CN115336402B - Laminated body for frame - Google Patents
Laminated body for frameInfo
- Publication number
- CN115336402B CN115336402B CN202180021929.0A CN202180021929A CN115336402B CN 115336402 B CN115336402 B CN 115336402B CN 202180021929 A CN202180021929 A CN 202180021929A CN 115336402 B CN115336402 B CN 115336402B
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- China
- Prior art keywords
- laminate
- frame
- polycarbonate
- photocurable compound
- substrate
- Prior art date
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(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
- C08F22/00—Homopolymers and 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
- C08F22/10—Esters
- C08F22/12—Esters of phenols or saturated alcohols
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K5/00—Casings, cabinets or drawers for electric apparatus
- H05K5/0017—Casings, cabinets or drawers for electric apparatus with operator interface units
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Casings For Electric Apparatus (AREA)
Abstract
The invention provides a laminate for a frame, which can satisfy steel wool resistance and low dielectric loss in a frequency band of 5GHz or more when used for a frame of a mobile phone or the like. A laminate for a frame, which is characterized by having a coating layer on a polycarbonate substrate or a substrate that is a composite plate composed of polymethyl methacrylate and polycarbonate and is used for the frame, and which satisfies the following conditions 1 and 2. Condition 1 the relation between the relative permittivity Dk and the dielectric loss tangent Df measured by the split dielectric resonator method in a frequency band of 5GHz or more satisfies the following expression.In condition 2, no flaw was visually observed after the steel wool #0000 was reciprocated 300 times on the coating layer with a load of 1.5kg/cm 2.
Description
Technical Field
The present invention relates to a laminate for a casing, which is used as a casing of a mobile communication device typified by a mobile phone and has excellent characteristics.
Background
In recent years, terminal devices excellent in portability, such as mobile phones, and tablet terminals with a communication function, have been widely used.
In communication devices, in order to cope with an increase in communication speed and data volume of transmission and reception signals, communication means in a high-frequency band region such as millimeter waves have been realized, and reduction of communication errors due to noise, dielectric loss, and the like in data transmission and reception signals has become an urgent issue.
In such communication equipment, metal and glass have been used so far, but metal has poor radio wave permeability, and high frequency radio waves are not easily reported by glass or the like. As a countermeasure for this, a plastic housing excellent in dielectric loss is expected to be used as the housing of the terminal device.
On the other hand, plastic housings have a disadvantage that the surface is easily scratched, and the appearance is inferior to that of glass housings or metal housings. Therefore, a method of providing a coating on the surface of the plastic frame is employed. Such coating is often performed using an acrylic resin, and is cured by irradiation with an active light to exhibit excellent surface hardness (steel wool resistance).
As a coating layer for a plastic frame, patent document 1 below proposes a method of transferring a functional hard coating layer so as to satisfy scratch resistance. In patent documents 2 to 4, the use of a silicon compound provides smoothness, releasability, flexibility (softness) and steel wool resistance due to stress relaxation.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2019-25739
Patent document 2 Japanese patent application 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
For the laminate as described above, it is generally required to improve steel wool resistance of the coating layer. On the other hand, in the case of a communication device, low dielectric loss is required in order to be suitable for communication in a high-frequency band region. Accordingly, an object of the present invention is to provide a laminate for a housing, which has steel wool resistance and low dielectric loss in a frequency band of 5GHz or more when used in a housing for a mobile phone or the like.
That is, the present invention relates to a laminate for a frame, which is characterized in that a polycarbonate substrate or a substrate as a composite plate composed of polymethyl methacrylate and polycarbonate has a coating layer thereon and is used for the frame, and the laminate satisfies the following conditions 1 and 2.
Condition 1 the relation between the relative permittivity Dk and the dielectric loss tangent Df measured by the split dielectric resonator method in a frequency band of 5GHz or more satisfies the following expression.
In condition 2, no flaw was visually observed after the steel wool #0000 was reciprocated 300 times on the coating layer with a load of 1.5kg/cm 2.
