JP2014051090A - Laminate - Google Patents

Abstract

【選択図】図１Provided is a laminate having not only excellent scratch resistance but also high adhesion between a first layer and a second layer located on the surface and excellent durability.
A first layer 3 laminated on at least a partial region of one surface 2a of a resin base material 2 and laminated on at least a partial region of the other surface 3b of the first layer 3. And the first layer 3 cures the first composition containing at least one of a monomer, oligomer and polymer having a polymerizable double bond and an alkoxysilane compound. The second layer 4 is at least one selected from the group consisting of a polymer having a repeating unit represented by the following general formula (2), and Ti, Al, Zr and Sn. The laminated body 1 which is a hardened | cured material of the 2nd composition containing the metal alkoxide compound.

[Selection] Figure 1

Description

  The present invention relates to a laminate in which a surface layer having excellent scratch resistance is formed on the surface of a resin substrate.

  Poly (meth) acrylate resin or polycarbonate resin is excellent in moldability. Moreover, the resin molded product formed of these resins is lighter than glass. Therefore, such resin molded products are widely used for glasses, contact lenses, lenses for optical devices, and the like. In particular, a resin molded product formed of a polycarbonate resin is excellent in impact resistance, and is suitably used as a large resin molded product. For example, resin molded products formed of polycarbonate resin have been put into practical use as automotive headlamp lenses, window materials for trains, bullet trains, and the like.

  However, these resin molded products have a lower surface hardness than glass. For this reason, the resin molded product is easily damaged during transportation, attachment of parts, and use. Moreover, the durability of these resin molded products is low.

  Conventionally, in order to increase the hardness of a resin molded product, a surface layer having a high hardness is formed on the surface of the resin molded product.

  For example, Patent Document 1 discloses a resin molded article having a surface layer formed of a composition containing a polyfunctional acrylate monomer, colloidal silica, acryloxy functional silane, and a photopolymerization initiator. Is disclosed. In the Example of Patent Document 1, 3-methacryloxypropyltrimethoxysilane is used as the acryloxy functional silane.

  Patent Document 2 discloses a resin molded article having a surface layer formed of a composition containing an ultraviolet curable resin and a surface modifier made of a siloxane compound. Specific examples of the ultraviolet curable resin include acrylic oligomers having two or more acryloyl groups in the molecule, and acrylic monomers or oligomers to which colloidal silica is bonded. Specific examples of the siloxane compound include a polyether-modified dimethylpolysiloxane copolymer, a polyether-modified methylalkylpolysiloxane copolymer, and a polyester-modified dimethylpolysiloxane.

  Patent Document 3 discloses a two-layer surface in which a primer layer is formed using a thermoplastic acrylic polymer, and then a topcoat layer is formed on the surface of the primer layer using an organopolysiloxane filled with colloidal silica. A resin molded article having a layer is disclosed.

JP-A-57-13214 JP 2003-338089 A Japanese Patent Publication No. 04-002614

  However, the resin molded bodies disclosed in Patent Documents 1 to 3 may have insufficient scratch resistance. Moreover, in patent document 3, the adhesive force of a primer layer and a topcoat layer is low, and it may be inferior to durability. In particular, when immersed in hot water of 90 ° C. or higher, the topcoat layer may peel off from the primer layer.

  The main object of the present invention is to provide a laminate having not only excellent scratch resistance but also high adhesion between the first layer and the second layer located on the surface and excellent durability. is there. A limited object of the present invention is to provide a laminate particularly excellent in durability in which adhesion between a primer layer and a topcoat layer is maintained even when immersed in hot water of 90 ° C. or higher. is there.

  In the laminate according to the present invention, a resin base material, a first layer laminated on at least a part of one surface of the resin base material, and the resin base material of the first layer are laminated. A second layer stacked on at least a partial region of the other surface opposite to the other surface.

  The first layer is a cured first composition containing at least one of a monomer, oligomer and polymer having a polymerizable double bond and an alkoxysilane compound represented by the following general formula (1). It is a layer obtained by making it.

Here, R ¹ is a linear alkylene oxide chain having 2 to 12 carbon atoms having a cyclic ether group, a branched alkylene oxide chain having 3 to 12 carbon atoms, or a cycloalkylene oxide chain having 5 to 15 carbon atoms. N represents an integer of 1 to 3. R ² independently represents an alkyl group having 1 to 8 carbon atoms or hydrogen.

