactured by Ciba-Geigy Co., or a seesaw series of Shiraishi calcium is used. Further, as the antioxidant, for example, IRGANOX series of Ciba Geigy is used.
In addition, commercially available products such as methyl hydroquinone (MeHQ) and phenothiazine can be used as the polymerization inhibitor.

As the other UV-curable hard coat, a commercially available one can be used as long as no photoinitiator is added. For example, an organic component may be used. Urethane acrylate, unsaturated polyester, epoxy acrylate, having a polyfunctional polymerizable group starting from the modified acrylic resin shown in (d) of (1) plasmamer or UNIDIC series of Dainippon Ink and Chemicals, Inc. Mixtures of compounds are also available.

(H) Hard coat curing catalyst The following hard coat curing catalyst may be added to the hard coat liquid. The following primary to tertiary amines are used as the amines. Polymethylenediamine, polyetherdiamine, diethylenetriamine, iminobispropylamine, bishexamethylenetriamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, pentaethylenehexamine, dimethylaminopropylamine, aminoethylethanolamine, methyliminobispropyl Amine, menthanediamine, N-aminomethylbiperazine, 1,3-diaminocyclohexane, isophoronediamine, metaxylenediamine, tetrachloroparaxylenediamine, metaphenylenediamine, 4.4'-methylenedianiline, diaminodiphenylsulfone, Benzidine, toluidine, diaminodiphenyl ether, 4,4'-thiodianiline, 4,4'-bis (o-toluidine) dia Shijin,
o-phenylenediamine, 2,4-toluenediamine,
Methylenebis (o-chloroaniline), diaminiditolyl sulfone, bis (3,4-diaminophenyl) sulfone, 2.6-diaminopyridine, 4-chloro-o-
Phenylenediamine, 4-methoxy-6-methyl-m-
Phenylenediamine, m-aminobenzylamine, N,
N, N ', N'-tetramethyl-1,3-butanediamine, N, N, N', N'-tetramethyl-p-phenylenediamine, tetramethylguanidine, triethanolamine, 2-dimethylamino-2 -Hydroxypropane, N, N'-dimethylpiperazine, N, N'-bis [(2-hydroxy) propyl] piperazine, N-methylformoline, hexamethylenetetramine, pyridine,
Pyrazine, quinoline, benzyldimethylamine, α-methylbenzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethylol) phenol, N-methylpiperazine, pyrrolidine, formolin

In addition, the following compounds can be used. Alkali metal salts and ammonium salts of carboxylic acids, Metal salts and ammonium salts of acetylacetone,
Metal salt of ethyl acetoacetate, metal salt of acetylacetone and ethyl acetoacetate coordinated, diamide,
Imidazole, organic sulfonic acid and its amine salt,
Organometallic salts such as magnesium perchlorate, ammonium perchlorate, zinc naphthenate, tin octylate, Sn
It is also possible to use a Lewis acid such as Cl ₄ , TiCl ₄ , ZnCl ₂ or the like, or a compound thereof with an organic mercaptan or mercaptoalkylenesilane.

To prepare the hard coat layer, a solvent is added to these compounds to form a uniform mixed solution. When the compound of (2) hard coat is used, the solvent may be stripped. Further, after stripping, it is possible to further dilute with a solvent.

(3) Solvents for Primer and Hard Coat The following compounds are used as solvents for the primer and hard coat. Alcohols, ethers, aromatic hydrocarbons, esters, ketones, methanol, ethanol, isopropyl alcohol, n-butanol,
2-butanol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, ethylene glycol, methyl acetate, ethyl acetate, diethyl ether, tetrahydrofuran, acetone, xylene, N, N
-Dimethylformamide, methyl ethyl ketone, dichloroethane, toluene

(4) Other Additives In addition to the above components, the following compounds may be added to the primer in order to impart other physical properties. Further, in order to increase the refractive index, the metal oxide fine particle sol exemplified as the component of the hard coat layer can be used. In particular,
Si, Ti, Ce, Fe, Sn, Zr, Al, W, S
It is a sol in which at least one or more kinds of metal oxide fine particles or complex oxide fine particles selected from b, Ta, La and In are dispersed in water or another solvent. Further, the metal oxide fine particle sol may be a single compound or a mixture. The size of the metal oxide fine particles is 1 to 100 nm
The surface of the metal oxide can be treated with a silicon compound. The organosilicon compound used at this time is represented by R ₃ SiX (R is an organic group having an alkyl group, a phenyl group, a vinyl group, a methacryloxy group, a mercapto group, an amino group, an epoxy group, and X is a hydrolyzable group). And monofunctional silanes. Further, as the primer, the compound having the infrared absorption and ultraviolet absorption properties used in the hard coat layer, the antioxidant and the weather resistance imparting agent may be used. Furthermore, a leveling agent as exemplified below may be used for both the hard coat layer and the primer. Copolymer of polyoxyalkylene and polydimethylsiloxane Copolymer of polyoxyalkylene and fluorocarbon