According to the present invention, a laminate for a frame having scratch resistance and low dielectric loss characteristics in a frequency band of 5GHz or more can be provided.
Detailed Description
The elements constituting the present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description unless departing from the gist thereof. In the present specification, the expression "to" is used as an expression including numerical values before and after the expression "to" and physical properties. In the present invention, when the expression "(meth) acryl" is used, it means one or both of "acryl" and "methacryl". The same applies to "(meth) acrylate", "(meth) acryl".
The laminate for a frame body of the present invention has a coating layer on a substrate, and the substrate is a polycarbonate substrate or a composite plate composed of polymethyl methacrylate and polycarbonate.
The dielectric loss of the laminate is obtained from the relative dielectric constant Dk, the dielectric loss tangent Df, and the frequency f of the signal by the following formula.
(K: constant, f: frequency of signal, df: dielectric loss tangent, dk: relative permittivity)
Therefore, for use in a high frequency region, it is necessary to addThe inhibition is lower. In the present invention, dk and Df measured by a separation medium resonator method in a frequency band of 5GHz or more,Preferably <0.015, more preferably <0.012. If it isEven in communication in a high frequency band, the present invention can be used as a laminate for a housing without any problem.
The dielectric resonator separation method is one of methods capable of measuring the relative dielectric constant Dk and the dielectric loss tangent Df in a frequency band of 1ghz to 20ghz with high accuracy. The present measurement is one type of resonance method, in which a space into which a substrate to be measured is inserted is provided in the center of a resonator, and the relative dielectric constant Dk and the dielectric loss tangent Df are measured by determining the resonance frequencies before and after insertion of the substrate to be measured into the space. The resonator used was an IEC-61189-based device.
The thickness of the polycarbonate substrate as the substrate of the present invention or the substrate as the composite plate composed of polymethyl methacrylate and polycarbonate is preferably 0.4mm to 2.0mm. This is because if the thickness of the supporting substrate is less than 0.4mm, the durability of the laminate may be problematic, and if it exceeds 2.0mm, the processability and transparency of the substrate may be problematic. The thickness of the base material also affects the dielectric characteristics, but if the thickness is within the range, the dielectric loss of the laminate for the frame body is affectedAnd not exceeding 0.02. Since the polycarbonate substrate has a low surface hardness, it is preferable to thicken the coating layer in order to achieve the desired steel wool resistance, but by using a composite board substrate composed of polymethyl methacrylate and polycarbonate having a high surface hardness, a laminated board excellent in steel wool resistance and impact resistance can be obtained even if the coating layer is thin.
Since the casing of a mobile communication device typified by a mobile phone is in contact with the outside, scratch resistance is required. As an evaluation thereof, steel wool resistance, specifically, #0000, was required to be observed visually after the steel wool was reciprocated 300 times with a load of 1.5kg/cm 2.
The coating layer is a cured product of the following photocurable resin composition. The photocurable resin composition forming the coating layer is preferably composed of (a) a photocurable compound, (b) a photopolymerization initiator, and (c) a solvent.
The photocurable compound of the component (a) preferably contains a photocurable polyfunctional monomer represented by the following formula (1) or (2) as an essential component.
By containing (1) and (2), the crosslinking density at the time of curing becomes high, and as a result, steel wool resistance can be satisfied. When (1) or (2) is not contained, the crosslinking density at the time of curing is insufficient, and it is not preferable because steel wool resistance is hardly satisfied.
(A) The molar number of the acryl groups per 100g of the photocurable compound of the component (A) is preferably in the range of 0.8 to 1.1, more preferably in the range of 0.9 to 1.1, and still more preferably in the range of 0.95 to 1.05. When the number of moles of the acryl is less than 0.8, the crosslinking density may be lowered, and the scratch resistance may be lowered. Conversely, if the amount is greater than 1.1, cracks due to excessive stress may be generated by shrinkage during curing, which may cause poor appearance.
The above-mentioned molar number of acryl per 100g represents the sum of the molar number of acryl (number of acryl functional groups/molecular weight g.mol -1) of each component per 100g of the photocurable compound.