  The second layer contains a polymer having a repeating unit represented by the following general formula (2) and at least one metal alkoxide compound selected from the group consisting of Ti, Al, Zr, and Sn. The cured product of the second composition.

In formula (2), R ⁴ represents a linear alkylene oxide chain having 2 to 12 carbon atoms, a branched alkylene oxide chain having 3 to 12 carbon atoms, or a cycloalkylene oxide chain having 5 to 15 carbon atoms. 3 R ⁵ each independently represents an alkyl group having 1 to 8 carbon atoms or hydrogen.

In a specific aspect of the laminate according to the present invention, R ¹ in the general formula (1) is the number of carbon atoms having a cyclic ether group is a linear alkylene oxide chain or the carbon number of 2-6 5-8 Each of R ² is independently an alkyl group having 1 to 6 carbon atoms.

In a specific aspect of the laminate according to the present invention, R ⁴ in the general formula (2) is a linear alkylene oxide chain having 2 to 6 carbon atoms obtained by ring-opening polymerization of a cyclic ether group, or It is a C5-C8 cycloalkylene oxide chain | strand, and three R < ⁵ > is a C1-C6 alkyl group each independently.

  In a specific aspect of the laminate according to the present invention, at least one of the monomer, oligomer and polymer having a polymerizable double bond contained in the first composition is at least one in the molecule. It is a monomer, oligomer or polymer containing a (meth) acrylate group. In this case, the first composition can be easily and quickly cured by ultraviolet irradiation or the like. In addition, a monomer, oligomer or polymer containing the (meth) acrylate group can be easily cured by adding a heat-decomposable organic peroxide and heating.

  In another specific aspect of the laminate according to the present invention, the monomer or oligomer having the polymerizable double bond contained in the first composition is a polyfunctional compound represented by the following general formula (3) ( (Meth) acrylate.

Here, R ^a represents a p-valent organic group, R ^b represents an alkylene group having 1 to 6 carbon atoms, R ^c represents a hydrogen atom or a methyl group, and R ^d represents a hydrogen atom or a methyl group. Represents a group, q represents an integer of 1 to 9, and p represents an integer of 2 or more.

  When the polyfunctional (meth) acrylate represented by the above formula (3) is used, the adhesion with the second layer containing the polymer having the repeating unit represented by the formula (2) may be further increased. it can.

  In a specific aspect of the laminate according to the present invention, the p-valent organic group in the general formula (3) is an p-valent aliphatic hydrocarbon group having 2 to 40 carbon atoms, ethylene glycol. Residue, propylene glycol residue, diethylene glycol residue, dipropylene glycol residue, diglycerin residue, polyethylene glycol residue, polypropylene glycol residue, polyglycerin residue, erythritol residue, pentaerythritol residue, dipentaerythritol It is an organic group selected from the group consisting of a residue, an isocyanuric acid residue and a bisphenol A residue.

On the specific situation with the laminated body which concerns on this invention, ^Rb in the said General formula (3) is an ethylene group or a propylene group.

  In still another specific aspect of the laminate according to the present invention, a polymer having a repeating unit represented by the general formula (2) contained in the second composition is represented by the following general formula (4):

Is a polymer of alkoxysilane obtained by ring-opening polymerization of γ-glycidoxyalkyltrialkoxysilane represented by the formula:

In Formula (4), R ¹⁰ represents an alkylene group having 1 to 9 carbon atoms, and three R ¹¹ each independently represents an alkyl group having 1 to 8 carbon atoms.

In still another specific aspect of the laminate according to the present invention, R ¹⁰ in the general formula (4) is an alkylene group having 1 to 4 carbon atoms.

  In the laminate according to the present invention, since the second layer is configured as described above, it is excellent in scratch resistance, and Ti contained in the second layer when the second layer is cured. At least one metal alkoxide compound selected from Al, Zr and Sn serves as a new catalyst and is represented by the general formula (1) of the first layer in contact with the interface between the first layer and the second layer. The cyclic ether of the alkoxysilane compound having a cyclic ether group is ring-opened and bonded to the terminal group, free hydroxyl group, or unreacted cyclic ether group of the polymer represented by the general formula (2) of the second layer. Therefore, it is possible to effectively enhance the adhesion between the first layer and the second layer and improve the durability.

