Classifications

• • 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
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • 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
  • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
  • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
• • 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
  • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/29—Laminated material
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
  • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
  • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
  • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
• • 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/536—Hardness
• • 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
  • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
  • B32B2309/08—Dimensions, e.g. volume
  • B32B2309/10—Dimensions, e.g. volume linear, e.g. length, distance, width
  • B32B2309/105—Thickness
• • 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
  • B32B2405/00—Adhesive articles, e.g. adhesive tapes
• • 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
  • B32B2457/00—Electrical equipment
  • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
  • B32B2457/208—Touch screens
• • G—PHYSICS
  • G06—COMPUTING; CALCULATING OR COUNTING
  • G06F—ELECTRIC DIGITAL DATA PROCESSING
  • G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
  • G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
  • G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices

Definitions

• the present invention relates to a laminate obtained by curing a photocurable composition to a transparent resin molded body, and more particularly, an antifouling function, and more particularly, excellent antifouling properties and transparency, scratch resistance,
• the present invention relates to a laminate that has excellent heat resistance and is useful as a protective sheet for display and a substrate for touch panel.
• glass has been widely used as a protective sheet for displays, and chemically tempered glass and ultrathin glass films are also used in addition to general blue plate glass having a thickness of about 0.5 to 1 mm.
• the protective sheet mentioned here is located on the outermost surface of a display such as a mobile phone or a personal computer, and plays a role of protecting internal devices. Such a protective sheet is sometimes referred to as a cover, window, or cover window.
• a protective sheet located on the outermost surface of the touch panel also serves as a protective sheet, it must be excellent in strength and scratch resistance.
• Such a protective sheet must be transparent, but some have a certain haze value from the viewpoint of antiglare effect, concealment of scratches and dirt, and / or slipperiness.
• a method of increasing the contact angle on the sheet surface using a fluorine-based material or a silicone-based material is generally used.
• a method of treating glass with a fluorinated alkyl group-containing silane coupling agent and a method of providing a cured film of a polysiloxane-containing urethane (meth) acrylate-based composition on the glass surface can be mentioned (see, for example, Patent Document 1). ).
• the former method has a problem in durability because only a thin fluorine film can be formed, and the latter method has a problem in adhesion between the glass and the cured film.
• a protective sheet made of plastic is also being used from the viewpoint of improving safety such as lightweight and thin display and resistance to cracking, and for the purpose of manufacturing flexible displays.
• PMMA polymethyl methacrylate
• PET polyethylene terephthalate
• these plastic protective sheets can satisfy various properties such as mechanical properties such as surface hardness and flexural modulus, thermal properties such as heat resistance, hygroscopicity, chemical and solvent resistance, and low retardation.
• mechanical properties such as surface hardness and flexural modulus
• thermal properties such as heat resistance, hygroscopicity, chemical and solvent resistance, and low retardation.
• the surface hardness even if a hard coat layer is provided on the surface of these plastic substrates, the hardness of the substrate itself is low, so that sufficient hardness as a protective sheet cannot be secured.
• a specific photopolymerizable composition is photocured.
• the resulting molded body can also be seen.
• a photopolymerizable composition comprising a polyfunctional urethane (meth) acrylate having an alicyclic structure and a polyfunctional (meth) acrylate having an alicyclic structure gives a resin molded article having high pencil hardness.
• the polymerizable composition gives a resin molded article having excellent optical properties and thermomechanical properties (see, for example, Patent Document 3), and a specific alicyclic skeleton bifunctional (meth) acrylate compound, specific An aliphatic tetrafunctional (meth) acrylate compound and a polyfunctional urethane (meth) acrylate compound having an alicyclic skeleton and a molecular weight of 200 to 2,000.
• Photopolymerizable composition it is disclosed to provide a resin molded product excellent in optical properties and thermomechanical properties (e.g., see Patent Document 4.).
• an object of the present invention is to provide a laminate having excellent antifouling property, high surface hardness and transparency under such a background.
• the resin molded body obtained by curing the photocurable composition has a contact angle with water obtained by curing the photocurable composition.
• the resin molded body and the cured resin layer have excellent adhesion, and accordingly, antifouling properties and excellent transparency, surface hardness, and scratch resistance.
• the gist of the present invention relates to a laminate in which a cured resin layer having a contact angle with water of 100 ° or more is formed on at least one surface of a resin molded body obtained by curing a photocurable composition. is there.
• a protective sheet for display and a touch panel using the laminate are also provided.
• antifouling agents such as fluorine-based materials and silicone-based materials that are generally used for photocured resin molded articles have adhesion problems, are difficult to use, and are photocured. Even if it was an antifouling layer, it was thought that it was difficult to use from the viewpoint of durability of adhesion, and surprisingly, it has excellent adhesion, and as described above, it has excellent antifouling property and transparency and The laminate had excellent surface hardness and scratch resistance.
• the reason why the adhesiveness is good as described above is not clear, but the photocurability that forms the surface of the base resin obtained by curing the photocurable composition and the cured resin layer having a contact angle of 100 ° or more. It is assumed that the composition has a high physical and / or chemical affinity.
• a laminate having excellent adhesion between the resin molded body and the cured resin layer, having excellent antifouling properties, and excellent transparency, surface hardness, and scratch resistance is obtained.
• (meth) acrylate is a generic term for acrylate and methacrylate
• (meth) acryl is a generic term for acrylic and methacrylic
• polyfunctional here means having two or more (meth) acryloyl groups in a molecule
• a cured resin layer [II] having a contact angle with water of 100 ° or more is formed on at least one surface of a resin molded product [I] obtained by curing the photocurable composition (i). Is a laminated body.
• the resin molding [I] is formed by curing the photocurable composition (i).
• photocurable composition (i) well-known compositions, such as an acrylic type, an epoxy type, a thiol / ene addition type
• a photocurable composition (i) it contains the following component (A1), (A2) and (A3), and adheres with the below-mentioned cured resin layer [II] used as an antifouling layer From the viewpoint of sex.
• A1 Polyfunctional urethane (meth) acrylate compound
• A2) Alicyclic skeleton-containing polyfunctional (meth) acrylate compound (A3) Photopolymerization initiator
• the polyfunctional urethane (meth) acrylate compound (A1) is polyfunctional, a crosslinked resin can be formed by curing, and a resin molded body having high surface hardness and heat resistance can be obtained. Moreover, since it has a urethane bond in a molecule
• the alicyclic skeleton-containing polyfunctional (meth) acrylate compound (A2) is polyfunctional, a crosslinked resin can be formed by curing, and a resin molded product having high surface hardness and heat resistance can be obtained. Moreover, since it has an alicyclic skeleton, the water absorption rate of the resin molded product can be reduced.
• the polyfunctional urethane (meth) acrylate compound (A1) is obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, and the polyisocyanate compound is not particularly limited.
• examples include polyisocyanates such as aliphatic, aliphatic and alicyclic, among which tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbo Polyisocyanates such as ene diisocyanate, 1,3-bis (isocyana
• alicyclic polyisocyanates such as hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and 1,3-bis (isocyanatomethyl) cyclohexane are preferable from the viewpoint that the water absorption of the resin molded product can be reduced.
• hydroxyl group-containing (meth) acrylate compound examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2 -Hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, caprolactone modified 2-hydroxyethyl (meth) acrylate , Pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified penta Risuri Tall tri (meth) acrylate, ethylene oxide-modified
• acrylate is preferable from the viewpoint of fast curing, and a carbon chain (carbon chain between a hydroxyl group and (meth) acryloyl) such as 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate is relatively short. A thing is more preferable at the point which can improve the bending elastic modulus of a resin molding.
• pentadecane di (meth) acrylate, bis (hydroxy) pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ]
• pentadecane acrylate methacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ]
• pentadecane di (meth) acrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 3,6 . 0 2,7 . 0 9,13 ]
• pentadecane di (meth) acrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 3,6 . 0 2,7 .
• Two or more kinds of the alicyclic skeleton-containing polyfunctional (meth) acrylate-based compound (A2) can be used in combination, or acrylate and methacrylate can be used in combination.
• the content of the polyfunctional urethane (meth) acrylate compound (A1) is preferably 5 to 50% by weight, particularly 8%, based on the total of the component (A1) and the component (A2). It is preferably -40% by weight, more preferably 10-30% by weight. If the content of the component (A1) is too small, the surface hardness of the resin molded product tends to decrease. Conversely, if the content is too large, the water absorption rate of the resin molded product tends to increase.
• the content of the alicyclic skeleton-containing polyfunctional (meth) acrylate compound (A2) is preferably 50 to 95% by weight, particularly with respect to the total of the component (A1) and the component (A2). It is preferably 60 to 92% by weight, more preferably 70 to 90% by weight. If the content of the component (A2) is too small, the water absorption rate of the resin molded product tends to increase. Conversely, if the content is too large, the surface hardness of the resin molded product tends to decrease.
• photopolymerization initiator (A3) known compounds can be used.
• radical cleavage type photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are preferable.
• These photopolymerization initiators (A3) may be used alone or in combination of two or more.
• the content of the photopolymerization initiator (A3) is 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, particularly with respect to 100 parts by weight in total of the components (A1) and (A2).
• the amount is preferably 0.3 to 3 parts by weight. If the content is too high, the retardation of the resin molded product tends to increase and yellowing tends to occur. If the content is too low, the polymerization rate decreases and the polymerization may not proceed sufficiently.