(5) Substrate The substrate of the present invention is preferably a transparent substrate such as a transparent plastic plate, a transparent film and a plastic lens. For example, it is used for a spectacle lens base material, an optical lens base material, a sheet, a film, etc., but a material made of diethylene glycol bisallyl carbonate, various transparent synthetic resins such as polymethamethyl acrylate (PMMA) and polycarbonate are preferably used. As a method for applying the coating composition of the present invention to a transparent substrate, methods such as a dipping method, a flow method, a spinner method, and a spray method can be adopted. Further, in order to prevent reflection of the hard coat film obtained by applying the composition of the present invention, it is possible to apply an antireflection coat on the hard coat film.

[0048]

According to the present invention, a substrate is coated with a primer,
After obtaining the coating film, the hard coat liquid is applied. At this time, the catalyst exuding from the primer coating film assists the curing of the hard coat film. Thus, for example, a coating film made of a thermosetting type silicone hard coat, which was difficult to cure on a primer coating film made of a urethane resin, is obtained.
Further, since the amount of the curing agent added to the hard coat can be reduced or removed, the life of the hard coat liquid can be extended.

Generally, a thermosetting type silicone hard coat is said to have a short liquid life, but the above-mentioned manufacturing method capable of removing the curing catalyst can prolong the life of the hard coat liquid.

[0050]

Embodiments of the present invention will be described below. Example 1 98 g of Desmophen 1200, a polyester polyol manufactured by Sumitomo Bayer Urethane Co., Ltd., 136 g of Desmodur LS-2759, a block polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd., and 751 g of methoxypropanol 751 g as a solvent were mixed. The mixture was thoroughly stirred until it became uniform. Next, 15 g of Nasem Al manufactured by Nippon Kagaku Sangyo Co., Ltd. was added and dissolved. further,
A uniform primer solution was obtained by adding 0.5 g of leveling agent Florard FC430 manufactured by 3M Co., Ltd. and stirring.

Next, 300 g of Snowtex O-40, which is colloidal silica manufactured by Nissan Chemical Industries, Ltd., was weighed into a flask, and 135 g of γ-glycidoxypropyltrimethoxysilane and 49 g of methyltrimethoxysilane were stirred and cooled. Is gradually added. After the addition was completed, the mixture was stirred for another hour. On the way, the cooling was stopped when the temperature rise of the mixed liquid stopped. Thereafter, while stirring the mixed solution, 450 g of isopropanol was added as a diluting solvent, and then 60 g of 4-hydroxybutyl acrylate was added. 0.4 g of leveling agent L-7001 manufactured by Nippon Unicar Co., Ltd. was added and stirred for 20 minutes to obtain a hard coat composition.

The above-mentioned primer was applied to a plastic lens made of diethylene glycol bisallyl carbonate by dipping and cured at 90 ° C. for 30 minutes. The film thickness was 1 to 1.2 μm. Next, the hard coat liquid was applied by dipping and cured at 120 ° C. for 1 hour.
The film thickness was 2-3 μm. The appearance of the obtained lens was good, the adhesion was 100%, and the hardness was 4. The dyeability was 40% in terms of light transmittance.

Example 2 54 g of Desmophen 800, a polyester polyol manufactured by Sumitomo Bayer Urethane Co., Ltd., 78 g of Desmodur LS-2759, a block type polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd., and 533 g of methoxypropanol as a solvent. Were mixed and thoroughly stirred until a uniform state was obtained. Next, 15 g of Nursem Al manufactured by Nippon Kagaku Sangyo Co., Ltd. was added and dissolved. Next, Optraque 113, which is a metal oxide sol of Catalyst Kasei Co., Ltd.
320 g of 0F2 (A-8) was added and stirred. Furthermore, the leveling agent Florard FC171 manufactured by 3M Co., Ltd.
Was added and stirred to obtain a uniform primer solution. Next, Optraque 1130F2 (A-8)
Weigh 499 g into a flask. There, distilled water 120
g was added with stirring. Next, 184 g of γ-glycidoxypropyltrimethoxysilane is gradually added.
After the addition was completed, the mixture was stirred for another 2 hours.