FIGS. 1A and 1B are a perspective view and a front sectional view showing a laminate according to an embodiment of the present invention. 2 (a) to 2 (c) are front cross-sectional views for explaining each step of obtaining a laminate according to an embodiment of the present invention.

  Hereinafter, the present invention will be clarified by describing specific embodiments of the present invention with reference to the drawings.

  The laminated body which concerns on FIG. 1 (a) and (b) at one Embodiment of this invention is shown with a perspective view and front sectional drawing.

  As shown in FIGS. 1A and 1B, the laminate 1 includes a resin base material 2, a first layer 3 laminated on the surface 2 a of the resin base material 2, and a resin of the first layer 3. It has the 2nd layer 4 laminated | stacked on the other surface 3b on the opposite side to the one surface 3a on which the base material 2 was laminated | stacked. The laminate 1 has first and second layers 3 and 4 as surface layers.

  The first layer 3 is laminated on the entire region of one surface of the resin base material 2. However, the 1st layer 3 may be laminated | stacked on the at least one part area | region of the surface 2a of the resin base material 2, and does not necessarily need to be laminated | stacked on the whole area | region of the surface 2a of the resin base material 2. FIG. Further, the second layer 4 may be laminated in at least a partial region of the other surface 3b opposite to the one surface 3a on which the resin base material 2 of the first layer 3 is laminated, The first layer 3 may not necessarily be stacked on the entire region of the other surface 3b. For example, the 1st, 2nd layers 3 and 4 may be laminated | stacked as a surface layer only in the area | region where the abrasion resistance and durability of the surface 2a of the resin base material 2 are calculated | required. Further, first and second layers 3 and 4 may be laminated as surface layers on both sides of the resin substrate 2.

  The resin base material 2 is formed of resin. The resin forming the resin base material 2 is not particularly limited. Examples of the resin that forms the resin base 2 include poly (meth) acrylate resins, polycarbonate resins, polyethylene terephthalate, polybutylene terephthalate, and styrene resins such as ABS, vinyl chloride resins, and cellulose acetate. Among these, a poly (meth) acrylate resin or a polycarbonate resin is preferable, and a polycarbonate resin is more preferable. Poly (meth) acrylate resin or polycarbonate resin is excellent in moldability. Moreover, the resin base material formed with poly (meth) acrylate resin or polycarbonate resin is light compared with glass. A resin substrate formed of a polycarbonate resin is excellent in impact resistance. Accordingly, the resin substrate 2 is preferably a poly (meth) acrylate resin substrate or a polycarbonate resin substrate, and more preferably a polycarbonate resin substrate.

  The shape of the resin substrate 2 is not particularly limited, and may be any shape such as a plate shape or a film shape.

  The first layer 3 is provided for the purpose of improving the adhesion between the resin substrate 2 and the second layer 4. For this reason, the thickness of the 1st layer 3 can be set suitably for the purpose of improving adhesiveness. The preferable lower limit of the thickness of the first layer 3 is 1 μm, and the preferable upper limit is 20 μm. From the viewpoint of sufficiently improving the scratch resistance, the preferable lower limit of the thickness of the second layer 4 is 0.1 μm, and the preferable upper limit is 20 μm.

  Hereinafter, details of the first composition 11 for forming the first layer 3 and the second composition 12 for forming the second layer 4 will be described.

(First composition)
In the present invention, as the first composition, a composition containing at least one of a monomer, an oligomer and a polymer each having a polymerizable double bond is used. The monomer, oligomer and polymer having such a polymerizable double bond are not particularly limited and can be appropriately selected according to the required quality.

  Examples of the polymerizable double bond include a (meth) acrylate group, a vinyl group, an allyl group, a methallyl group, and a propenyl group. In the present invention, a monomer, oligomer or polymer containing at least one (meth) acrylate group in the molecule is preferably used as the monomer, oligomer and polymer having a polymerizable double bond. In this case, the first composition can be easily cured by radical polymerization or thermal radical polymerization by irradiation with active energy rays.

  Examples of the monomer having at least one (meth) acrylate group include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate , Diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate , Dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) Acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, phenoxyethyl (meth) acrylate, butoxyethyl (Meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyltriethylene diglycol (meth) Examples thereof include compounds having one (meth) acryloyl group in the molecule such as acrylate, cyclohexyl (meth) acrylate, nonylphenyl (meth) acrylate, derivatives thereof such as caprolactone modified products thereof, acrylic acid, and the like, and mixtures thereof.