• the photocurable composition (i) used in the present invention may further contain a small amount of auxiliary components to such an extent that the surface hardness and heat resistance of the resin molded product [I] are not impaired.
• auxiliary components for example, the component (A1) And monomers having an ethylenically unsaturated bond other than (A2), chain transfer agent, antioxidant, ultraviolet absorber, thermal polymerization initiator, polymerization inhibitor, antifoaming agent, leveling agent, bluing agent , Dyes and pigments, and the like.
• Examples of the monomer having an ethylenically unsaturated bond other than components (A1) and (A2) include, for example, methyl methacrylate, 2-hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl Monofunctional (meth) acrylates such as (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, di (meth) acrylate of polyethylene glycol higher than tetraethylene glycol 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy-1,3-di (meth) acrylo Polyfunctional (meth) acrylates such as xylpropane,
• the content of the monomer having an ethylenically unsaturated bond other than components (A1) and (A2) is 30 parts by weight or less with respect to a total of 100 parts by weight of component (A1) and component (A2). It is preferably 20 parts by weight or less, particularly 10 parts by weight or less. When there is too much content, it exists in the tendency for the surface hardness and heat resistance of resin molding [I] to fall.
• a polyfunctional mercaptan compound is preferable.
• the polyfunctional mercaptan compound include pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, and the like.
• These polyfunctional mercaptan-based compounds are preferably used in a proportion of usually 10 parts by weight or less, more preferably 5 parts by weight or less, particularly with respect to 100 parts by weight of the total of component (A1) and component (A2). Is preferably 3 parts by weight or less. When there is too much this usage-amount, there exists a tendency for the surface hardness and rigidity of resin molding [I] obtained to fall.
• antioxidants examples include 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,4,6-tri-t-butylphenol, and 2,6-di- t-butyl-4-s-butylphenol, 2,6-di-t-butyl-4-hydroxymethylphenol, n-octadecyl- ⁇ - (4'-hydroxy-3 ', 5'-di-t-butylphenyl) ) Propionate, 2,6-di-t-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 2,4 -Bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-t-butylanilino) -1,3,5-triazine, 4,4-methylene-bis (2,6-di-)
• the content of the antioxidant is usually preferably 0.001 to 1 part by weight, particularly preferably 0.01 to 0.5 part by weight based on 100 parts by weight in total of the component (A1) and the component (A2). Parts by weight. If the amount of the antioxidant is too small, the heat resistance of the resin molded product [I] tends to be reduced, and if the amount is too large, the light transmittance tends to be reduced.
• the ultraviolet absorber is not particularly limited as long as it is soluble in the (meth) acrylate compound, and various ultraviolet absorbers can be used. Specific examples include salicylic acid ester, benzophenone, triazole, hydroxybenzoate, and cyanoacrylate. These ultraviolet absorbers may be used in combination. Among these, in terms of compatibility with (meth) acrylate compounds, benzophenone or triazole, specifically, (2-hydroxy-4-octyloxy-phenyl) -phenyl-methanone, 2-benzotriazole- UV absorbers such as 2-yl-4-t-octyl-phenol are preferred.
• the content of the ultraviolet absorber is usually preferably 0.001 to 1 part by weight, particularly preferably 0.01 to 0.1 part by weight based on 100 parts by weight in total of the component (A1) and the component (A2). Parts by weight. If the amount of the ultraviolet absorber is too small, the light resistance tends to decrease. If the amount is too large, it may take a long time to cure the photocurable composition, or sufficient curing may not be possible.
• thermal polymerization initiator known compounds can be used, such as hydroperoxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and the like.
• Hydroperoxides dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide, t-butyl peroxybenzoates, peroxyesters such as t-butylperoxy (2-ethylhexanoate), benzoyl
• peroxides such as diacyl peroxides such as peroxides, peroxycarbonates such as diisopropylperoxycarbonate, peroxyketals, and ketone peroxides.
• the photocurable composition (i) is cured to produce the resin molded product [I].
• the resin molded product [I] is produced by the following method.
• the photocurable composition (i) is provided on a flat mold or between two flat molds, and active energy rays, particularly ultraviolet rays having a wavelength of 200 to 400 nm, are formed from both sides or one side.
• active energy rays particularly ultraviolet rays having a wavelength of 200 to 400 nm
• Is preferably photocured in the range of 1 to 100 J / cm 2 of the irradiation light quantity.
• a more preferable range of the irradiation light amount is 5 to 70 J / cm 2 , and more preferably 10 to 50 J / cm 2 .
• Illuminance of ultraviolet radiation is typically 10 ⁇ 5000mW / cm 2, preferably 100 ⁇ 1000mW / cm 2. If the illuminance is too small, there is a tendency that the resin molded body is not sufficiently cured, and if the illuminance is too large, polymerization tends to run away and retardation tends to increase.
• the material of the mold is not particularly limited as long as at least one of the molds transmits the active energy ray, and glass, metal, or resin can be used. Among these, a glass or transparent resin mold is preferable in terms of translucency of active energy rays. When an opaque mold is used, a mold made of a transparent material is used for the mold on the opposite surface, and active energy rays are irradiated from the opposite surface side.
• irradiating with ultraviolet rays it is preferable to irradiate it by dividing it into a plurality of times because a resin molded product having a smaller retardation can be obtained.
• a method of irradiating about 1/100 to 1/10 of the total irradiation amount at the first time and irradiating a necessary remaining amount after the second time can be mentioned.
• Examples of the ultraviolet ray source include a metal halide lamp, a high pressure mercury lamp lamp, and an electrodeless mercury lamp.
• a filter that blocks infrared rays, a mirror that does not reflect infrared rays, or the like for the lamp.
• the resin molded body obtained in the present invention may be heat-treated for improving the degree of polymerization or releasing stress strain, and it is particularly preferable to heat-treat at 100 ° C. or higher.
• the thickness of the resin molded body [I] directly affects the rigidity of the protective sheet, and is preferably 0.1 to 3 mm. If the thickness is too thin, the internal device tends to be easily bent and it is difficult to protect the internal device. Conversely, if the thickness is too thick, it is difficult to reduce the weight of the entire display.
• a preferable range of the thickness is 0.2 to 2 mm, more preferably 0.3 to 1.5 mm, and particularly preferably 0.4 to 1 mm.
• the resin molded product [I] of the present invention preferably has a glass transition temperature of 100 ° C. or higher from the viewpoint of heat resistance. When the glass transition temperature is too low, undulation occurs or the hue tends to deteriorate.
• a preferable range of the glass transition temperature is 100 to 500 ° C, more preferably 150 to 400 ° C, and still more preferably 200 to 300 ° C.
• the method of controlling suitably the kind of photocurable composition (i) mentioned above, and content of a component is mentioned.
• an acrylate-based compound and a methacrylate-based compound are used in combination, and a larger amount of the methacrylate-based compound is blended in the mixing ratio.
• the resin molded body [I] of the present invention preferably has a pencil hardness of 3H or more from the viewpoint of surface hardness.
• the pencil hardness is more preferably 3H to 10H, particularly preferably 4H to 8H.
• a method of appropriately controlling the type of the above-described photopolymerizable composition (i) and the content of the components can be used.
• a polyfunctional urethane (meth) acrylate compound having 3 to 6 functional compounds may be used.
• the bending elastic modulus of the resin molding [I] of the present invention is 3 GPa or more. If the flexural modulus is too low, the rigidity tends to decrease.
• the flexural modulus is more preferably 3 to 5 GPa, still more preferably 3.5 to 4 GPa.
• a method of appropriately controlling the type of the photocurable composition (i) and the content of the components described above can be used.
• the polyfunctional urethane (meth) acrylate compound (A1) may be a trifunctional to hexafunctional compound.
• the resin molded product [I] of the present invention usually has a total light transmittance of preferably 80% or more, particularly preferably 85% or more, and more preferably 90% or more.
• a cured resin layer [II] having a contact angle with water of 100 ° or more is formed on at least one surface of the resin molded body [I]. It is the biggest feature to do.
• the contact angle with water is preferably 100 to 150 °, more preferably 105 to 140 °, and particularly preferably 110 to 120 ° from the viewpoint of the antifouling function. If the contact angle is too small, the antifouling property is lowered. If the contact angle is too large, the adhesion to the substrate (specifically, the resin molded product [I] or the cured resin layer [III] described later) tends to decrease.
• the cured resin layer [II] if the contact angle is 100 ° or more, for example, a known material such as a fluorine-based material or a silicone-based material may be used for photocuring, but in particular, the following component (B1) , (B2) and (B3) are preferably cured from the photocurable composition (ii) in terms of adhesion to the resin molded body.
• B1 Polysiloxane structure-containing urethane (meth) acrylate compound
• B3 Reactive fluorine-containing compound represented by the following general formula (1)
• R1, R2, R3 and R4 each independently represents a hydrogen atom or a methyl group.
• X 1 is an alkylene group
• X 2 is an arylene group
• X 3 is a substituent represented by the following general formula (2) or (3)
• X 4 is an alkylene group or an oxyalkylene group
• X 5 is an alkylene group
• X 6 is a hydrogen atom or an ester bond residue.
• a and b are each an integer of 1 to 30, and c and d are each an integer of 0 to 60 (however, the bonding order of the structural units is arbitrary).
