Antiblocking photocurable resin composition, antiblocking structure comprising substrate and antiblocking photocurable resin composition applied and cured thereon, and production method thereof
A technology of curing resin and anti-blocking, applied in the direction of coating, etc., can solve the problems of loss of photochemical properties, deterioration of coating film properties, and easy damage of coating film.
Inactive Publication Date: 2007-09-19
NIPPON PAINT CO LTD
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AI-Extracted Technical Summary
Problems solved by technology
When particles are mixed in, the thickness of the film needs to be thinned in order to form unevenness on the surface, the strength of the coating film is re...
In order to provide a technic for preventing problems such as conglutination (i.e., an adhering phenomena) between layers of a thermoplast film, the invention provides an anti-conglutination hardenable resin composition and application thereof, the composition includes a first component containing at least one or more resin, and a second component selected from at least one or more monomers or low-molecular polymers, wherein the resin of the first component are deposited by phase separation after applying the composition to form superfine non-flatness on surfaces.
- Experimental program(14)
- Comparison scheme(2)
 The preparation of the anti-blocking curable resin composition of the present invention includes mixing the first and second components, if necessary, together with a solvent, a polymerization initiator, a catalyst, a photosensitizer and/or a curing agent. The weight ratio of the first component: the second component in the anti-blocking curable resin composition is preferably 0.1:99.9 to 50:50, more preferably 0.3:99.7 to 20:80, still more preferably 0.5:99.5 to 10:90 . When a polymerization initiator, catalyst and/or photosensitizer is used, based on 100 parts by weight of the first and second components and other optional resins (here, the first and second components and other optional resins are referred to as "Resin component"), 0.01 to 20 parts by weight, preferably 1 to 10 parts by weight of these agents may be added. When a curing agent is used, 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight of the agent may be added based on 100 parts by weight of the resin component. When a solvent is used, 1 to 9900 parts by weight, preferably 10 to 900 parts by weight of the solvent may be added based on 100 parts by weight of the resin component.
The solvent in the anti-blocking curable resin composition of the present invention is not particularly limited, and is appropriately selected in consideration of the first and second components, the material of the substrate under the coating, the coating method of the composition, and the like. Specifically, examples of the solvent include aromatic solvents such as toluene, xylene; ketone-based solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxygen Hexacyclic, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenethyl ether; ester solvents such as ethyl acetate , butyl acetate, isopropyl acetate and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide and N-methylpyrrolidone; cellosolve solvents such as methyl cellosolve, Ethyl cellosolve and butyl cellosolve; alcoholic solvents such as methanol, ethanol and propanol; halogen solvents such as dichloromethane and chloroform; and the like. These solvents may be used alone or in combination of two or more. Among these solvents, ester-based solvents, ether-based solvents, alcohol-based solvents and ketone-based solvents are preferable.
 The anti-blocking curable resin composition of the present invention may contain any additives if necessary. The additives include conventional additives such as antistatic agents, plasticizers, surfactants, antioxidants, and ultraviolet absorbers.
 Anti-blocking hard coat film
 The anti-blocking curable resin composition of the present invention is cured into a film shape to obtain an anti-blocking hard coat film. Curing methods and curing conditions include those described in the anti-block laminate below.
 anti-block laminate
 The anti-blocking laminate member of the present invention, ie, a laminate, includes a resin base material layer and a coating film having fine unevenness. A coating film having fine unevenness can be formed by the above-described anti-blocking curable resin composition.
 The resin substrate of the layer includes various plastic films, plastic plates, and the like. Plastic films include, for example, triacetyl cellulose (TAC) films, polyethylene terephthalate (PET) films, diacetylenecellulose films, cellulose acetate butyrate films, polyethersulfone films, Polyacryl resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth)acrylonitrile film, etc. The thickness of the resin base material layer can be appropriately selected according to the application, and is generally about 25 to about 1000 μm.
 The coating film having the fine unevenness can be formed by applying the anti-blocking curable resin composition on the resin base material layer. The application method of the anti-blocking curable resin composition may be appropriately selected according to the anti-blocking curable resin composition and coating process conditions. Application can be by, for example, dip coating, air knife coating, curtain coating, roll coating, wire bar coating, gravure coating, extrusion coating (see USP 2681294), and the like way to implement.
 The thickness of the coating film with fine unevenness is not particularly limited and can be appropriately set in consideration of various factors. For example, the anti-blocking curable resin composition may be applied so that the thickness of the dry film is 0.01 to 20 μm.