  (A) C2-C12 alkylene glycol (meth) acrylic acid diesters: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, (B) Polyoxyalkylene glycol (meth) acrylate diesters such as neopentyl glycol di (meth) acrylate and 1,6-hexanediol (meth) acrylate: diethylene glycol di (meth) acrylate, triethylene glycol di (meta) ) Acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. c) (Meth) acrylic acid diesters of polyhydric alcohols: (d) (meth) acrylic acid diesters of ethylene oxide and propylene oxide adducts of hydrides of bisphenol A or bisphenol A, such as pentaerythritol di (meth) acrylate: (E) a polyvalent isocyanate compound and two or more alcoholic hydroxyl group-containing compounds such as 2,2′-bis (4-acryloxyethoxyphenyl) propane and 2,2′-bis (4-acryloxypropoxyphenyl) propane Urethane (meth) acrylates having two (meth) acryloyloxy groups in the molecule obtained by further reacting an alcoholic hydroxyl group-containing (meth) acrylate with a terminal isocyanate group-containing compound obtained by previously reacting (F) Two or more residues in the molecule Two (meth) acryloyl in one molecule, such as epoxy (meth) acrylates having two (meth) acryloyloxy groups in the molecule obtained by reacting a compound having a xyl group with acrylic acid or methacrylic acid And a compound having a group.

  Also, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (B) a terminal isocyanate group-containing compound obtained by reacting a polyvalent isocyanate compound and two or more alcoholic hydroxyl group-containing compounds in advance, such as (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. Urethane (meth) acrylates having 3 or more (meth) acryloyloxy groups in the molecule obtained by reacting (meth) acrylate, (c) 3 or more epoxy groups in the molecule Compounds having 3 or more methacryloyl groups in one molecule, such as epoxy (meth) acrylates having 3 or more (meth) acryloyloxy groups in the molecule obtained by reacting the compound to be reacted with acrylic acid or methacrylic acid Is mentioned.

  In addition, as the oligomer and polymer containing at least one (meth) acrylate group in the molecule, a urethane (meta) obtained by reacting a hydroxyl-containing (meth) acrylate at the terminal of a polymer of polyol and polyisocyanate is used. ) Acrylate oligomers. Polyether diol obtained by ring-opening polymerization of a kind of ion-polymerizable cyclic compound such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyheptamethylene glycol, polydecamethylene glycol as the polyol. Or polyether diol obtained by ring-opening copolymerization of two or more ion-polymerizable cyclic compounds.

  As the polyol compound, the above-mentioned polyether diol is preferable, but in addition, polyester diol, polycarbonate diol, polycaprolactone diol, and the like can be used, and these diols can be used in combination with the polyether diol. The polymerization mode of these structural units is not particularly limited, and may be any of random polymerization, block polymerization, and graft polymerization.

  Examples of the diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and m-phenylene diisocyanate. P-phenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 3,3′-dimethylphenylene diisocyanate, 4,4′-biphenylene diisocyanate, 1,6- Hexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanate ester) F) Fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,5-bis (isocyanate methyl) -Bicyclo [2.2.1] heptane, 2,6-bis (isocyanatemethyl) -bicyclo [2.2.1] heptane and the like.

  Furthermore, examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) ) Acrylate, 1,4-butanediol mono (meth) acrylate, 2-hydroxyalkyl (meth) acryloyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol Mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta ( Data) acrylate, and the like.

  More preferably, a polyfunctional (meth) acrylate represented by the following general formula (3) can be suitably used as the monomer or oligomer having a polymerizable double bond.

  The first composition 11 for forming the first layer 3 includes a polyfunctional (meth) acrylate. The polyfunctional (meth) acrylate is represented by the following general formula (3).

In General Formula (3), R ^a is a p-valent organic group. Examples of the p-valent organic group include p-valent aliphatic hydrocarbon groups having 2 to 40 carbon atoms, ethylene glycol residue, propylene glycol residue, diethylene glycol residue, dipropylene glycol residue, diglycerin. Organic group selected from the group consisting of residues, polyethylene glycol residues, polypropylene glycol residues, polyglycerin residues, erythritol residues, pentaerythritol residues, dipentaerythritol residues, isocyanuric acid residues and bisphenol A residues X is preferred. When the p-valent organic group is the organic group X, the adhesion between the first layer 3 and the second layer 4 is further improved.