(A) The photocurable compound of the component (a) preferably has at least 3 (meth) acryloyl groups in the molecule in an amount of 75% by mass or more. If it is less than 75wt%, the crosslink density decreases, and it is difficult to satisfy steel wool resistance.
Examples of the compound having 3 or more (meth) acryloyl 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, and tris (2-acryloyloxyethyl) isocyanurate.
(A) The molar number of hydroxyl groups per 100g of the photocurable compound of the component is preferably in the range of 0.06 to 0.20, preferably 0.07 to 0.15, more preferably 0.08 to 0.12. If the amount is not within this range, the elastic modulus may be lowered, and the desired steel wool resistance may not be obtained. On the other hand, even if the content exceeds this range, further improvement cannot be expected.
The above-mentioned number of moles of hydroxyl groups per 100g represents the sum of the number of hydroxyl groups (number of hydroxyl groups/molecular weight g. Mol -1) of each component per 100g of the photocurable compound.
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 of component (a) may contain 2 or less acrylic esters in the molecule in order to adjust the number of moles of the acryl groups and the number of moles of the hydroxy groups per 100 g.
Specific examples of the compound containing 2 or less 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, tetraethyleneglycol dimethacrylate, dicyclopentyl dimethylol di (meth) acrylate, and the like.
The photocurable compound of component (a) may contain urethane-modified (meth) acrylates and ethylene oxide-modified (meth) acrylates. They are effective in suppressing cracks generated by shrinkage upon curing.
Examples of the photopolymerization initiator (b) of the photocurable resin composition include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, etc., thioxanthones such as acetophenone, 2-diethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxy acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropane-1-one, etc., acetophenones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone, etc., thioxanthones such as 2, 4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc., ketals such as dimethyl ketal, benzil, etc., ketals such as benzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 4' -bis (4, 4' -methylbenzophenone), 2, 6-dimethylbenzoyl phosphine oxide, etc.
These components (b) may be used alone or as a mixture of 2 or more kinds, and may be further used in combination with a tertiary amine such as triethanolamine or methyldiethanolamine, a promoter such as a benzoic acid derivative such as ethyl N, N-dimethylaminobenzoate or isoamyl N, N-dimethylaminobenzoate, and the like.
The amount of the photopolymerization initiator used in the component (b) is preferably 0.1 to 20wt%, more preferably 1 to 10wt%, based on 100wt% of the total of the components (a). If the amount is not within this range, crosslinking may be insufficient, and the elastic modulus may be lowered, whereby the desired steel wool resistance may not be obtained. On the other hand, if the content exceeds this range, further improvement in the reaction rate may not be expected.
As the solvent of the component (c), known organic solvents such as aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester organic solvents such as ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate, alcohol organic solvents such as methanol, ethanol, n-propanol, isopropanol and n-butanol, and glycol ether organic solvents such as propylene glycol monomethyl ether can be used. Particularly preferably, the organic solvent contains a glycol.
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 monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and butoxypropanol, and among them, propylene glycol monomethyl ether is preferred.
The thickness of the coating layer is preferably 1 to 30 μm. More preferably 5 μm to 20 μm. If the particle diameter is less than 1. Mu.m, the effect of the supporting substrate is likely to be exerted, and the desired steel wool resistance may not be obtained. Conversely, if the amount exceeds this range, cracks due to excessive stress may be generated by shrinkage during curing, which may cause appearance defects. If the dielectric loss is within this range, the dielectric loss of the laminate for the frame is affectedAnd not exceeding 0.02.
Various additives may be added to the photocurable resin composition 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 resin composition can be cured by irradiation with ultraviolet rays having a wavelength of 10 to 400nm or visible rays having a wavelength of 400 to 700 nm. The wavelength of the light to be used is not particularly limited, and near ultraviolet rays having a wavelength of 200 to 400nm are particularly preferably used. Examples of the lamp used as the ultraviolet light generating source include a low-pressure mercury lamp (output: 0.4 to 4W/cm), a high-pressure mercury lamp (40 to 160W/cm), an ultra-high-pressure mercury lamp (173 to 435W/cm), and a metal halide lamp (80 to 160W/cm).