• the said polysiloxane structure containing urethane (meth) acrylate type compound (B1) should just contain a polysiloxane structure in the structure, Especially in one end shown by following General formula (4).
• a (meth) acrylate compound (B1-2) is preferred.
• the said polysiloxane structure containing urethane (meth) acrylate type compound (B1) may have a structure site
• R 1 represents an alkyl group
• R 2 independently represents an alkyl group, a cycloalkyl group or a phenyl group
• R 3 represents a hydrocarbon group or an organic group containing an oxygen atom.
• a is an integer of 1 or more
• b is an integer of 1 to 3.
• R 1 and R 3 represent a hydrocarbon group or an organic group containing an oxygen atom
• R 2 independently represents an alkyl group, a cycloalkyl group or a phenyl group, and a is an integer of 1 or more, b and c are integers of 1 to 3.
• the urethane (meth) acrylate compound (B1-1) includes a polysiloxane compound (x1) having a hydroxyl group at one end represented by the general formula (4), a polyisocyanate compound (x2), and a hydroxyl group-containing compound.
• a (meth) acrylate compound (x3) and, if necessary, a polyol compound (x4) are further reacted.
• R 1 in the general formula (4) is an alkyl group, and the alkyl group preferably has a relatively small carbon number. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
• R 2 in the general formula (4) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
• the alkyl group preferably has a relatively small carbon number. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
• the carbon number of the cycloalkyl group is usually 3 to 10, preferably 5 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a norbornyl group.
• the alkyl group, cycloalkyl group, and phenyl group may have a substituent.
• substituent usually include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group.
• the substituent has a carbon atom, the carbon atom is not included in the number of carbons defined in the description of R 2 above.
• R 3 in the general formula (4) is a hydrocarbon group or an organic group containing an oxygen atom.
• the hydrocarbon group usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and examples thereof include divalent or trivalent hydrocarbon groups.
• Examples of the divalent hydrocarbon group include an alkylene group.
• the alkylene group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.
• Examples of the organic group containing an oxygen atom include an oxyalkylene group and a polyoxyalkylene group.
• a in the general formula (4) is an integer of 1 or more, preferably 5 to 200, particularly preferably an integer of 5 to 120.
• b is an integer of 1 to 3, and preferably an integer of 1 to 2.
• the weight average molecular weight of the polysiloxane compound (x1) used in the present invention is usually preferably 100 to 50,000, particularly 500 to 10,000, and more preferably 1,000 to 10,000. It is preferable. When the weight average molecular weight is too small, the antifouling performance tends to be lowered, and when it is too large, the hardness and scratch resistance of the cured resin layer (hereinafter sometimes referred to as “coating film”) tend to be lowered.
• polysiloxane compound (x1) represented by the general formula (4) include, for example, “X-22-170BX”, “X-22-170DX”, “X-22-2” manufactured by Shin-Etsu Chemical Co., Ltd. 176DX “,” X-22-176F “,” Silaplane FM-0411 “,” Silaplane FM-0421 “,” Silaplane FM-0425 “,” Silaplane FM-DA11 “,” Silaplane “manufactured by Chisso Corporation Products such as “FM-DA21” and “Silaplane FM-DA26”.
• polyisocyanate compound (x2) used in the present invention examples include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate.
• Aromatic polyisocyanates hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate and other aliphatic polyisocyanates, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1 , 3-bis Alicyclic polyisocyanates such as natomethyl) cyclohexane, trimer compounds or multimeric compounds of these polyisocyanates, allophanate polyisocyanates, burette polyisocyanates, water-dispersed polyisocyanates (for example, manufactured by Nippon Polyurethane Industry Co., Ltd.) "Aquanate 100", “Aquanate 110", “Aquanate 200", “Aquanate 210", etc.).
• isocyanate compound having 3 or more isocyanate groups in one molecule in particular, a polyisocyanate trimer or multimer compound, and the film hardness, scratch resistance, solvent resistance, and bleed. It is more preferable in that the amount of unreacted low molecular weight components that cause the above can be reduced.
• Examples of the hydroxyl group-containing (meth) acrylate compound (x3) used in the present invention include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone modified 2 -Hydroxyethyl (meth) acrylate, dipropylene glycol (meth) acrylate, fatty acid modified-glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene Cole mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acryl
• pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are preferable in that a coating film having high hardness can be obtained.
• a polyol compound (x4) may be used as long as the effects of the present invention are not impaired.
• the polyol compound (x4) include polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, (meth) acrylic polyols, and the like.
• polyether polyols examples include polyether polyols containing alkylene structures such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, and polyhexamethylene glycol, and random or block copolymers of these polyalkylene glycols. Is mentioned.
• polyester-based polyol examples include a condensation polymer of a polyhydric alcohol and a polycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polycarboxylic acid, and a cyclic ester. And reactants.
• the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene diol, 1,3-tetramethylene diol, 2-methyl-1,3-trimethyl.
• Methylene diol 1,5-pentamethylene diol, neopentyl glycol, 1,6-hexamethylene diol, 3-methyl-1,5-pentamethylene diol, 2,4-diethyl-1,5-pentamethylene diol, glycerin , Trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).
• cyclohexanediols such as 1,4-cyclohexanediol
• bisphenols such as bisphenol A
• sugar alcohols such as xylitol and sorbitol
• polyvalent carboxylic acid examples include aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid; -Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid, trimellitic acid, and the like.
• cyclic ester examples include propiolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
• the weight average molecular weight of the polyol compound (x4) is preferably 50 to 8000, particularly preferably 50 to 5000, and further preferably 600 to 3000. If the weight-average molecular weight of the polyol compound (x4) is too large, mechanical properties such as coating film hardness tend to decrease during curing, and if it is too small, curing shrinkage tends to be large and stability tends to decrease.
• the urethane (meth) acrylate compound (B1-1) preferably has one or more ethylenically unsaturated groups, and has three or more ethylenically unsaturated groups in terms of hardness of the cured coating film. It is particularly preferable that it has one, and further preferably one having 6 or more ethylenically unsaturated groups.
• the upper limit of the ethylenically unsaturated group contained in the urethane (meth) acrylate compound (B1-1) is usually 30 and preferably 25 or less.
• the method for producing the urethane (meth) acrylate compound (B1-1) is not particularly limited.
• the polyisocyanate compound (x3) After reacting the hydroxyl group of the polysiloxane compound (x1) with the isocyanate group of the polyisocyanate compound (x2) under the condition that the isocyanate group remains, the polyisocyanate compound ( The residual isocyanate group of x2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (x3).
• the reaction molar ratio between the polysiloxane compound (x1) and the polyisocyanate compound (x2) is, for example, two isocyanate groups of the polyisocyanate compound (x2), and a hydroxyl group-containing (meth) acrylate compound (x3).
• the number of hydroxyl groups is one
• the polysiloxane compound (x1): the polyisocyanate compound (x2) is approximately 0.001 to 1: 1
• the polyisocyanate compound (x2) has three isocyanate groups.
• the polysiloxane compound (x1): polyisocyanate compound (x2) may be about 0.001 to 2: 1.
• the weight of the structural portion derived from the polysiloxane compound (x1) contained in 100 parts by weight of the urethane (meth) acrylate compound (B1-1) is 0.1 to 80 within the above molar ratio range. It is preferable that it is a weight part.
• a catalyst for the purpose of accelerating the reaction.
• a catalyst include organic metal compounds such as dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, zinc octoate, Metal salts such as stannous octoate, cobalt naphthenate, stannous chloride, stannous chloride, triethylamine, benzyldiethylamine, 1,4-diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4 , 0] undecene, amine catalysts such as N, N, N ′, N′-tetramethyl-1,3-butanediamine, N-ethylmorpholine, bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc.
• organic bismuth compounds such as dibutyl bismuth dilaurate and dioctyl bismuth dilaurate, and 2-ethyl Bismuth xanthate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth Examples include bismuth-based catalysts such as bismuth salts of organic acids, such as bismuth decanoate, bismuth disalicylate, and bismuth digallate. Undecene is preferred.
• an organic solvent having no functional group that reacts with an isocyanate group for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene
• esters such as ethyl acetate and butyl acetate
• ketones such as methyl ethyl ketone and methyl isobutyl ketone
• aromatics such as toluene and xylene
• the reaction temperature of such a reaction is usually 30 to 100 ° C., preferably 40 to 90 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
• the weight average molecular weight of the urethane (meth) acrylate compound (B1-1) thus obtained is preferably 500 to 50,000, and more preferably 500 to 30,000. If the weight average molecular weight is too small, the curing shrinkage tends to be large, and the physical properties such as hardness and scratch resistance of the cured resin layer tend to decrease, and if it is too large, the viscosity tends to be high and the handling property tends to decrease.
• the above-mentioned weight average molecular weight is a weight average molecular weight in terms of standard polystyrene molecular weight, and the column: Shodex GPC KF-806L (shown by Shoden GPC system-11 type, manufactured by Showa Denko KK) Exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plate / piece, filler material: styrene-divinylbenzene copolymer, filler particle size: 10 ⁇ m) Measured by using this series.
• the measurement of the weight average molecular weight of the urethane (meth) acrylate compound described later is measured according to the above method.
• the viscosity of the urethane (meth) acrylate compound (B1-1) at 60 ° C. is preferably 500 to 150,000 mPa ⁇ s, particularly 500 to 120,000 mPa ⁇ s, more preferably 1000 to 100,000 mPa ⁇ s. It is preferable that it is s. When the viscosity is out of the above range, the coatability tends to be lowered. The viscosity is measured with an E-type viscometer.
