CN112574456B - Coating film for frame and photocurable coating resin composition for frame - Google Patents

Coating film for frame and photocurable coating resin composition for frame Download PDF

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Publication number
CN112574456B
CN112574456B CN202011039546.XA CN202011039546A CN112574456B CN 112574456 B CN112574456 B CN 112574456B CN 202011039546 A CN202011039546 A CN 202011039546A CN 112574456 B CN112574456 B CN 112574456B
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Prior art keywords
frame
photocurable
film
resin composition
coating
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CN112574456A (en
Inventor
矶崎正义
斋藤宪
河谷俊宏
森亮
梅田研二
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel and Sumikin Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2435/02—Characterised by the use of homopolymers or copolymers of esters

Abstract

The invention provides a coating film for a frame, which can satisfy both steel wool resistance and bending resistance when used for a frame of a smart phone and the like, and a photo-hardening coating resin composition for a frame. A coating film for a frame, which is formed on a frame comprising polymethyl methacrylate and/or polycarbonate, and wherein #0000 steel wool is formed at a rate of 1.5kg/cm relative to the surface of the coating film, and a photocurable coating resin composition for a frame for obtaining the coating film 2 After 300 times of load round-trip, a film having a thickness of 10 μm was formed on the frame body, and the film was pressed against a cylinder having a diameter of 30mm with the coated film as the outside, and wound so that the bending angle became 180 degrees, and at this time, deformation or crack was not substantially confirmed.

Description

Coating film for frame and photocurable coating resin composition for frame
Technical Field
The present invention relates to a coating film for a casing and a photocurable coating resin composition which exhibit excellent characteristics as a casing for a portable communication device represented by a smart phone.
Background
In recent years, terminal devices excellent in portability, such as smart phones, mobile phones, and tablet terminals with communication functions, have been widely used.
In such a communication device, communication means in a high frequency band such as millimeter waves have been realized in response to an increase in communication speed and the amount of data transmitted and received, and it has become an urgent problem to reduce communication errors caused by noise, transmission loss, and the like at the time of data transmission and reception.
As a means for this, a plastic housing excellent in low dielectric characteristics is being studied as a housing of the terminal equipment. Plastic frames are widely used in terminal equipment from the middle end to the high end because of their excellent processability, mass productivity, and cost performance in addition to their excellent low dielectric characteristics.
On the other hand, plastic frames have the following disadvantages: the surface is easily damaged, and the appearance is inferior to that of a glass or metal frame. Therefore, a method of providing a coating layer on the surface of the plastic frame is used.
In many cases, an acrylic resin is used for such a coating layer, and the coating layer is cured by irradiation with actinic rays to exhibit excellent surface hardness (steel wool resistance).
As a coating layer for a plastic frame, the following patent documents 1 and 2 propose a method of transferring a functional hard coating layer to satisfy scratch resistance. In patent documents 2 to 4, lubricity, releasability, flexibility (softness) and steel wool resistance obtained by stress relaxation are obtained by using a silicon compound.
[ Prior Art literature ]
[ patent literature ]
Patent document 1 Japanese patent laid-open publication No. 2019-25739
Patent document 2 Japanese patent laid-open No. 2015-196748
[ patent document 3] International publication No. WO 2015/152288
[ patent document 4] International publication No. WO 2015/152289
Disclosure of Invention
[ problem to be solved by the invention ]
For the laminate as described above, improvement in steel wool resistance of the coating layer has been demanded. On the other hand, if the steel wool resistance is improved, the bending resistance is lowered, when used in a portable communication device, the coating layer of the housing may be deformed or cracked. Accordingly, the present invention has an object to provide a coating film for a frame that can satisfy both steel wool resistance and bending resistance when used for a frame application such as a smart phone, and a photocurable coating resin composition for obtaining the coating film for a frame.
[ means of solving the problems ]
That is, the present invention is a coating film for a frame, which is a coating film formed on a frame comprising polymethyl methacrylate and/or polycarbonate, and is characterized in that,
on the surface opposite to the coating film, the #0000 steel wool is used for 1.5kg/cm 2 After 300 load rounds, virtually no damage is generated, and
a film having a thickness of 10 μm was formed on the frame, pressed onto a cylinder having a diameter of 30mm with the coated film as the outside, and wound so that the bending angle became 180 degrees, and at this time, substantially no deformation or crack was observed.