Then, 147 g of isopropanol was added while stirring the mixed solution, and then P from Nippon Oil & Fats Co., Ltd. was added.
40 g of E200 was added. Further, 1 g of ammonium perchlorate was added as a curing catalyst. 0.4g of leveling agent L-7001 manufactured by Nippon Unicar Co., Ltd. was added,
After stirring for 20 minutes, a hard coat composition was obtained. The above-mentioned primer is applied to a plastic lens made of high refractive index monomer MR-7 manufactured by Mitsui Toatsu Co., Ltd. by dipping,
It was cured at 95 ° C for 30 minutes. The film thickness was 1 to 1.1 μm. Next, apply the hard coat liquid by dipping,
It was cured at 120 ° C. for 1 hour. Film thickness is 1.5-2 μm
Met. The appearance of the obtained lens is good and the adhesion is 100.
%, And the hardness was 4. The dyeability was 35% in terms of light transmittance.

Example 3 Witco Bond W, a water-soluble urethane resin manufactured by Witco
333 g of -240, butyl cellosolve 13 as a solvent
0 g and 437 g of distilled water were mixed and sufficiently stirred until a uniform state was obtained. Next, 100 g of a 10% aqueous solution of ammonium perchlorate was added and stirred. Further, 1 g of a leveling agent L-77 manufactured by Nippon Unicar Co., Ltd. was added and stirred to obtain a primer solution. Next, 300 g of Snowtex O-40 was weighed into a flask and γ-glycidoxypropyltrimethoxysilane 20 was added while cooling and stirring.
3 g and 73 g of methyltrimethoxysilane are gradually added. After the addition was completed, the mixture was stirred for another hour. On the way, the cooling was stopped when the temperature rise of the mixed liquid stopped. Then, while stirring the mixed solution, 4 parts of isopropanol was used as a diluting solvent.
24 g was added. Further, ammonium perchlorate was added to 0.
5 g, leveling agent L-70 manufactured by Nippon Unicar Co., Ltd.
0.4 g of 01 was added and stirred for 1 hour to obtain a hard coat composition.

The above-mentioned primer was applied to a plastic lens made of diethylene glycol bisallyl carbonate by dipping and cured at 90 ° C. for 30 minutes. The film thickness was 1 to 1.2 μm. Next, the hard coat liquid was applied by dipping and cured at 120 ° C. for 1 hour.
The film thickness was 2-3 μm. The appearance of the obtained lens was good, the adhesion was 100%, and the hardness was 4. The dyeability was 45% in terms of light transmittance.

Example 4 Acryloid A-10, an acrylic resin manufactured by Rohm & Haas
280 g of S, 600 g of ethylene glycol monopropyl ether as a solvent, and 20 g of UV absorber Seesorb 100 manufactured by Shiraishi Calcium Co., Ltd. were mixed and sufficiently stirred until a uniform state was obtained. Next, 100 g of 10% IPA solution of choline acetate was added and stirred. Further, 0.1 g of Paintad 31 which is a leveling agent manufactured by Dow Corning Asia Co., Ltd. was added and stirred to obtain a uniform primer solution. Snowtex O-40
Was weighed into a flask, and 365 g of methyltrimethoxysilane was gradually added while cooling and stirring. After the addition was completed, stirring was continued for 6 hours. On the way, the cooling was stopped when the temperature rise of the mixed liquid stopped. Then, while stirring the mixed solution, 335 g of isopropanol was used as a diluting solvent.
Was added. Furthermore, 0.2 g of Paintad 31 was added and stirred to obtain a hard coat composition. The above primer was applied on a polycarbonate sheet by dipping and air dried. The film thickness was 1.5 to 3 μm. Next, the hard coat solution was applied by dipping and cured at 120 ° C. for 1 hour. The film thickness was 3 to 4 μm. The appearance of the obtained sheet was good, the adhesion was 100%, and the hardness was 5.

Example 5 250 g of Acryloid A-10S was dissolved in 730 g of methoxypropanol, and 1 part of Seesaw 100 was dissolved.
0 g, photoinitiator Darocur 1173 made by Ciba Geigy
Was added and stirred to obtain a primer. Next, 150 g of trimethylolpropane triacrylate and 1,6-
50 g of hexanediacrylate is added to isopropanol 33
It was dissolved in 0 g, 40 g of γ-aminopropyltrimethoxysilane was added thereto, and the mixture was stirred for 30 minutes. In addition, 60 g of acrylic acid dimer was added, and Snowtex O-
130 g of 40 and 240 g of IPA-ST, which is colloidal silica manufactured by Nissan Chemical Industries, Ltd., were added and stirred for 1 hour. Further, 1 g of Paintad 31 was added and stirred to obtain a hard coat liquid. The above primer was applied on a polycarbonate sheet by dipping and air dried. The film thickness is 1.
It was 5 to 3 μm. Next, the hard coat liquid was applied by dipping, and was irradiated with ultraviolet rays with a metal halide lamp of 120 w / cm so as to have an integrated light amount of 1 J / cm ² , and cured. The film thickness was 4 to 6 μm. The appearance of the obtained sheet was good, the adhesion was 100%, and the hardness was 4.