• the urethane (meth) acrylate compound (B1-1) may be used alone or in combination of two or more.
• R 1 and R 3 represent a hydrocarbon group or an organic group containing an oxygen atom
• R 2 independently represents an alkyl group, a cycloalkyl group or a phenyl group, and a is an integer of 1 or more, b and c are integers of 1 to 3.
• the urethane (meth) acrylate compound (B1-2) includes a polysiloxane compound (y1) having hydroxyl groups at both ends represented by the general formula (5), a polyisocyanate compound (y2), and a hydroxyl group-containing compound.
• the (meth) acrylate compound (y3) is further reacted with a polyol compound (y4) as necessary.
• R 1, R 3 in the general formula (5) is an organic group containing a hydrocarbon group or an oxygen atom.
• the hydrocarbon group usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and examples thereof include divalent or trivalent hydrocarbon groups.
• Examples of the divalent hydrocarbon group include an alkylene group.
• the alkylene group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a tetramethylene group.
• Examples of the organic group containing an oxygen atom include an oxyalkylene group and a polyoxyalkylene group.
• R 2 in the general formula (5) is each independently an alkyl group, a cycloalkyl group, or a phenyl group.
• the alkyl group preferably has a relatively small carbon number. Specifically, it usually has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
• the carbon number of the cycloalkyl group is usually 3 to 10, preferably 5 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a norbornyl group.
• the alkyl group, cycloalkyl group, and phenyl group may have a substituent.
• substituent usually include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group.
• the substituent has a carbon atom, the carbon atom is not included in the number of carbons defined in the description of R 2 above.
• a in the general formula (5) is an integer of 1 or more, preferably 5 to 200, particularly preferably an integer of 5 to 120.
• b and c are integers of 1 to 3, preferably integers of 1 to 2.
• the weight average molecular weight of the polysiloxane compound (y1) is usually preferably 100 to 50,000, particularly 500 to 10,000, and more preferably 1,000 to 10,000. If the weight average molecular weight is too small, the antifouling performance tends to decrease, and if it is too large, the transparency and scratch resistance tend to decrease.
• polysiloxane compound (y1) examples include “X-22-160AS”, “KF-6001”, “KF-6002”, “KF-6003” manufactured by Shin-Etsu Chemical Co., Ltd., “ Examples of such products include Sailor Plane FM-4411, Silaplane FM-4421, Silaplane FM-4425, and Macromonomer HK-20 manufactured by Toagosei Co., Ltd.
• polyisocyanate compound (y2) examples include those exemplified as the polyisocyanate compound (x2) in the description of the urethane (meth) acrylate compound (B1-1).
• Examples of the hydroxyl group-containing (meth) acrylate compound (y3) include those exemplified as the hydroxyl group-containing (meth) acrylate compound (x3) in the description of the urethane (meth) acrylate compound (B1-1). The same thing is mentioned.
• a polyol compound (y4) may be used as long as the effects of the present invention are not impaired.
• the polyol compound (x4) The thing similar to what was illustrated as is mentioned.
• the urethane (meth) acrylate compound (B1-2) preferably has 2 or more ethylenically unsaturated groups, and has 4 or more ethylenically unsaturated groups in terms of the hardness of the cured resin layer. It is particularly preferable that it has one, and further preferably one having 6 or more ethylenically unsaturated groups. Further, the upper limit of the ethylenically unsaturated group contained in the urethane (meth) acrylate compound (B1-2) is usually 30 and preferably 25 or less.
• the method for producing the urethane (meth) acrylate compound (B1-2) is not particularly limited.
• the polyisocyanate compound (y2) After reacting the hydroxyl group of the polysiloxane compound (y1) with the isocyanate group of the polyisocyanate compound (y2) under the condition that the isocyanate group remains, the polyisocyanate compound ( The residual isocyanate group of y2) is reacted with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (y3).
• the reaction molar ratio between the polysiloxane compound (y1) and the polyisocyanate compound (y2) is, for example, that the polyisocyanate compound (y2) has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound (y3).
• the number of hydroxyl groups is one
• the polysiloxane compound (y1): the polyisocyanate compound (y2) is about 0.001 to 1: 1
• the polyisocyanate compound (y2) has three isocyanate groups.
• the polysiloxane compound (y1): polyisocyanate compound (y2) may be about 0.001 to 2: 1.
• the weight of the structural portion derived from the polysiloxane compound (y1) contained in 100 parts by weight of the urethane (meth) acrylate compound (B1-2) is 0.1 to 80 weights within the above molar ratio range. Part.
• a catalyst for the purpose of accelerating the reaction, and examples of the catalyst include the same as described above.
• an organic solvent having no functional group that reacts with an isocyanate group for example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and xylene
• esters such as ethyl acetate and butyl acetate
• ketones such as methyl ethyl ketone and methyl isobutyl ketone
• aromatics such as toluene and xylene
• the reaction temperature of such a reaction is usually 30 to 100 ° C., preferably 40 to 90 ° C., and the reaction time is usually 2 to 10 hours, preferably 3 to 8 hours.
• the weight average molecular weight of the urethane (meth) acrylate compound (B1-2) thus obtained is usually preferably 500 to 50,000, and more preferably 500 to 30,000. If the weight average molecular weight is too small, curing shrinkage tends to be large, and physical properties such as hardness and scratch resistance of the cured resin layer tend to be lowered. If too large, the viscosity tends to be high and handling properties tend to be lowered.
• the viscosity of the urethane (meth) acrylate compound (B1-2) at 60 ° C. is preferably 500 to 150,000 mPa ⁇ s, particularly 500 to 120,000 mPa ⁇ s, more preferably 1000 to 100,000 mPa ⁇ s. It is preferable that it is s. When the viscosity is out of the above range, the coatability tends to be lowered. The viscosity is measured with an E-type viscometer.
• the urethane (meth) acrylate compound (B1-2) may be used alone or in combination of two or more.
• the polysiloxane structure-containing urethane (meth) acrylate compound (B1) it is preferable to use the urethane (meth) acrylate compound (B1-1) and / or the urethane (meth) acrylate compound (B1-2). However, it is particularly preferable to use the urethane (meth) acrylate compound (B1-1) in terms of excellent antifouling performance.
• the urethane (meth) acrylate compounds (B1-1) and (B1-2) are used in combination, the urethane (meth) acrylate compound (B1-1) and the urethane (meth) acrylate compound (B1-).
• R1, R2, R3 and R4 each independently represents a hydrogen atom or a methyl group.
• X 1 is an alkylene group
• X 2 is an arylene group
• X 3 is a substituent represented by the following general formula (2) or (3)
• X 4 is an alkylene group or an oxyalkylene group
• X 5 is an alkylene group
• X 6 is a hydrogen atom or an ester bond residue.
• a and b are each an integer of 1 to 30, and c and d are each an integer of 0 to 60 (however, the bonding order of the structural units is arbitrary).
• the reactive fluorine-containing compound (B2) represented by the general formula (1) contains a fluorine atom-containing structural moiety represented by X 3 and a (meth) acryloyl group in its structure.
• X 3 fluorine atom-containing structural moiety represented by X 3
• a (meth) acryloyl group in its structure.
• X 4 is an oxyalkylene group
• compatibility with the urethane (meth) acrylate compound (B1) is particularly improved, which is preferable.
• R1 to R4 are each independently a hydrogen atom or a methyl group.
• X 1 in the general formula (1) is an alkylene group, and the number of carbon atoms of the alkylene group is usually 1 to 12, preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.
• X 2 in the general formula (1) is an arylene group, and the carbon number of the arylene group is usually 6 to 12, preferably 6. Specific examples include a phenylene group and a naphthylene group.
• X 3 in the general formula (1) is a fluorine atom-containing substituent represented by the following general formula (2) or (3).
• the reactive fluorine-containing compound (B2) when a is 2 or more, it may include both of the substituents represented by the general formulas (2) and (3), or include only one of them. It may be a thing.
• X 4 in the general formula (1) is an alkylene group or an oxyalkylene group.
• the number of carbon atoms of the alkylene group is usually 1 to 12, preferably 1 to 8, and particularly preferably 1 to 4.
• Specific examples include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.
• oxyalkylene group it may be a structure represented by the following general formula (7).
• n is a polyoxyalkylene group of 2 or more, it may be a homopolymer of the same oxyalkylene chain or different.
• the oxyalkylene chain may be random or block copolymerized.
• Y is an alkylene group, and n is an integer of 1 or more.
• Y in the general formula (7) is an alkylene group, and the number of carbon atoms of the alkylene group is usually 1 to 12, preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.
• n is an integer of 1 or more, preferably 1 to 30, particularly preferably 2 to 20, and more preferably 5 to 15.
• X 5 in the general formula (1) is an alkylene group, and the carbon number of the alkylene group is usually 1 to 12, preferably 1 to 8, and particularly preferably 1 to 4. Specific examples include a methylene group, an ethylene group, a propylene group, and a tetramethylene group.
• X 6 in the general formula (1) is a hydrogen atom or an ester bond residue.
• the ester bond residue include a monovalent saturated hydrocarbon group or an aryl group.