[ Effect of the invention ]
According to the present invention, a coating film having both scratch resistance and bending resistance can be provided. The coating film of the present invention having such characteristics is particularly useful for a housing of a terminal device excellent in portability, such as a smart phone, a mobile phone, and a tablet terminal having a communication function.
Detailed Description
The following description is given in detail of each element constituting the present invention, but the following description is an example of the embodiment of the present invention, and the present invention is not limited to the following description unless departing from the gist of the present invention. In the present specification, the expression "to" is used to include the numerical value before and after the expression and the expression of the physical property value. In the present invention, when "(meth) acrylic acid" is used, it means either or both of "acrylic acid" and "methacrylic acid". The same is true for "(meth) acrylate", "(meth) acryl".
The coating film for a frame body of the present invention is a coating film formed on a frame body (substrate) comprising polymethyl methacrylate and/or polycarbonate, and #0000 steel wool is formed at a rate of 1.5kg/cm on the surface of the coating film 2 After 300 times of load round-trip, a film having a thickness of 10 μm was formed on the frame (substrate), and the film was pressed onto a cylinder having a diameter of 30mm with the coated film as the outside, and wound so that the bending angle became 180 degrees, and at this time, deformation or crack was not substantially confirmed.
A photocurable coating resin composition (hereinafter, sometimes simply referred to as "composition") for providing such a coating film contains (a) a photocurable compound, (b) a photopolymerization initiator, and (c) a solvent.
(a) The photocurable compound of the component (c) contains a photocurable polyfunctional monomer represented by the following formula (1) or (2) as an essential component.
[ chemical 1]
[ chemical 2]
By containing (1) and (2), the crosslinking density at the time of hardening becomes high, and as a result, steel wool resistance can be satisfied. If the above-mentioned components (1) and (2) are not contained, the crosslinking density at the time of hardening is insufficient, and it is difficult to satisfy the steel wool resistance.
(a) The molar number of acrylic acid per 100g of the photocurable compound of the component (A) is in the range of 0.8 to 1.1. When the molar number of acrylic acid is less than 0.8, the crosslinking density becomes low and the scratch resistance becomes low. Conversely, if it exceeds 1.1, cracks are generated during bending.
The molar number of acrylic acid per 100g represents the molar number of acrylic acid (the number of acrylic acid functional groups/the molecular weight g.mol -1 ) Is a sum of (a) and (b).
(a) More than 75 mass percent (wt%) of the photo-hardening compound of the component has more than three (meth) acrylic groups in the molecule. If the amount is less than 75wt%, the crosslinking density is lowered, and it is difficult to satisfy the steel wool resistance.
Examples of the compound having three or more (meth) acrylic groups in the molecule include: pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, trimethylolpropane tetraacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, pentaerythritol ethylene oxide modified tetraacrylate, dipentaerythritol ethylene oxide modified pentaacrylate, dipentaerythritol ethylene oxide modified hexaacrylate, tris (2-acryloyloxyethyl) isocyanurate.
(a) The number of moles of hydroxyl groups per 100g of the photocurable compound of the component (A) is in the range of 0.06 to 0.20. If the above range is not satisfied, the elastic modulus decreases, and the desired steel wool resistance cannot be obtained. On the other hand, even if the content exceeds the above range, further improvement cannot be expected.
The number of moles of hydroxyl groups per 100g represents the number of moles of hydroxyl groups (number of hydroxyl groups/molecular weight g.mol -1 ) Is a sum of (a) and (b).
Examples of the hydroxyl group-containing (meth) acrylate include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, glycerol di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like. Among them, trifunctional or more hydroxyl group-containing (meth) acrylates are preferable.
The photocurable compound as the component (a) may contain two or less acrylic acid esters in the molecule in order to adjust the molar number of acrylic acid and the molar number of hydroxyl groups per 100 g.
Specific examples of the compound containing two or more acrylic acid esters in the molecule include: 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, tetraethylene glycol dimethacrylate, dicyclopentyl dimethylol di (meth) acrylate group, and the like.
The photocurable compound of component (a) may contain urethane-modified (meth) acrylates or ethylene oxide-modified (meth) acrylates. These compounds are effective for improving the bending resistance of the coating film for a frame.