The method for obtaining a coating film by irradiation with light may be either an atmosphere in which oxygen is blocked or an atmosphere, and the composition of the present invention can impart a good coating even if it is polymerized and cured in an atmosphere. Examples thereof include casting, roll coating, bar coating, spray coating, air knife coating, spin coating, flow coating, curtain coating, and dipping. The film thickness of the coating film was adjusted by the solid content concentration in consideration of the film thickness of the molded film after drying and curing.
Examples
Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the following examples.
Reference example 1 production of photocurable resin composition A1 for coating film
The photo-curable resin composition for coating a film was obtained by mixing 60 parts by weight of dipentaerythritol hexaacrylate having mw= 578.57, number of acryl=6, and number of hydroxyl groups=0 (wherein 35% of dipentaerythritol pentaacrylate having mw= 524.52, number of acryl=5, and number of hydroxyl groups=1) (manufactured by co-company, product name DPHA), 8 parts by weight of pentaerythritol triacrylate having mw= 298.29, number of acryl=3, and number of hydroxyl groups=1 (wherein 40% of pentaerythritol tetraacrylate having mw= 352.34, number of acryl=4, and number of hydroxyl groups=0) (manufactured by co-company, LIGHT ACRYLATE PE-3A), 20 parts by weight of trimethylolpropane triacrylate having mw= 296.32, number of acryl=3, and number of hydroxyl groups=0 (manufactured by co-company, LIGHT ACRYLATE TMP-a), and further mixing 8 parts by weight of 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropane-1-one (IGM RESINS b.v. company, omni 907) as a photopolymerization initiator, and adjusting propylene glycol mono-rad as an organic solvent so that the solid content becomes 40%. In this composition A1, the molar number of the photocurable compound per 100g of hydroxyl groups was [ (1/524.52 ×0.35) ×0.6+ (1/298.29 ×0.6) ×0.2] ×100=0.08, with the molar number of the photocurable compound per 100g of the acryl groups being {[(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,. The ratio of the component (meth) acryloyl group to the component having three or more functions in the constituent components of the photocurable compound is 100%.
(Reference example 2 to 4 and comparative reference example 1 to 4)
The same procedure as in reference example 1 was followed except that the raw materials and the composition ratios shown in Table 1 were used, to obtain photocurable resin compositions A2 to A4 and B1 to B4 for coating films.
The other abbreviations in the table are as follows.
PE-4A pentaerythritol tetraacrylate, mw= 352.34, acryl number=4 (manufactured by Kabushiki Kaisha chemical Co., ltd.)
DCPA Dimethylol-tricyclodecane diacrylate, mw= 304.39, acryl number=2 (manufactured by Kabushiki Kaisha chemical Co., ltd.)
G201P 2-hydroxy-3-acryloxypropyl methacrylate, mw= 214.22, (meth) acryl number=2, hydroxyl number=1 (co-processed chemical Co., ltd.)
TMP-6EO-3A:6 EO-modified trimethylolpropane triacrylate, mw= 560.64, acryl number=3 (made by Kagrong chemical Co., ltd.)
EBECRYL210 aromatic urethane acrylate, mw=1500, acryl number=2 (DAICEL-ALLNEX Co., ltd.)
The sum of the number of moles of acryl groups per 100g of the photocurable compound=the number of moles of acryl groups per 100g of each component of the photocurable compound (number of acryl functional groups/molecular weight g.mol -1)
The sum of the hydroxyl numbers (hydroxyl numbers/molecular weights g.mol -1) of each component of the photocurable compound per 100g of the photocurable compound=the hydroxyl number of each 100g of the photocurable compound
(Examples 1 and 2) < production of laminate S1 and S2 for frame body)
The photocurable resin composition A1 was applied by spin coating to a polycarbonate substrate (thickness: 0.54mm, length: 10cm, width: 10cm,Escarbo Sheet Co.) so that the film thickness after drying became 10 μm (S1) and 20 μm (S2), and dried at 80℃for 5 minutes, and then cooled at room temperature for 5 minutes. Thereafter, films were formed at 2800mJ/cm 2 cumulative exposure (in 365 nm) under an oxygen atmosphere using a high-pressure mercury lamp of 2kW/cm 2, to obtain respective laminate S1 and S2 for a frame.