 The coating film applied on the resin substrate layer may be subjected to phase separation at room temperature, or may be dried before curing, and phase separation may be performed in advance before curing. When the coating film is dried or heated before curing, phase separation can be performed in advance by drying the coating film at 30 to 200°C, more preferably 40 to 150°C for 0.01 to 30 minutes, more preferably 0.1 to 10 minutes. When the mixture of the first and second components is photocurable, drying the mixture before curing in order to perform phase separation in advance brings the advantage that the solvent can be effectively removed from the coating film having fine unevenness, And the unevenness of the desired size can be obtained.
 As another method of carrying out phase separation before curing, a method of carrying out phase separation by irradiating light on the coating film can also be used. For example, exposures of 0.1 to 3.5 J/cm can be used 2 , preferably 0.5 to 1.5 J/cm 2 irradiated light. The irradiation light is not particularly limited, but may include, for example, irradiation light having a wavelength of 360 nm or less, and the like. For example, when 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one is used as the photoinitiator, it is preferable to carry out the irradiation with light having a wavelength of about 310 nm as the irradiation light. For irradiation, it is more preferable to irradiate with light having a wavelength of about 360 nm as irradiation light. Such light can be obtained by a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like. Upon light irradiation, phase separation and curing can occur. There is an advantage that undesired irregularities on the surface, that is, white surface irregularities, which are generated due to surface irregularities caused by any solvent contained in the drying anti-blocking curable resin composition, can be Its occurrence is prevented by light irradiation carried out in order to effect the phase separation.
 The coating film having fine unevenness can be formed by curing a coating film obtainable by/by applying an anti-blocking curable resin composition or by curing a dried coating film. When the mixture of the first and second components is thermosetting, the mixture can be cured by heating at 40 to 280°C, more preferably 80 to 250°C, for 0.1 to 180 minutes, more preferably 1 to 60 minutes. When the mixture of the first and second components is photocurable, the mixture can be cured by light irradiation using a light source emitting light having a given wavelength as required. Light irradiation can also be used to effect phase separation as described above.
 Figure 1 is a schematic cross-sectional view of an anti-block laminate formed in accordance with the present method. An anti-blocking laminate (1) includes a coating film (3) having fine unevenness and a resin base material layer (5). Since the surface unevenness of the anti-blocking laminate of the present invention is naturally aligned, a desired unevenness shape can be formed on the surface of the resin layer.
 The roughness shape of the surface of the coating film having the fine roughness can be evaluated according to the parameter Rz JIS (ten points average roughness). Here, Rz JIS is a parameter defined in Table 1 of Annex 1 of JIS B0601. Rz JIS is an index representing the roughness height of the unevenness on the surface. Figure 2 is a schematic diagram of the parameter Rz JIS. The undulating curve in this figure shows the ridges of the coating film with fine irregularities. The ten-point average roughness (Rz JIS) can be measured in accordance with Annex 1 of JIS B0601 using, for example, an ultra-deep profile measuring microscope produced by Keyence Corporation or the like. Here, JIS B0601 is the Japan Industrial Standard corresponding to ISO 4287, which is a translation of ISO 4287 without changing the technical standard and representation.
 The anti-blocking laminate of the present invention preferably has an R of 0.1 μm or less a (arithmetic mean height). when R a When it exceeds 0.1 micrometer, since the haze value of a film increases, transparency falls. R a More preferably, it is 0.07 μm or less. The lower limit is preferably 0.01 μm.
 The anti-blocking laminate of the present invention preferably has an R of 0.5 μm or less z JIS. Here, R z JIS is ten points average roughness of a roughness curve, and is a parameter defined in JIS B0601-2001. R z The JIS is more preferably 0.3 μm or less, and still more preferably 0.2 μm or less. The lower limit is preferably 0.01 μm. In order to control the shape of unevenness, the anti-blocking laminate of the present invention may contain particles having an average particle diameter of 0.5 μm or less as an antiaggregation agent, which can prevent precipitation due to resin during phase separation resulting in aggregation. The particles are not used to create anti-blocking properties, and the particles do not produce sparkle. When the Rz JIS value (ten-point average roughness) of the anti-blocking laminate exceeds 0.5 μm, there is a disadvantage that white cloudiness occurs on the anti-blocking laminate, that is, white surface irregularities, the haze increases, and the Hence the loss of transparency.