• the monovalent saturated hydrocarbon group include those having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Specifically, linear alkyl groups such as methyl group and ethyl group, branched alkyl groups such as isooctyl group and 2-ethylhexyl group, alicyclic alkyl groups such as cyclohexyl group, isobornyl group and dicyclopentanyl group, etc. Can be mentioned.
• aryl group examples include those having usually 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms. Specific examples include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, and a naphthyl group.
• X 1 , X 2 , X 4 , X 5 and X 6 may have a substituent.
• the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an amino group, a mercapto group, Examples thereof include a sulfanyl group, a vinyl group, an acryloxy group, a methacryloxy group, an aryl group, and a heteroaryl group.
• the carbon atom shall not be included in the number of carbons defined in the above description of X 1 , X 2 , X 4 , X 5 , X 6. .
• a and b are each an integer of 1 to 30, and c and d are each an integer of 0 to 60. Furthermore, The ratio of a to (b + c + d) is preferably 0.1 ⁇ a / (b + c + d) ⁇ 10, particularly preferably 0.1 ⁇ a / (b + c + d) ⁇ 8, The ratio of c to (b + c) is preferably 0 ⁇ c / (b + c) ⁇ 0.95, particularly preferably 0 ⁇ c / (b + c) ⁇ 0.9, The ratio of d to (a + b + c) is preferably 0 ⁇ d / (a + b + c) ⁇ 5, particularly preferably 0 ⁇ d / (a + b + c) ⁇ 3.
• each structural site enclosed by [] in the general formula (1) may be the same structure or different structures. May be repeated.
• the weight average molecular weight of the reactive fluorine-containing compound (B2) is usually 1,000 to 100,000, preferably 2,500 to 40,000, particularly preferably 3,000 to 30,000.
• the method for producing the reactive fluorine-containing compound (B2) may be in accordance with a known general method for producing a fluorine-containing compound, for example, according to the method described in JP 2010-47680 A.
• the content of the reactive fluorine-containing compound (B2) is preferably 0.5 to 500 parts by weight, particularly preferably 2 to 100 parts by weight of the polysiloxane structure-containing urethane (meth) acrylate compound (B1). Up to 200 parts by weight, more preferably 5 to 100 parts by weight. If the content is too large, the compatibility is lowered and phase separation tends to occur or the cured resin layer tends to become cloudy. If the content is too small, the antifouling performance tends to be insufficient.
• an ethylenically unsaturated compound [provided that (B1) and (B2) Excluding] (B4) is preferable from the viewpoint of excellent hardness and scratch resistance of the cured resin layer.
• the content of the ethylenically unsaturated compound (B4) is preferably 0 to 99% by weight, particularly preferably 25 to 98% by weight, based on the total of the components (B1), (B2) and (B4). In particular, it is preferably 50 to 97% by weight, more preferably 75 to 96% by weight.
• it is preferably 50 to 97% by weight, more preferably 75 to 96% by weight.
• the ethylenically unsaturated compound (B4) is preferably, for example, a urethane (meth) acrylate compound (B4-1) and / or an ethylenically unsaturated monomer (B4-2).
• the urethane (meth) acrylate compound (B4-1) represented by the following general formula (6) was used for various applications. In particular, it is preferable in that the required physical properties are easily provided.
• R 1 is a urethane bond residue of a polyvalent isocyanate compound
• R 2 is a urethane bond residue of a hydroxyl group-containing (meth) acrylate compound
• a is an integer of 2 to 50.
• the urethane (meth) acrylate compound (B4-1-1) represented by the general formula (6) is obtained by reacting a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound.
• a in the general formula (6) may be an integer of 2 to 50, preferably 2 to 20, particularly preferably 2 to 10.
• polyisocyanate compound (x2) examples of such a polyisocyanate compound are the same as those exemplified as the polyisocyanate compound (x2) in the description of the urethane (meth) acrylate compound (B1-1), or a polyisocyanate compound. What reacted the compound (x2) and the polyol type compound (x4) is mentioned.
• hydroxyl group-containing (meth) acrylate compound examples are the same as those exemplified as the hydroxyl group-containing (meth) acrylate compound (x3) in the description of the urethane (meth) acrylate compound (B1-1). Can be mentioned.
• the method for producing the urethane (meth) acrylate compound (B4-1-1) may be produced in accordance with a known method for producing a urethane (meth) acrylate compound.
• a known method for producing a urethane (meth) acrylate compound For example, the same thing as the said polyisocyanate type compound (x2) and the same thing as a hydroxyl-containing (meth) acrylate type compound (x3) should just be charged to a reactor collectively or made to react.
• the reaction molar ratio between the polyisocyanate compound and the hydroxyl group-containing (meth) acrylate compound is, for example, that the polyisocyanate compound has two isocyanate groups and the hydroxyl group-containing (meth) acrylate compound has one hydroxyl group.
• the polyisocyanate compound: hydroxyl group-containing (meth) acrylate compound is about 1: 2 to 3
• the polyisocyanate compound has three isocyanate groups
• the hydroxyl group-containing (meth) acrylate compound has hydroxyl groups.
• polyisocyanate compound: hydroxyl group-containing (meth) acrylate compound is about 1: 3 to 4.
• the number of ethylenically unsaturated groups contained in the urethane (meth) acrylate compound (B4-1-1) obtained above is preferably 2 to 30, particularly preferably 3 to 20, and still more preferably. Is 6-15. If the number of ethylenically unsaturated groups is too small, there is a tendency that the hardness and scratch resistance of the coating film cannot be obtained. If the number is too large, the curing shrinkage of the coating film increases and the substrate adhesion decreases, There is a tendency to become brittle.
• the weight average molecular weight of the urethane (meth) acrylate compound (B4-1) is preferably 700 to 50,000, more preferably 800 to 30,000, and particularly preferably 1000 to 10,000. If the weight average molecular weight is too small, it tends to be difficult to maintain a balance between the hardness and shrinkage resistance of the cured resin layer, and the wettability to the substrate tends to decrease, and the weight average molecular weight is large. If it is too high, it tends to be difficult to maintain scratch resistance and hardness when a bi- or trifunctional polyfunctional oligomer is used.
• the viscosity of the urethane (meth) acrylate compound (B4-1) at 60 ° C. is preferably 200 to 150,000 mPa ⁇ s, particularly 500 to 120,000 mPa ⁇ s, more preferably 500 to 100,000 mPa ⁇ s. It is preferable that it is s. When the viscosity is out of the above range, the coatability tends to be lowered. The viscosity is measured with an E-type viscometer.
• the ethylenically unsaturated monomer (B4-2) is an ethylenically unsaturated monomer having one or more ethylenically unsaturated groups in one molecule (excluding urethane (meth) acrylate compounds (B4-1)
• a monofunctional monomer a bifunctional monomer, or a trifunctional or higher monomer.
• the monofunctional monomer may be any monomer containing one ethylenically unsaturated group.
• Michael adduct of acrylic acid or 2-acryloyloxyethyl dicarboxylic acid monoester examples include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer. Methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer and the like.
• 2-acryloyloxyethyl dicarboxylic acid monoester which is a carboxylic acid having a specific substituent include 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, and 2-acryloyloxyethyl.
• Examples thereof include phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, and 2-methacryloyloxyethyl hexahydrophthalic acid monoester. Furthermore, oligoester acrylate is also mentioned.
• the bifunctional monomer may be any monomer containing two ethylenically unsaturated groups.
• the tri- or higher functional monomer may be any monomer containing three or more ethylenically unsaturated groups.
• ethylenically unsaturated monomers may be used alone or in combination of two or more.
• the ethylenically unsaturated monomer (B4-2) is preferably a monomer containing two or more ethylenically unsaturated groups, and more preferably an ethylenically unsaturated group from the viewpoint of obtaining a high-hardness coating film. It is a monomer containing 3 or more.
• pentaerythritol tri (meth) acrylate pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate to obtain a hardened cured resin layer. Therefore, it is preferable.
• a photoinitiator (B3) can further be contained.
• the photopolymerization initiator (B3) include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2 -Hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Acetophenones such as morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomers; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl Ether etc.
• auxiliary agents include triethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid.
• Ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Etc. can be used in combination.
• the content of the photopolymerization initiator (B3) is such that the polysiloxane structure-containing urethane (meth) acrylate compound (B1), the reactive fluorine-containing compound (B2), and the ethylenically unsaturated compound (
• the amount is preferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight with respect to 100 parts by weight of the total of B4). If the content is too small, the curing rate in the case of ultraviolet curing tends to be extremely slow, and if too large, the curability is not improved and is inefficient.
• fillers in addition to the components (B1) to (B4), fillers, electrolyte salts, dyes and pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, emulsifiers, gelling agents. , Stabilizers, antifoaming agents, leveling agents, thixotropy imparting agents, antioxidants, flame retardants, fillers, reinforcing agents, matting agents, crosslinking agents, and the like can also be blended.
• unsaturated polyester resins vinyl urethane resins, vinyl ester urethane resins, polyisocyanates, polyepoxides, acrylic resins, alkyd resins, urea resins, melamine resins for the purpose of suppressing the curing shrinkage of the coating film
• Polymers such as polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters, saturated polyethers, and cellulose derivatives such as nitrocellulose and cellulose acetate butyrate may be blended.
• the polysiloxane structure-containing urethane (meth) acrylate compound (B1) of the present invention, the reactive fluorine-containing compound (B2) represented by the general formula (1), the photopolymerization initiator (B3), preferably further ethylenic A photocurable composition (ii) containing the unsaturated compound (B4) is obtained.