Examples of the photopolymerization initiator (b) of the photocurable coating resin composition include: benzoin such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc.; acetophenones such as acetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one, and the like; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, and 2-pentylalnthraquinone; thioxanthones such as 2, 4-diethyl thioxanthone, 2-isopropyl thioxanthone and 2-chloro thioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone such as benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, and 4,4' -dimethylaminobenzophenone; phosphine oxides such as 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide and bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide.
These compounds may be used alone or as a mixture of two or more, and may be used in combination with a tertiary amine such as triethanolamine or methyldiethanolamine, a benzoic acid derivative such as ethyl N, N-dimethylaminobenzoate or isoamyl N, N-dimethylaminobenzoate, and the like.
The photopolymerization initiator of the component (b) is 0.1 to 20wt%, preferably 1 to 10wt%, based on 100wt% of the total of the components (a). If the content is not within the above range, crosslinking is insufficient, the elastic modulus is lowered, and the desired steel wool resistance cannot be obtained. On the other hand, even if the content exceeds the above range, further improvement in the reaction rate cannot be expected.
As the solvent of the component (c), an aromatic organic solvent such as toluene or xylene can be used; ketone-based organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ester-based organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate, isobutyl acetate, and the like; alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; conventional organic solvents such as glycol ether-based organic solvents, e.g., propylene glycol monomethyl ether. Particularly preferred is an organic solvent containing a glycol ether.
Examples of the glycol ether-based organic solvent include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol dipropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isopentyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, methoxyethoxyethanol, and ethylene glycol monoallyl ether; propylene glycol such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and butoxypropanol, and among them, propylene glycol monomethyl ether is preferable.
Various additives may be added to the photocurable coating resin composition for a frame of the present invention within a range not departing from the object of the present invention. Examples of the various additives include organic/inorganic fillers, slip agents, plasticizers, flame retardants, heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, mold release agents, foaming agents, nucleating agents, colorants, crosslinking agents, dispersing aids, and resin components.
The photocurable coating resin composition for a frame of the present invention can be cured by irradiation with ultraviolet rays having a wavelength of 10nm to 400nm or visible rays having a wavelength of 400nm to 700 nm. The wavelength of the light to be used is not particularly limited, and near ultraviolet rays having a wavelength of 200nm to 400nm are particularly suitably used. Examples of the lamp used as the ultraviolet light generating source include a low-pressure mercury lamp (output: 0.4W/cm to 4W/cm), a high-pressure mercury lamp (40W/cm to 160W/cm), an ultra-high-pressure mercury lamp (173W/cm to 435W/cm), and a metal halide lamp (80W/cm to 160W/cm).
The method for obtaining a coating film by irradiation with light may be either an oxygen-blocked environment or an atmospheric environment, but the composition of the present invention provides a good coating even if it is polymerized and cured in an atmospheric environment. Examples include: casting, roll coating, bar coating, spray coating, air knife coating, spin coating, flow coating, curtain coating, and dipping. The thickness of the coating film is adjusted according to the solid content concentration in consideration of the thickness of the molded film after drying and hardening.
As a material used in the frame of the present invention, polymethyl methacrylate and/or polycarbonate are used. The photocurable coating resin composition is applied in a state where these raw materials are formed into a flat plate shape or a box shape with one surface open. The thickness of the frame is preferably as thin as possible in order to achieve weight reduction, but in order to maintain a constant strength, the thickness of the frame is preferably in the range of 0.1mm to 2mm, more preferably in the range of 0.1mm to 1 mm.
Examples (example)
Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the examples.
Production example 1 < production of Photocurable coating resin composition A1 for frame body >
60 parts by weight of dipentaerythritol hexaacrylate: mw= 578.57, number of acrylic groups=6, number of hydroxyl groups=0 [ 35% dipentaerythritol pentaacrylate (mw= 524.52, number of acrylic groups=5, number of hydroxyl groups=1) ] (product name DPHA manufactured by co-company chemical company), 20 parts by weight of pentaerythritol triacrylate: mw= 298.29, number of acrylic groups=3, number of hydroxyl groups=1 [ comprising 40% pentaerythritol tetraacrylate (mw= 352.34, number of acrylic groups=4, number of hydroxyl groups=0) ] (Light Acrylate) PE-3A manufactured by co-company chemical company), 20 parts by weight of trimethylolpropane triacrylate: mw= 296.32, the number of acrylic groups=3, the number of hydroxyl groups=0 (Light Acrylate) TMP-a manufactured by co-company chemical company) were mixed, and 8 parts by weight of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one (IGM resin b.v. (IGM Resins b.v.) 907 manufactured by IGM Resins b.v.), which was a photopolymerization initiator, and propylene glycol monomethyl ether as an organic solvent were used, and were adjusted so that the solid content became 40%, to obtain a coated resin composition for A1 for a frame. The photocurable compound has a molar number of acrylic acid of { [ (6/578.57 ×0.65) + (5/524.52 ×0.35) ]×0.6 [ (4/352.34 ×0.4) + (3/298.29 ×0.6) ]×0.2+ (3/296.32) ×0.2} ×100=1.02, a molar number of hydroxyl groups of [ (1/524.52 ×0.35) ×0.6+ (1/298.29 ×0.6) ×0.2] ×100=0.08, and a ratio of three or more functions of 100%.