 When the anti-blocking laminate of the present invention has transparency, the transparency is represented by total light transmittance and haze. The total light transmittance is 85% or more, preferably 90% or more, and the haze is 2.0% or less, preferably 1.8% or less, more preferably 1.5% or less. Total transmittance (T t (%)) according to the following formula from the measured incident light intensity (T 0 ) and the measured total transmitted light intensity (T 1 ) (ie, the intensity of light passing through the anti-block laminate). Figure 3 is a schematic diagram of total light transmittance.
 T t ( % ) = T 1 T 0 × 100
 The measurement of the total light transmittance can be achieved by a turbidity meter, for example, a turbidity meter manufactured by Suga Test Instruments Co., Ltd.
 According to the present invention, an anti-blocking hard coat film having excellent transparency properties can be produced which does not adversely affect the transparency of the substrate due to the reduced haze as described above.
 The turbidity can be calculated according to the following formula according to JIS K7105.
 H ( % ) = T d T t × 100
 H: turbidity (turbidity value) (%)
 T d : Diffusion transmittance (%)
 T t : Total light transmittance (%)
 The measurement of turbidity can be achieved by a turbidity meter, for example, a turbidity meter manufactured by Suga Test Instruments Co., Ltd.
 According to the anti-blocking laminate of the present invention, the arrangement of the desired non-uniform unevenness shape of the surface of the coating film having the fine unevenness is naturally determined.
 The anti-blocking laminate of the present invention exhibits anti-blocking properties when multiple resin substrate layers are used in the laminate. Various embodiments of the anti-block laminate are contemplated, but include, for example, rolls in which the resin substrate has been wound.
 One embodiment of such a roll material includes a roll material prepared according to a method comprising the steps of: applying the anti-blocking curable resin composition of the present invention to a layer of resinous substrate, curing the composition and rolling up the substrate.
 Although only a few exemplary embodiments of this invention have been described in detail above, those skilled in the art will readily appreciate modifications to these exemplary embodiments without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are included within the scope of the present invention.
 Preparation Example 1
 Preparation of Acryloyl Copolymer
 A mixture of 1263.6 grams of isobornyl methacrylate, 18.9 grams of methyl methacrylate and 67.5 grams of methacrylic acid was stirred. The mixture was added dropwise at a constant rate over 3 hours to 2430 g of propylene glycol monomethyl ether heated at 110°C under a nitrogen atmosphere in a 5000 ml reactor equipped with a stirring paddle, a nitrogen inlet tube, a condenser and dropping funnel, and then the mixture was reacted at 110°C for 30 minutes.
 A solution of 540 grams of propylene glycol monomethyl ether containing 67.5 grams of tert-butylperoxy-2-ethyl hexanoate was added dropwise over 30 minutes to give a number average molecular weight of 2700 and a weight average molecular weight Acryloyl copolymer of 5200. The resin had an SP value of 10.2 and a Tg of 113°C.
 Preparation Example 2
 Preparation of Acryloyl Copolymers Containing Unsaturated Double Bonds
 A mixture of 441.6 grams of isobornyl methacrylate, 8.4 grams of methyl methacrylate, 120 grams of ethylhexyl acrylate, and 30 grams of methacrylic acid was stirred. This mixture was added dropwise with a solution of 240.0 g of propylene glycol monomethyl ether containing 6.0 g of t-butylperoxy-2-ethyl hexanoate in a 5000 ml reactor at a constant rate over 3 hours and heated at 110 °C under nitrogen atmosphere. In heated 1080 g of propylene glycol monomethyl ether, the reactor was equipped with a stirring paddle, a nitrogen introduction tube, a condenser and a dropping funnel, and then the mixture was reacted at 110°C for 1 hour.
 Subsequently, a solution of 51 g of propylene glycol monomethyl ether containing 0.6 g of tert-butylperoxy-2-ethyl hexanoate was added dropwise, and the mixture was reacted at 110° C. for 30 minutes.
 A solution of 4.5 grams of tetrabutylammonium bromide and 0.17 grams of hydroquinone in 6 grams of propylene glycol monomethyl ether was added to the reaction mixture. A solution of 51.9 g of glycidyl methacrylate and 15.0 g of propylene glycol monomethyl ether was further added dropwise over one hour while air bubbling, and the mixture was further reacted for 5 hours.
 An unsaturated double bond-containing acryl copolymer was obtained with a number average molecular weight of 6700 and a weight average molecular weight of 15000. The resin had an SP value of 9.8 and a Tg of 55°C.
|Thickness||0.01 ~ 20.0||µm|
|The average particle size||<= 0.5||µm|
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