• Such a photocurable composition (ii) can be used after blending an organic solvent and adjusting the viscosity, if necessary, and is usually diluted to 10 to 70% by weight, preferably 20 to 60% by weight. And can be applied to a substrate.
• organic solvents examples include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene Aromatic glycols such as propylene glycol monomethyl ether, acetates such as ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents may be used alone or in combination of two or more.
• the organic solvent may be added to the above mixture, or the respective compositions may be dissolved in the organic solvent and then mixed.
• the method of adding (B3) at the end after blending (B1), (B2), and (B4) is preferably used.
• the photocurable composition (ii) is applied to at least one side of the resin molded product [I] (when the composition diluted with an organic solvent is applied, the photocurable composition (ii) is further dried. And then cured as a cured resin layer [II] by irradiation with active energy rays.
• the coating method is not particularly limited, and examples thereof include wet coating methods such as spray, shower, dipping, roll, spin, screen printing, and the like.
• the cured film thickness of the cured resin layer [II] is usually preferably 1 to 50 ⁇ m, particularly preferably 3 to 30 ⁇ m.
• active energy rays for example, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X-rays and ⁇ rays, electron beams, proton rays, neutron rays and the like can be used. Curing by ultraviolet irradiation is advantageous because of the availability of the irradiation device and the price.
• a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm an ultra high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless lamp, and the like are used. Irradiation of about / cm 2 is sufficient. After the ultraviolet irradiation, heating can be performed as necessary to complete the curing. Thus, the cured resin layer [II] is formed on at least one surface of the resin molding [I].
• the photocurable composition (iii) containing the following components (C1), (C2) and (C3) is cured between the resin molded body [I] and the cured resin layer [II]. It is preferable that the cured resin layer [III] is formed from the viewpoint of improving the adhesion between the resin molded body [I] and the cured resin layer [II].
• the acrylic resin (C1) in the present invention is obtained by polymerizing a monomer component containing a (meth) acrylic monomer, and can be used alone or in combination of two or more.
• the acrylic resin (C1) preferably contains, as a polymerization component, a (meth) acrylic acid ester monomer (c1) as a main component, and if necessary, a functional group-containing monomer (c2) and other copolymers.
• the polymerizable monomer (c3) can also be used as a copolymerization component.
• Examples of the (meth) acrylic acid ester monomer (c1) include, for example, aliphatic (meth) acrylic acid ester monomers such as (meth) acrylic acid alkyl ester, and aromatic monomers such as (meth) acrylic acid phenyl ester. Examples include (meth) acrylic acid ester monomers.
• Examples of such aliphatic (meth) acrylate monomers include alkyl (meth) acrylates in which the alkyl group generally has 1 to 12, particularly preferably 1 to 10, and more preferably 1 to 8 carbon atoms. Examples thereof include esters and (meth) acrylic acid esters having an alicyclic structure.
• (meth) acrylic acid alkyl ester examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth).
• n-propyl (meth) acrylate n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) Examples include acrylate and stearyl (meth) acrylate.
• Specific examples of the (meth) acrylic acid ester having an alicyclic structure include cyclohexyl (meth) acrylate and isobornyl (meth) acrylate.
• aromatic (meth) acrylic acid ester monomers examples include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyldiethylene glycol (meth) acrylate, and 2-hydroxy-3-phenoxypropyl.
• aromatic (meth) acrylic acid ester monomers include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenyldiethylene glycol (meth) acrylate, and 2-hydroxy-3-phenoxypropyl.
• examples include (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol-polypropylene glycol- (meth) acrylate, and nonylphenol ethylene oxide adduct (meth) acrylate.
• (meth) acrylic acid ester monomer examples include tetrahydrofurfuryl (meth) acrylate. These can be used alone or in combination of two or more.
• methyl (meth) acrylate, n-butyl (meth) acrylate are excellent in copolymerizability and coating film strength, easy to handle and easy to obtain raw materials.
• Acrylate and isobornyl (meth) acrylate are preferably used, and methyl (meth) acrylate is particularly preferable.
• Examples of the functional group-containing monomer (c2) include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an alkoxy group or phenoxy group-containing monomer, an amide group-containing monomer, an amino group-containing monomer, a nitrogen-containing monomer, a glycidyl group-containing monomer, and phosphoric acid. Examples thereof include a group-containing monomer and a sulfonic acid group-containing monomer. These can be used alone or in combination of two or more.
• hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters, caprolactone-modified 2-hydroxyethyl (meth) acrylate and the like Primary hydroxyl group-containing monomers such as caprolactone-modified monomers, 2-acryloyloxyethyl-2-hydroxyethylphthalic acid, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc.
• polyethylene glycol derivatives such as diethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate
• polypropylene glycol derivatives such as polypropylene glycol mono (meth) acrylate, polyethylene glycol-polypropylene glycol-mono (meth) acrylate
• poly (ethylene Oxyalkylene-modified monomers such as glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate may be used.
• carboxyl group-containing monomer examples include acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, fumaric acid, acrylamide-N-glycolic acid, cinnamic acid, and (meth) acrylic acid Michael.
• Additives eg, acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer, etc.
• 2- (meth) acryloyloxyethyl dicarboxylic acid monoester eg, 2-acryloyloxy
• Ethyl succinic acid monoester 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxyethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hex Hydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid mono ester
• Such a carboxyl group-containing monomer may be used as an acid, or may be used in the form of a salt neutralized with an alkali.
• alkoxy group-containing monomer examples include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and 2-butoxydiethylene glycol.
• Examples of the amide group-containing monomer include acrylamide, methacrylamide, N- (n-butoxyalkyl) acrylamide, N- (n-butoxyalkyl) methacrylamide, N, N-dimethyl (meth) acrylamide, N, N- Examples include diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, acrylamide-3-methylbutylmethylamine, dimethylaminoalkylacrylamide, and dimethylaminoalkylmethacrylamide.
• amino group-containing monomer examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and a quaternized product thereof.
• nitrogen-containing monomer examples include acryloyl morpholine.
• Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
• Examples of the phosphate group-containing monomer include 2- (meth) acryloyloxyethyl acid phosphate, bis (2- (meth) acryloyloxyethyl) acid phosphate, for example, a phosphate ester of polyethylene glycol monomethacrylate (for example, Rhodia "Sipomer PAM100" and “Sipomer PAM4000” manufactured by Hua Co., Ltd., phosphate ester of polyethylene glycol monoacrylate (for example, "Sipomer PAM5000” manufactured by Rhodia Nikka Co., Ltd.), and phosphate ester of polypropylene glycol monomethacrylate (for example, Rhodia Nikka Co., Ltd.
• a phosphate ester of polyethylene glycol monomethacrylate for example, Rhodia "Sipomer PAM100" and "Sipomer PAM4000” manufactured by Hua Co., Ltd.
• phosphate ester of polyethylene glycol monoacrylate for example, "
• Polypropylene glycol monoacrylate phosphate ester for example, Rhodia Nikka Co., Ltd.
• Polypropylene glycol monoacrylate phosphate ester for example, Rhodia Nikka Co., Ltd.
• Polypropylene glycol mono (meth) acrylate such as methylene phosphate (meth) acrylate, trimethylene phosphate (meth) acrylate, propylene phosphate (meth) acrylate, tetraphosphate phosphate
• alkylene phosphate (meth) acrylates such as methylene (meth) acrylate.
• sulfonic acid group-containing monomer examples include olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid, and methallyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, and salts thereof. .
• These functional group-containing monomers (c2) can be used alone or in combination of two or more.
• Examples of other copolymerizable monomer (c3) include acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether, vinyl toluene, Examples thereof include vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl ester, fumaric acid dialkyl ester, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinylketone.
• ethylene glycol di (meth) acrylate For the purpose of increasing the molecular weight, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate
• a compound having two or more ethylenically unsaturated groups such as divinylbenzene can also be used in combination.
• the content ratio of the (meth) acrylic acid ester monomer (c1), the functional group-containing monomer (c2), and the other copolymerizable monomer (c3) is (meth) acrylic acid ester monomer (C1) is preferably 10 to 100% by weight, particularly preferably 20 to 95% by weight, and the functional group-containing monomer (c2) is preferably 0 to 90% by weight, particularly preferably 5 to 80% by weight, and other copolymerizable properties.
• the monomer (c3) is preferably 0 to 50% by weight, particularly preferably 0 to 40% by weight.
• the acrylic resin (C1) in the present invention is preferably a polymer comprising a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms as a polymerization component, and particularly methyl (meth) acrylate is polymerized. It is preferably a polymer as a component, more preferably a polymer having methyl metallate as a polymerization component, and particularly preferably polymethyl methacrylate from the viewpoint of excellent strength of the cured resin layer. .
• acrylic resin (C1) For the polymerization of the acrylic resin (C1), conventionally known methods such as solution radical polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization can be employed.
• a polymerization monomer such as the (meth) acrylic acid ester monomer (c1), a functional group-containing monomer (c2), other copolymerizable monomer (c3), a polymerization initiator (azobisisobutyrate) Ronitrile, azobisisovaleronitrile, benzoyl peroxide, etc.
• a polymerization initiator azobisisobutyrate
• Ronitrile azobisisovaleronitrile
• benzoyl peroxide etc.