Example 1 preparation of coating film on polymethyl methacrylate/polycarbonate laminate substrate
The photo-curable coating resin composition for frame A1 was applied by spin coating to the side of polymethyl methacrylate on a polymethyl methacrylate/polycarbonate laminate substrate (thickness: 650 μm, length: 10cm, width: 10cm, ai Sika Boschmitt (ESCARBOSHEET)) so that the film thickness after drying became 10. Mu.m, dried at 80℃for 5 minutes, and then cooled at room temperature for 5 minutes. Thereafter, 2kW/cm was used under an oxygen atmosphere 2 Is 2,800mJ/cm 2 The film was formed by accumulating the exposure (365 nm conversion), and a laminate S1 for the housing was obtained.
Example 5 preparation of coating film on polycarbonate substrate
The frame photo-curable coating resin composition A1 was applied to a polycarbonate substrate (thickness: 500 μm, length: 10cm, width: 10cm, manufactured by Asahi glass Co., ltd.) by spin coating so that the film thickness after drying became 10. Mu.m, dried at 80℃for 5 minutes, and then cooled at room temperature for 5 minutes. Thereafter, 2kW/cm was used under an oxygen atmosphere 2 Is 2,800mJ/cm 2 The film was formed by accumulating the exposure (365 nm conversion), and a laminate T1 for the housing was obtained.
Production examples 2 to 8
The same procedure as in production example 1 was followed except that the raw materials and the composition ratios shown in table 1 were used to obtain a frame photocurable coating resin composition A2 to a frame photocurable coating resin composition A4 (production example 2 to production example 4) and a frame photocurable coating resin composition B1 to a frame photocurable coating resin composition B4 (production example 5 to production example 8).
The abbreviations in the tables refer to the following.
PE-4A: pentaerythritol tetraacrylate: mw= 352.34 acrylic group number=4 (co-Rong chemical Co., ltd.)
DCPA: dimethylol-tricyclodecane diacrylate: mw= 304.39 acrylic group number=2 (co-Rong chemical Co., ltd.)
G201P: 2-hydroxy-3-acryloxypropyl methacrylate: mw= 214.22 (meth) acrylic group number=2 hydroxyl group number=1 (co-processing chemical company)
TMP-6EO-3A:6 EO-modified trimethylolpropane triacrylate: mw= 560.64 acrylic group number=3 (co-Rong chemical Co., ltd.)
Ai Bake force (EBECRYL) 210: aromatic urethane acrylate: mw=1500, acrylic group number=2 (Daicel-ALLNEX) company
Mole of acrylic acid per 100g of photocurable compound = mole of acrylic acid per 100g of each component of photocurable compound (number of acrylic acid functional groups/molecular weight g.mol -1 ) Sum of (2)
Number of moles of hydroxyl groups per 100g of photocurable compound=number of moles of hydroxyl groups per 100g of each component of photocurable compound (number of hydroxyl groups/molecular weight g.mol -1 ) Sum of (2)
(examples 2 to 4 and examples 6 to 8)
< production of laminate S2 to laminate S4, laminate T2 to laminate T4)
The frame laminate S2 to the frame laminate S4 (examples 2 to 4) were produced in the same procedure as in example 1, and the frame laminate T2 to the frame laminate T4 (examples 6 to 8) were produced in the same procedure as in example 5, except that the frame photocurable coating resin compositions A2 to A4 prepared in the composition ratios shown in table 1 were used.