  The lower limit and the upper limit of the carbon number of the polyethylene glycol residue are not particularly limited, but are preferably 6 or more, preferably 30 or less, more preferably 24 or less, and further preferably 12 or less. preferable. If the said carbon number is more than the said preferable minimum, the handleability of a 1st composition will improve. If the said carbon number is below a preferable upper limit, the adhesiveness of the 1st layer 3 and the 2nd layer 4 will improve further.

  The lower limit and the upper limit of the carbon number of the polypropylene glycol residue are not particularly limited, but are preferably 9 or more, preferably 45 or less, more preferably 36 or less, and further preferably 18 or less. preferable. If the said carbon number is more than the said preferable minimum, the handleability of a 1st composition will improve. If the said carbon number is below a preferable upper limit, the adhesiveness of the 1st layer 3 and the 2nd layer 4 will improve further.

  The lower limit and upper limit of the carbon number of the polyglycerin residue are not particularly limited, but are preferably 9 or more, preferably 45 or less, more preferably 36 or less, and further preferably 18 or less. preferable. If the said carbon number is more than the said preferable minimum, the handleability of a 1st composition will improve. If the said carbon number is below a preferable upper limit, the adhesiveness of the 1st layer 3 and the 2nd layer 4 will improve further.

R ^b represents an alkylene group having 1 to 6 carbon atoms. When ^Rb is an alkylene group having 1 to 6 carbon atoms, the adhesion between the first layer 3 and the second layer 4 is improved. Since the adhesiveness between the first layer 3 and the second layer 4 is further improved, the R ^b is more preferably an ethylene group or a propylene group. R ^c represents a hydrogen atom or a methyl group. R ^d represents a hydrogen atom or a methyl group. q shows the integer of 1-9. p represents an integer of 2 or more.

  The upper limit of p is not particularly limited, but is preferably 12 or less, more preferably 9 or less, because the adhesion between the first layer 3 and the second layer 4 can be further enhanced. preferable.

  In the general formula (3), p q's may be the same value or different. Further, the lower limit and upper limit of the total of p q are preferably 30 or less, more preferably 27 or less, further preferably 12 or less, and preferably 2 or more, 9 or more It is more preferable that When the total of the p qs is equal to or greater than the preferable lower limit, the adhesion between the first layer 3 and the second layer 4 is further improved. If the total of the p q is less than or equal to the preferable upper limit, the adhesion between the first layer 3 and the resin base material is further improved.

  A “residue” is a p-valent structure in which at least one atom or atomic group is removed from a compound. However, in the case of a polyethylene glycol residue and a polyglycerin residue, it is preferably bonded in the form of the following structural formulas A and B. In the following structural formulas A and B, the portions surrounded by a broken line indicate a polyethylene glycol residue and a polyglycerol residue, respectively. However, in the following structural formulas A and B, k is an integer. The upper limit of k is not particularly limited, but k is preferably 10 or less, and more preferably 7 or less, because the adhesion between the first layer 3 and the second layer 4 is improved.

  When the 1st composition 11 contains the polyfunctional (meth) acrylate represented by the said General formula (3), the adhesiveness of a 1st layer and a 2nd layer can be made higher.

  Moreover, content of the polyfunctional (meth) acrylate represented by General formula (3) in the 1st composition 11 is 10 mass%-99.5 mass% with respect to the component which forms solid content. It is preferably 20% by mass to 90% by mass. When it exists in these ranges, the adhesiveness of the resin base material 2 and the 1st layer 3, and the adhesiveness of the 1st layer 3 and the 2nd layer 4 can be improved much more effectively.

  Since the adhesion between the first layer 3 and the resin base material 2 can be further improved, the polyfunctional (meth) acrylate represented by the general formula (3) is a polyfunctional p having an integer of 2 to 4. A functional (meth) acrylate is preferred. As for polyfunctional (meth) acrylate whose p is an integer of 2-4, only 1 type may be used and 2 or more types may be used. In particular, a trifunctional (meth) acrylate having p of 3 is more preferably used because high adhesion can be obtained. Moreover, since the sclerosis | hardenability by the active energy ray or heat energy of the 1st layer 3 can be improved further, the polyfunctional (meth) acrylate represented by the said General formula (3) is an integer whose p is 6 or more. It is preferable that it is a certain polyfunctional (meth) acrylate, and the polyfunctional (meth) acrylate whose p is 6 is more preferable. When the polyfunctional (meth) acrylate represented by the general formula (3) is used in combination with a hexafunctional (meth) acrylate having a p of 6, and a trifunctional (meth) acrylate having a p of 3, the adhesion and the curing. It is preferable because the property can be improved and the scratch resistance and productivity can be improved.