Example 9 and 10 < production of laminate for frame T1 and T2)
The photocurable resin composition A1 was applied by spin coating to the polymethyl methacrylate side of a composite plate (thickness: 650 μm, length: 10cm, width: 10cm,Escarbo Sheet company) composed of polymethyl methacrylate/polycarbonate so that the film thickness after drying became 10 μm (T1) and 20 μm (T2), dried at 80 ℃ for 5 minutes, and then cooled at room temperature for 5 minutes. Thereafter, films were formed at 2800mJ/cm 2 cumulative exposure (in 365 nm) under an oxygen atmosphere using a high-pressure mercury lamp of 2kW/cm 2, to obtain respective laminate for frame T1 and T2.
(Example 3. About.8)
< Production of laminate S3 to S8 >
Laminates S3 to S8 for the frame were produced in the same manner as in examples 1 and 2, except that the photocurable resin compositions A2 to A4 blended in the composition ratios shown in table 1 were used.
(Example 11 to 12)
< Production of laminate T3 to T4 >
Laminates T3 to T4 for the frame were produced in the same manner as in examples 9 and 10, except that the photocurable resin composition A2 blended in the composition ratio shown in table 1 was used.
Comparative examples 1,2 and 3
Comparative examples 1, 2 and 3 were respectively made of an uncoated diamond glass (reinforced product, manufactured by Corning corporation), an uncoated polycarbonate and an uncoated polymethyl methacrylate/polycarbonate composite plate.
(Comparative examples 4 to 11)
Laminates U1 to U8 for the frame were produced in the same manner as in examples 9 and 10, except that the photocurable resin compositions B1 to B4 blended in the composition ratios shown in table 1 were used.
< Evaluation >
The laminate S1 to S8 for a frame (examples), T1 to T4 (examples), an uncoated diamond glass, an uncoated polycarbonate, and an uncoated polymethyl methacrylate/polycarbonate composite plate (comparative example), and the laminate U1 to U8 for a frame (comparative example) obtained as described above were used for the following evaluation. The evaluation results are shown in tables 2 and 3.
< Steel wool resistance >
A steel wool #0000 was used and was subjected to reciprocating abrasion 300 times on the surface of the coating layer with a load of 1.5kg/cm 2 by a reciprocating abrasion tester (model: 30S, manufactured by HEIDON Co.). The presence or absence of the occurrence of the flaws was visually observed under a fluorescent lamp, and the number of flaws was evaluated based on the following criteria.
No flaw
Delta less than 10 flaws
X more than 10 flaws
< Dielectric loss tangent Df, relative permittivity Dk),>
For a sample which was allowed to stand at 23℃and 50% RH for 24hr or more, the dielectric loss tangent Df and the relative dielectric constant Dk at frequencies of 5GHz and 10GHz were measured by the split dielectric resonator method using a product name Network Analyzer E8363C manufactured by Agilent Technologies Co., ltd. Under an atmosphere of 23 ℃. Further, from the obtained values, calculation is performed
TABLE 1
Claims (5)
1. A laminate for a frame, characterized in that the laminate is used for a frame, the laminate comprising a polycarbonate substrate or a substrate as a composite sheet comprising polymethyl methacrylate and polycarbonate, and a coating layer which is a cured product of a photocurable resin composition comprising (a) a photocurable compound, (b) a photopolymerization initiator and (c) a solvent, the photocurable compound comprising, as essential components, a photocurable polyfunctional monomer represented by the following formula (1) or (2), the photocurable compound having a molar number of acryloyl groups per 100g of the photocurable compound of 0.8 to 1.1, the laminate satisfying the following conditions 1 and 2,
Condition 1 the relation between the relative permittivity Dk and the dielectric loss tangent Df measured by the split dielectric resonator method in a frequency band of 5GHz or more satisfies the following expression,
In condition 2, no flaw was visually observed after the steel wool #0000 was reciprocated 300 times on the coating layer with a load of 1.5kg/cm 2.