Comparative examples 1 to 8
< production of laminate U1 to laminate U4, laminate V1 to laminate V4)
The frame laminates U1 to U4 (comparative examples 1 to 4) and the frame laminates V1 to V4 (comparative examples 5 to 8) were produced in the same steps as described above, except that the frame photocurable coating resin compositions B1 to B4 prepared in the composition ratios shown in table 1 were used.
< evaluation >
The following evaluations were performed using the obtained laminate S1 to S4 for a frame and laminate T1 to T4 for a frame (examples), and laminate U1 to U4 for a frame and laminate V1 to V4 for a frame (comparative examples). The evaluation results are shown in tables 2 and 3.
< Steel wool resistance >)
A laminate S1 for frame, a laminate S4 for frame, a laminate T1 for frame, a laminate T4 for frame (example), a laminate U1 for frame, a laminate U4 for frame, a laminate V1 for frame, a laminate V4 for frame (comparative example) were used, and for each, #0000 steel wool was used, and a round trip abrasion tester (Type: 30S manufactured by HEIDON) was used to load 1.5kg/cm 2 The surface of the coating film was abraded 300 times back and forth. The presence or absence of occurrence of damage was visually observed, and the presence or absence of damage was determined based on the following criteria, and the number of 7 points or more was defined as "o".
10 points: 0 root of Chinese character
7 points: more than 1 and less than 5
4 points: more than 5 and less than 10
1 point: more than 10
< bending resistance >
The laminate S1 to the laminate S4 for the frame and the laminate T1 to the laminate T4 for the frame (examples), and the laminate U1 to the laminate U4 and the laminate V1 to the laminate V4 (comparative examples) were cut into 80mm×50mm squares as test materials, and each of the test materials was wound with the coated film surface as the outer side and the long edge of the test material (substrate surface side) along the circumference of the cylinder with respect to an acrylic cylinder having a diameter of 30mm until the bending angle became 180 degrees (U-shape), and the deformation or crack of the coated film was visually observed.
O: no deformation or crack is generated
X: producing deformation or cracking
TABLE 1
TABLE 2
TABLE 3

Claims (4)

1. A coating film for a frame, which is formed on a frame comprising polymethyl methacrylate and/or polycarbonate, characterized in that,
the coating film is a cured product of a photocurable coating resin composition for a frame body, which comprises (a) a photocurable compound, (b) a photopolymerization initiator, and (c) a solvent, wherein the photocurable compound (a) contains a photocurable polyfunctional monomer represented by the following formula (1) and a photocurable polyfunctional monomer represented by the following formula (2) as essential components, and the molar number of hydroxyl groups of the photocurable compound per 100g is 0.06 to 0.2;
on the surface opposite to the coating film, the #0000 steel wool is used for 1.5kg/cm 2 After 300 times of load round trip, no damage is generated, and
a film having a thickness of 10 μm was formed on the frame, the film was pressed onto a cylinder having a diameter of 30mm with the coated film as the outside, and the film was wound so that the bending angle became 180 degrees, and at this time, no deformation or crack was confirmed,
2. a photocurable coating resin composition for a frame, which is used to obtain a coating film for a frame that is formed on a frame that contains polymethyl methacrylate and/or polycarbonate and that satisfies the following (i) and (ii), wherein the photocurable coating resin composition for a frame contains (a) a photocurable compound, (b) a photopolymerization initiator, and (c) a solvent, wherein the (a) photocurable compound contains, as essential components, a photocurable polyfunctional monomer represented by the following formula (1) and a photocurable polyfunctional monomer represented by the following formula (2), and wherein the molar number of hydroxyl groups per 100g of the photocurable compound is 0.06 or more and 0.2 or less;
(i) On the surface opposite to the coating film, the #0000 steel wool is used for 1.5kg/cm 2 After 300 times of load round trip, no damage is generated;
(ii) A film having a thickness of 10 μm was formed on the frame, the film was pressed onto a cylinder having a diameter of 30mm with the coated film as the outside, and the film was wound so that the bending angle became 180 degrees, and at this time, no deformation or crack was confirmed,
3. the photocurable coating resin composition for a frame according to claim 2, wherein the molar number of acrylic acid per 100g of the photocurable compound is 0.8 or more and less than 1.1.
4. The photocurable coating resin composition for a frame according to claim 2, wherein 75% by weight or more of the photocurable compound has three or more (meth) acrylic groups in the molecule.
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