  Examples of the trifunctional (meth) acrylate having p of 3 include a modified alkylene oxide of trimethylolpropane tri (meth) acrylate represented by the following general formula (6).

In the general formula (6), three R ^b , R ^c and R ^d are each independently the same R ^b , R ^c and R ^d as in the general formula (3), and the three r are independently It is the same as q in the general formula (3).

  Moreover, as hexafunctional (meth) acrylate whose p is 6, the compound represented by following General formula (7) is mentioned, for example.

In General formula (7), six R ^<b > shows an ethylene group or a propylene group each independently. Six R ^c is a hydrogen atom or a methyl group independently. Six R ^d represents a hydrogen atom or a methyl group independently. Six s each independently represent an integer of 1 to 9.

  Other specific examples of polyfunctional (meth) acrylates having p of 6 or more include alkylene oxide modified products of dipentaerythritol hexaacrylate monomers, alkylene oxide modified polyester acrylates, alkylene oxide modified epoxy acrylates, alkylene oxide modified urethane acrylates. And oligomers such as alkylene oxide-modified polyol acrylate and alkylene oxide-modified polyglycerin acrylate. Other specific examples of hexafunctional (meth) acrylates having p of 6 include alkylene oxide-modified products of dipentaerythritol hexamethacrylate monomer, alkylene oxide-modified polyester methacrylate, alkylene oxide-modified epoxy methacrylate, and alkylene oxide-modified urethane. Examples thereof include oligomers such as methacrylate, alkylene oxide-modified polyol methacrylate, and alkylene oxide-modified polyglycerin methacrylate.

  The oligomer of an alkylene oxide-modified polyester acrylate is obtained by, for example, reacting a hydroxyl group of a polyester oligomer having 6 or more hydroxyl groups at the terminal obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with an alkylene oxide having hydroxyl groups at both ends. It can be obtained by modifying it and esterifying the hydroxyl group at the other end with acrylic acid. It can also be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid. The oligomer of the alkylene oxide-modified polyester methacrylate is obtained by, for example, reacting a hydroxyl group of a polyester oligomer having 6 or more hydroxyl groups at a terminal obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with an alkylene oxide having hydroxyl groups at both ends. It can be obtained by denaturation and esterification of the other terminal hydroxyl group with methacrylic acid. It can also be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to a polyvalent carboxylic acid with methacrylic acid.

  The oligomer of the alkylene oxide-modified epoxy acrylate is, for example, an ester of a low molecular weight bisphenol type epoxy resin or a novolac epoxy resin having an hydroxyl group having hydroxyl groups at both ends to the oxirane ring, and an ester of a hydroxyl group at the other end with acrylic acid. It is obtained by the chemical reaction. The alkylene oxide-modified epoxy methacrylate oligomer is, for example, an ester of a low molecular weight bisphenol type epoxy resin or a novolak epoxy resin with an alkylene oxide having a hydroxyl group at both ends added to the oxirane ring and an ester of a hydroxyl group at the other end with methacrylic acid. It is obtained by the chemical reaction.

  The alkylene oxide-modified urethane acrylate oligomer is a reaction product of an isocyanate compound obtained by reacting a polyol and diisocyanate and an acrylate monomer having a hydroxyl group. Examples of the polyol include polyester polyol, polyether polyol, and polycarbonate diol. The oligomer of alkylene oxide-modified urethane methacrylate is a reaction product of an isocyanate compound obtained by reacting a polyol and diisocyanate and a methacrylate monomer having a hydroxyl group. Examples of the polyol include polyester polyol, polyether polyol, and polycarbonate diol.

  The oligomer of alkylene oxide-modified polyglycerin acrylate is a reaction product obtained by, for example, reacting one hydroxyl group of alkylene oxide with the hydroxyl group of polyglycerol and adding hydroxyalkyl acrylate to the other terminal hydroxyl group. The oligomer of alkylene oxide-modified polyglycerol methacrylate is a reaction product obtained by, for example, reacting one hydroxyl group of alkylene oxide with the hydroxyl group of polyglycerol and adding hydroxyalkyl methacrylate to the other terminal hydroxyl group.