Next, the measuring method of the performance test of the obtained hard coat film will be described. Cross-hatch test It was based on the goggle test LISK5400. Steel wool test Rubbing with steel wool # 0000 under a load of 1 kg,
The relative scratches were compared based on the following criteria. 5: No scratches 4: Slight scratches 3: Scratch 2: Severe scratches 1: Scratch on the base material

Dyeability BPI of Brain Power Inc (USA)
A GRAY diluted with distilled water to 9% was heated to 90 ° C., and a lens coated with each coating solution was immersed in this aqueous solution for 5 minutes, and then the lens was taken out and washed with water. The total light transmittance after dyeing was measured to compare the dyeability.

According to the present invention, for example, a coating film made of a thermosetting type silicone hard coat liquid, which is difficult to cure on a primer coating film of urethane resin or the like, can be obtained.
Furthermore, since the amount of the curing agent added to the hard coat can be reduced or removed, the life of the coating liquid can be extended.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location B32B 27/18 B32B 27/18 Z 27/30 27/30 A 27/36 27/36 27/38 27/38 27/40 27/40 27/42 27/42 102 102

Claims (11)

[Claims] 1. A primer containing a catalyst which can cure a hard coat liquid applied on a substrate through a primer layer and which does not react with a primer component or does not affect the properties of the primer. A layered product comprising a layer and a hard coat layer on the primer layer. 2. The primer layer is made of polyester resin, epoxy resin, melamine resin, acrylic resin, amino resin,
A urethane resin or at least one of modified resins of the respective resins is contained.
The laminate described. 3. The primer layer comprises a blocked polyisocyanate and a urethane resin obtained by heat-curing a composition containing polyester polyol, polyether polyol, polycaprolactone, polycarbonate polyol or polyacrylic polyol as a main component. The laminate according to claim 1, which is characterized in that. 4. The laminate according to claim 1, wherein the primer layer is made of a urethane resin obtained by evaporating the water content of an aqueous urethane resin dispersed in water. 5. The hard coat curing catalyst in the primer layer is a metal salt or ammonium salt of acetylacetone, a metal salt of ethylacetoacetate, a metal salt of coordinated acetylacetone and ethylacetoacetate, an alkali metal salt of carboxylic acid or ammonium. Salts, choline acetate, primary to tertiary amines, diamides, imidazoles,
Amines such as polyalkylene amine, magnesium perchlorate, ammonium perchlorate, etc., organic metal salts such as zinc naphthenate, tin octylate, SnCl ₄ , TiCl ₄ , Z
The laminate according to claim 1, which is any compound or mixture selected from the group consisting of Lewis acids such as nCl ₂ . 6. The laminate according to claim 1, wherein the hard coat curing catalyst in the primer layer comprises a photopolymerization initiator. 7. The laminate according to claim 1, wherein the hard coat layer is formed of a silicone paint. 8. The silicone coating comprises (1) a metal oxide fine particle dispersed sol, (2) an epoxy group-containing silicon compound or a partial hydrolyzate thereof, or (3) only one O in a molecule.
A functional group having an H group or an SH group and further represented by the following structural formula in the main chain of the molecule: —O—, —CO—O—, —S—,
The laminate according to claim 7, which comprises at least one of -CO-S- or -CS-S- and has a compound soluble in water or a lower alcohol having 4 or less carbon atoms as a main component. 9. The silicone coating composition is mainly composed of a compound containing (1) a sol of fine metal oxide particles dispersed therein and (2) a composition containing an alkyl group-containing silicon compound or a partial hydrolyzate thereof as a main component. The laminate described. 10. The silicone coating comprises (1) a sol containing fine metal oxide particles dispersed therein, (2) a silane having at least one or more functional groups, and (3) at least one of a vinyl group, an allyl group, a methacrylic group or an epoxy group. The laminate according to claim 7, which comprises a compound having a plurality of polymerizable functional groups as a main component. 11. A catalyst in which a catalyst capable of curing a hard coat is added to a primer, a primer is applied to a substrate to obtain a coating film, and then a hard coat liquid is applied to exude from the primer coating film. A method for producing a laminate, which comprises accelerating the curing of a hard coat film by means of.