• the glass transition temperature (Tg) of the acrylic resin (C1) is usually 0 to 180 ° C., preferably 15 to 175 ° C., particularly preferably 50 to 130 ° C. If the glass transition temperature is too high, the effect of alleviating the thermal shrinkage of the cured product tends to decrease, and if it is too low, the thermal durability of the cured product tends to decrease.
• the weight average molecular weight of the acrylic resin (C1) thus obtained is usually 10,000 to 500,000, preferably 10,000 to 100,000. If the weight average molecular weight is too large, the strength of the cured resin layer tends to decrease. If the weight average molecular weight is too small, adhesion to various substrates such as a glass substrate and a plastic substrate and coating film appearance tend to decrease. .
• the degree of dispersion (weight average molecular weight / number average molecular weight) of the acrylic resin (C1) is usually 1 to 4, preferably 1.5 to 2.5.
• said weight average molecular weight and number average molecular weight are based on standard polystyrene molecular weight conversion, a column is added to a high performance liquid chromatography (Nippon Waters company, "Waters2695 (main body)” and “Waters2414 (detector)”). : ShodexGPCKF-806L (exclusion limit molecular weight: 2 ⁇ 10 7 , separation range: 100 to 2 ⁇ 10 7 , theoretical plate number: 10,000 plates / piece, filler material: styrene-divinylbenzene copolymer, filler particle size : 10 ⁇ m), and the degree of dispersion is determined from the weight average molecular weight and the number average molecular weight.
• the glass transition temperature is calculated from the Fox equation.
• the unsaturated compound (C2) containing two or more ethylenically unsaturated groups (hereinafter sometimes referred to as “polyfunctional unsaturated compound (C2)”) is an ethylenically unsaturated group in one molecule. It contains at least 2 saturated groups, preferably 2-15, particularly preferably 3-6, and excludes the phosphate group-containing ethylenically unsaturated compound (C4) described later.
• a polyfunctional unsaturated compound (C2) can be used individually by 1 type or in combination of 2 or more types. For example, bifunctional monomers, trifunctional or higher monomers, urethane (meth) acrylate compounds, epoxy (meth) acrylate compounds, polyester (meth) acrylate compounds, and the like can be used.
• the bifunctional monomer is a monomer containing two ethylenically unsaturated groups.
• the trifunctional or higher monomer is a monomer containing three or more ethylenically unsaturated groups, such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate.
• the urethane (meth) acrylate compound is a (meth) acrylate compound having a urethane bond in the molecule, and a (meth) acrylic compound containing a hydroxyl group and a polyisocyanate compound (if necessary, a polyol compound ) are obtained by a known general method, and those having a weight average molecular weight of usually 300 to 50,000 are mentioned.
• the polyfunctional unsaturated compound (C2) in the present invention is preferably pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Particularly preferred is a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate in terms of excellent coating strength.
• the content of the polyfunctional unsaturated compound (C2) is usually 10 to 900 parts by weight and 10 to 500 parts by weight with respect to 100 parts by weight (in terms of solid content) of the acrylic resin (C1). It is preferably 15 to 300 parts by weight, more preferably 20 to 150 parts by weight, particularly preferably 30 to 100 parts by weight.
• a polyfunctional unsaturated compound (C2) there exists a tendency for adhesiveness with resin molding [I] to fall, and when too small, there exists a tendency for the intensity
• benzyl dimethyl ketal 1-hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1- It is preferable to use phenylpropan-1-one.
• the content of the photopolymerization initiator (C3) is 0.1 to 20 parts by weight when the total of the component (C2) and the component (C4) described later is 100 parts by weight (in terms of solid content). It is preferably 1 to 18 parts by weight, particularly preferably 2 to 15 parts by weight. If the content of the photopolymerization initiator (C3) is too small, curing tends to be poor, and if it is too much, mechanical properties such as hardness tend to decrease, and embrittlement and coloring problems tend to occur. There is.
• the addition of the phosphoric acid group-containing ethylenically unsaturated compound (C4) as the photocurable composition (iii) further improves the adhesion to the resin molded product [I].
• the photocurable composition (iii) further improves the adhesion to the resin molded product [I].
• the phosphate group-containing ethylenically unsaturated compound (C4) in the present invention contains one or more phosphate groups, preferably 1 to 5 in one molecule, and one or more ethylenically unsaturated groups, An unsaturated compound containing 1 to 3 is preferable.
• a phosphoric acid group containing ethylenically unsaturated compound (C4) can be used individually by 1 type or in combination of 2 or more types.
• Examples of the phosphoric acid group-containing ethylenically unsaturated compound (C4) include 2-acryloyloxyethyl acid phosphate (for example, “Light Acrylate P-1A” manufactured by Kyoeisha Chemical Co., Ltd.), bis (2-acryloyloxyethyl), etc.
• Acid phosphate for example, “light acrylate P-2A” manufactured by Kyoeisha Chemical Co., Ltd.
• 2-methacryloyloxyethyl acid phosphate for example, “light ester P-1M” manufactured by Kyoeisha Chemical Co., Ltd.
• bis (2-methacryloyloxy, etc.) Ethyl) acid phosphate for example, “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd., “EM39” manufactured by Eternal Chemical Co., Ltd., “KAYAMER PM-2” manufactured by Nippon Kayaku Co., Ltd.
• 6-hexanolide of 2-hydroxyethyl methacrylate Reaction of adducts with phosphoric anhydride Composition for example, “KAYAMER PM-21” manufactured by Nippon Kayaku Co., Ltd.
• trisacryloyloxyethyl phosphate for example, “Biscoat # 3PA” manufactured by Osaka Organic Chemical Industry Co., Ltd
• “Biscoat # 3PMA”) polyethylene glycol monomethacrylate phosphoric acid ester (eg, “Sipomer PAM100” and “Sipomer PAM4000” manufactured by Rhodia Nikka Co., Ltd.), polyethylene glycol monoacrylate phosphoric acid Esters (for example, “Sipomer PAM5000” manufactured by Rhodia Nikka Co., Ltd.), phosphate esters of polypropylene glycol monomethacrylate (for example, “Sipomer PAM manufactured by Rhodia Nikka Co., Ltd.) 00 ”and the like, and polyalkylene glycol mono (meth) acrylate phosphate esters such as polypropylene glycol monoacrylate phosphate esters (eg,“ Sipomer PAM300 ”manufactured by Rhodia Nikka Co., Ltd.), methylene phosphate (meth) Examples thereof include alkylene phosphate (meth) acrylates such as acrylate, trimethylene phosphate (me
• phosphonic acid group-containing monoethylene such as vinylphosphonic acid, dimethylvinylphosphonic acid, diethylvinylphosphonic acid, diisopropylvinylphosphonic acid, diisobutylvinylphosphonic acid, dibutylvinylphosphonic acid, phenylvinylphosphonic acid, p-vinylbenzenephosphonic acid, etc.
• Unsaturated compounds divinylphosphonic acid, bis (diethylvinyl) phosphonic acid, bis (dimethylvinyl) phosphonic acid, bis (diisopropylvinyl) phosphonic acid, (diisobutylvinyl) phosphonic acid, (dibutylvinyl) phosphonic acid, bis (phenyl) And phosphonic acid group-containing diethylenically unsaturated compounds such as vinyl) phosphonic acid.
• These vinyl compounds can be used alone or in combination of two or more.
• the phosphoric acid group-containing ethylenically unsaturated compound (C4) is preferably bis (2- (meth) acryloyloxyethyl) acid phosphate or 2- (meth) acryloyloxyethyl acid phosphate. Seeds can be used in combination.
• the content of the phosphoric acid group-containing ethylenically unsaturated compound (C4) is usually 0.1 to 30 parts by weight with respect to 100 parts by weight (in terms of solid content) of the acrylic resin (C1).
• the amount is preferably 20 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, and further preferably 1 to 5 parts by weight. If the content of the phosphoric acid group-containing ethylenically unsaturated compound (C4) is too large, the substrate adhesion to the resin molded product [I] and the strength of the cured resin layer tend to decrease. There is a tendency for adhesion to decrease.
• the photocurable composition (iii) used in the present invention comprises the acrylic resin (C1), the polyfunctional unsaturated compound (C2), the photopolymerization initiator (C3), preferably a phosphate group-containing ethylenic unsaturated.
• a silane coupling agent (C5) can be further contained.
• silane coupling agent (C5) examples include an epoxy group-containing silane coupling agent, a (meth) acryloyl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a hydroxyl group-containing silane coupling agent, and a carboxyl group-containing silane.
• a coupling agent, an amino group-containing silane coupling agent, an amide group-containing silane coupling agent, an isocyanate group-containing silane coupling agent, and the like can be mentioned.
• a (meth) acryloyl group-containing silane coupling agent is preferable. These can be used alone or in combination of two or more.
• the content of the silane coupling agent (C5) is usually 0.1 to 30 parts by weight with respect to 100 parts by weight (converted to solid content) of the acrylic resin (A), and 0.1 to 20 parts by weight. It is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight. If the content of the silane coupling agent (C5) is too large, the strength and appearance of the cured resin layer tend to be lowered, and if too small, the substrate adhesion to the resin molded product [I] tends to be lowered. .
• the photocurable composition (iii) used in the present invention further includes a filler, an electrolyte salt, a dye / pigment, an oil, a plasticizer, a wax, a desiccant, a dispersant, a wetting agent, an emulsifier, a gelling agent, and a stabilizer.