2. The laminate for a frame according to claim 1, wherein the thickness of the polycarbonate substrate or the substrate as a composite plate composed of polymethyl methacrylate and polycarbonate is 0.4 to 2.0mm.
3. The laminate for a frame according to claim 1 or 2, wherein 75 mass% or more of the photocurable compound has 3 or more (meth) acryloyl groups in a molecule.
4. The laminate for a frame according to claim 1 or 2, wherein the number of moles of hydroxyl groups per 100g of the photocurable compound is 0.06 to 0.2.
5. The laminate for a frame according to claim 1 or 2, wherein the thickness of the coating layer is 1 to 30 μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2020-049047 | 2020-03-19 | ||
| JP2020049047 | 2020-03-19 | ||
| PCT/JP2021/010750 WO2021187509A1 (en) | 2020-03-19 | 2021-03-17 | Housing laminate |
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| CN115336402A CN115336402A (en) | 2022-11-11 |
| CN115336402B true CN115336402B (en) | 2025-08-26 |
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| JP (1) | JP7597791B2 (en) |
| KR (1) | KR102878411B1 (en) |
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| CN108290970A (en) * | 2015-11-13 | 2018-07-17 | 株式会社德山 | Photocurable resin composition |
| CN109957321A (en) * | 2017-12-14 | 2019-07-02 | 日华化学株式会社 | The manufacturing method of laminated body, coating agent and laminated body |
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| JP5204459B2 (en) | 2007-10-17 | 2013-06-05 | 共栄社化学株式会社 | Method for producing curable resin component |
| JP4638954B2 (en) * | 2008-09-16 | 2011-02-23 | 日本ペイント株式会社 | Fingerprint-resistant photocurable composition and painted product provided with fingerprint-resistant coating layer |
| JP2013029828A (en) * | 2011-06-21 | 2013-02-07 | Mitsubishi Rayon Co Ltd | Light-transmitting molding and antireflection article using the same |
| TWI484013B (en) * | 2012-03-12 | 2015-05-11 | Showa Denko Kk | A polymerizable composition, a polymer, an image display device, and a method for manufacturing the same |
| JP2014097605A (en) * | 2012-11-14 | 2014-05-29 | Daicel Value Coating Ltd | Laminate sheet and production method of the same |
| HUE042057T2 (en) * | 2013-06-26 | 2019-06-28 | Momentive Performance Mat Gmbh | Method and Application of Coating Coating Composition for Light Crosslinking |
| US10189999B2 (en) * | 2014-03-31 | 2019-01-29 | Jnc Corporation | Resin composition for coating agent, molded article, and image display device |
| JP6330433B2 (en) * | 2014-03-31 | 2018-05-30 | Jnc株式会社 | Silicon compound, resin composition for coating agent, molded product, image display device |
| JP6638646B2 (en) | 2014-03-31 | 2020-01-29 | Jnc株式会社 | Silicon compound, resin composition for coating agent, molded product, image display device |
| JP6965186B2 (en) * | 2017-03-13 | 2021-11-10 | 三洋化成工業株式会社 | Photocurable resin composition |
| JP6950330B2 (en) | 2017-07-28 | 2021-10-13 | 東レ株式会社 | Laminated body and resin film |
| CN111936880B (en) | 2018-05-02 | 2024-01-02 | 三菱化学株式会社 | Millimeter wave radar cover and millimeter wave radar module equipped with the cover |
| JP7259220B2 (en) * | 2018-06-13 | 2023-04-18 | 株式会社レゾナック | Photosensitive resin composition, wiring layer and semiconductor device |
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| CN109957321A (en) * | 2017-12-14 | 2019-07-02 | 日华化学株式会社 | The manufacturing method of laminated body, coating agent and laminated body |
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