• a filler an electrolyte salt, a dye / pigment, an oil, a plasticizer, a wax, a desiccant, a dispersant, a wetting agent, an emulsifier, a gelling agent, and a stabilizer.
• a metal salt such as a lithium salt, a conductive filler such as a metal oxide, a conductive polymer, an antistatic agent, and the like may be included.
• the photocurable composition (iii) used in the present invention does not contain inorganic fine particles such as silica, the transparency of the cured resin layer, and the stability and compatibility of the photocurable composition (iii). Is preferable.
• the photocurable composition (iii) used in the present invention can contain an organic solvent and adjust the viscosity as necessary.
• organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone, cellosolves such as ethyl cellosolve, toluene, xylene And the like, glycol ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, acetates such as ethyl acetate and butyl acetate, and diacetone alcohol. These organic solvents can be used alone or in combination of two or more.
• a combination of acetates such as ethyl acetate and butyl acetate, a combination of acetates such as ethyl acetate and butyl acetate and an aromatic such as toluene, methyl ethyl ketone and methyl isobutyl ketone
• ketones such as methanol and propyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol and propyl alcohol, and aromatics such as toluene are included in the cured resin layer. It is preferable in terms of appearance.
• the photocurable composition (iii) used in the present invention can be applied usually diluted to 10 to 60% by weight, preferably 20 to 40% by weight, using the organic solvent.
• the acrylic resin (C1) the polyfunctional unsaturated compound (C2), the photopolymerization initiator (C3), preferably a phosphoric acid group-containing ethylenic unsaturated
• Various methods can be employed for mixing the compound (C4) and the silane coupling agent (C5).
• acrylic resin (C1) and polyfunctional unsaturated compound (C2) After mixing acrylic resin (C1) and polyfunctional unsaturated compound (C2), adding phosphoric acid group-containing ethylenically unsaturated compound (C4), adding silane coupling agent (C5), and finally The method of adding a photoinitiator (C3) is mentioned,
• the solution which dissolved acrylic resin (C1) and polyfunctional unsaturated compound (C2) in organic solvents, such as ethyl acetate and toluene is prepared, A method of mixing with a phosphoric acid group-containing ethylenically unsaturated compound (C4) dissolved in an organic solvent and further mixing a silane coupling agent (C5) and a photopolymerization initiator (C3) in this order is employed.
• the photocurable composition (iii) after the photocurable composition (iii) is applied to the resin molded body [I], it can be cured by irradiation with active energy rays, and the resin molded body [I] A cured resin layer [III] is formed thereon. And said cured resin layer [II] will be formed on cured resin layer [III], and resin molding [I] and cured resin layer [II] will be strengthened.
• the photocurable composition (ii) is applied and cured on the cured resin layer [II].
• the cured resin layer [II] can be formed according to the method for forming the cured resin layer [II] on the resin molded body [I].
• Examples of the coating method include wet coating methods such as spraying, showering, dipping, flow coating, gravure coating, roll, spin, and screen printing.
• rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and ⁇ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of easy availability and price.
• a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm
• an ultrahigh pressure mercury lamp a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc.
• a method of irradiating about 30 to 3000 mJ / cm 2 can be mentioned. After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.
• the cured film thickness of the cured resin layer [III] is usually preferably 1 to 30 ⁇ m, and particularly preferably 2 to 20 ⁇ m.
• the heat shrinkage of the cured resin layer [III] increases in a durability test that requires a large heat load such as a boiling water immersion test, and the adhesion to the substrate tends to decrease.
• the desired surface hardness as an ultraviolet cured film cannot be obtained.
• a laminated body in which is formed is obtained.
• the pencil hardness of the surface of the cured resin layer [II] of the laminate of the present invention is preferably 3H or more from the viewpoint of the durability of the protective sheet.
• the pencil hardness is more preferably 3H to 10H, particularly preferably 4H to 8H. In adjusting such a pencil within the above range, a method of appropriately controlling the type of the above-described cured resin layer [II] and the blending amount of the components can be used.
• the laminate of the present invention can be formed as a protective sheet with an adhesive layer by forming an adhesive layer on one side.
• the material of the pressure-sensitive adhesive layer is not particularly limited, and an acrylic or silicone pressure-sensitive adhesive is appropriately used.
• the laminate of the present invention can be formed as a touch panel by forming a transparent conductive film on one side.
• the material of the transparent electrode is not particularly limited, and examples thereof include inorganic conductive films such as ITO and IGZO, and organic conductive films such as PEDOT.
• the surface resistance value of the transparent conductive film is preferably 1000 ⁇ / ⁇ or less, more preferably 10 to 900 ⁇ / ⁇ or less, and still more preferably 200 to 800 ⁇ / ⁇ or less. If the surface resistance is too high, the conductivity tends to be insufficient.
• Antifouling property (ink wiping property) A line was drawn with blue magic ink on the surface of the resin molded body, and after standing for 24 hours, the appearance after wiping with a waste cloth was visually observed and evaluated as follows. ⁇ ⁇ ⁇ ⁇ Can be wiped clean ⁇ ⁇ ⁇ ⁇ While it can be wiped off, the trace of the line remains ⁇ ⁇ ⁇ ⁇ Cannot be wiped off (ink repellency) A line was drawn with blue magic ink on the surface of the resin molding, and the mark of the magic ink was visually observed and evaluated as follows. ⁇ ... Repels ink and the traces of the lines are dotted. ⁇ ... Repels ink and the traces of the lines become thin.
• a photocurable composition (i) is poured at 23 ° C. into a mold using two optical polishing glasses facing each other and a silicon plate having a thickness of 0.2 mm as a spacer, and a metal halide lamp is used from both sides. Ultraviolet rays were irradiated with a light amount of 20 J / cm 2 .
• the resin sheet obtained by demolding was heated in a vacuum oven at 150 ° C. for 2 hours to obtain a resin molded body [I] having a length of 400 mm, a width of 300 mm, and a thickness of 0.2 mm.
• the obtained resin molded product [I] had a total light transmittance of 92%, a glass transition temperature of 250 ° C. or higher, a pencil hardness of 5H, and a flexural modulus of 4 GPa.
• the photocurable composition (ii) solution was applied on the resin molded body [I] using a 50 ⁇ m applicator so that the film thickness after drying was 15 ⁇ m, and dried at 60 ° C. for 5 minutes. Then, using a high pressure mercury lamp 80W and one lamp, two passes of UV irradiation (cumulative irradiation amount 450 mJ / cm 2 ) were carried out at a conveyor speed of 5.1 m / min from a height of 18 cm, and a cured resin layer [II] (Film thickness 15 ⁇ m) was formed. Each performance was evaluated as above about the obtained laminated body. The evaluation results are as shown in Table 2.
• the photocurable composition (iii) solution was placed on the resin molded body [I] with a bar coater NO. 7 was applied so that the film thickness after curing was 5 ⁇ m, and dried at 80 ° C. for 3 minutes. Thereafter, using a high pressure mercury lamp 80W and one lamp, two passes of ultraviolet irradiation (accumulated irradiation amount: 500 mJ / cm 2 ) are performed at a conveyor speed of 5.1 m / min from a height of 18 cm, and the cured resin layer [III] Formed.
• the photocurable composition (ii) solution is applied onto the cured resin layer [III] using a 50 ⁇ m applicator so that the film thickness after drying is 15 ⁇ m, and dried at 60 ° C. for 5 minutes.
• a high pressure mercury lamp 80W and one lamp two passes of ultraviolet irradiation (accumulated irradiation amount 450 mJ / cm 2 ) are performed at a conveyor speed of 5.1 m / min from a height of 18 cm, and the cured resin layer [II ] (Film thickness 15 ⁇ m) was formed.
• Each performance was evaluated as above about the obtained laminated body (resin molding [I] / cured resin layer [III] / cured resin layer [II]). The evaluation results are as shown in Table 2.
• a cured resin layer [III] was formed in the same manner as in Example 2 using the photocurable composition (iii) solution.
• the cured resin layer [II] was formed on the cured resin layer [III] in the same manner as in Example 2.
• Each performance was evaluated as above about the obtained laminated body (resin molding [I] / cured resin layer [III] / cured resin layer [II]). The evaluation results are as shown in Table 2.
• Example 1 ⁇ Comparative Example 1>
• the cured resin layer [II] was not formed, and each performance was evaluated as described above for the resin molded body [I]. The evaluation results are as shown in Table 2.
• the antifouling property cannot be obtained even if the resin molded body [I] is used as it is, whereas a laminate or a cured resin layer in which the cured resin layer [II] is formed on the resin molded body [I].
• the laminate in which the cured resin layer [II] is formed on the resin molded body [I] through [III] it has excellent adhesion, antifouling property, high surface hardness and transparency. It can be seen that it is.
• the laminate of the present invention can be advantageously used for various optical materials and electronic materials.
• protective sheet, touch panel, liquid crystal substrate, organic / inorganic EL substrate, PDP substrate, electronic paper substrate, light guide plate, phase difference plate, optical filter, etc. It can be used for recording applications, energy applications such as thin film battery substrates and solar cell substrates, optical communication applications such as optical waveguides, and functional films / sheets and various optical films / sheets.
• optical materials and electronic materials it can also be used in, for example, automotive materials, building materials, medical materials, stationery, and the like.

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