  The first composition further contains an alkoxysilane compound represented by the general formula (1).

Here, R ¹ is a linear alkylene oxide chain having 2 to 12 carbon atoms having a cyclic ether group, a branched alkylene oxide chain having 3 to 12 carbon atoms, or a cycloalkylene oxide chain having 5 to 15 carbon atoms. N represents an integer of 1 to 3. R ¹ is preferably a linear alkylene oxide chain having 2 to 6 carbon atoms having a cyclic ether group or a cycloalkylene oxide chain having 5 to 8 carbon atoms. R ² independently represents an alkyl group having 1 to 8 carbon atoms or hydrogen. R ² is preferably independently an alkyl group having 1 to 6 carbon atoms. In the present invention, as described later, the second composition contains at least one metal alkoxide compound selected from Ti, Al, Zr and Sn. The metal alkoxide compound acts as a catalyst for ring-opening polymerization of the compound containing the cyclic ether group represented by the general formula (1) constituting the first layer at the interface between the first layer and the second layer, By further polymerizing the terminal residue of the polymer having the repeating unit represented by the general formula (2) constituting the second layer, the interfacial adhesion between the first layer and the second layer is enhanced.

  Specific examples of the alkoxysilane compound having a cyclic ether group represented by the general formula (1) include γ-glycidoxypropyl (methyl) dimethoxysilane, γ-glycidoxypropyl (methyl) diethoxysilane, γ -Glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3 -Epoxypropyl (methyl) dimethoxysilane, 2,3-epoxypropyl (phenyl) dimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltributoxysilane 2- (3,4-epoxycyclohexyl) eth Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, and 2,3-epoxypropyl triethoxysilane and the like. Only one type of alkoxysilane compound containing a cyclic ether group may be used, or two or more types may be used.

  Moreover, it is preferable that content of the alkoxysilane compound represented by General formula (1) in the 1st composition 11 is 0.5 mass%-30 mass% with respect to the component which forms solid content. 0.8 mass% to 10 mass% is more preferable. When it exists in these ranges, the adhesiveness of the resin base material 2 and the 1st layer 3, and the adhesiveness of the 1st layer 3 and the 2nd layer 4 can be improved much more effectively.

  The first composition 11 may contain a polymerization initiator. When the 1st composition 11 contains a polymerization initiator, polyfunctional (meth) acrylate becomes easy to superpose | polymerize. As the polymerization initiator, an active energy ray polymerization initiator or a thermal decomposition polymerization initiator can be used. Among them, an active energy ray polymerization initiator that generates radicals when irradiated with active energy rays such as light is preferable.

  Specific examples of the active energy ray polymerization initiator include 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2, Monoacylphosphine oxide compounds such as 6-dimethoxybenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dimethylbenzoyl)- 2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4 , 4-Trimethylpentylph Bisacylphosphine oxide compounds such as sphinoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethoxybenzoyl) -phenylphosphine oxide, benzophenol, Acetophenone, 4,4′-dichlorobenzophenone, methylphenylglyoxylate, thioxanthone, 2,4-dimethylthioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, diisopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichloro Thioxanthone, 2-isopropylthioxanthone, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titania 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 ″ -diethylisophthalophenone, 9,10 -Phenanthrenequinone, 1-phenyl-1,2-propanedione-2 (O-ethoxycarbonyl) oxime, benzophenone, methyl orthobenzoylbenzoate, orthobenzoylbenzoic acid, 4-benzoyl-4'-methyldiphenyl sulfide, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one, 1-hydroxy-cyclohexyl- Enyl-ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 4-phenylbenzophenone, hydroxybenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 4-phenoxydichloroacetophenone, 4-t -Butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)- - hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) - phenyl (2-hydroxy-2-propyl) ketone.

  The active energy ray polymerization initiator can be used in a range of 0.1 to 15 parts by mass with respect to a total of 100 parts by mass of at least one of a monomer, oligomer and polymer having a polymerizable double bond. . Only one type of active energy ray polymerization initiator may be used, or two or more types may be mixed and used.

  Although it does not specifically limit as a thermal decomposition type polymerization initiator, The commercially available organic peroxide which can fully decompose | disassemble at the temperature lower than the heat-resistant temperature of the synthetic resin used as a base material can be used. For example, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3-di-t-butyl peroxide, t-butyl Cumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, α, α′-bis (t-butylperoxyisopropyl) benzene, n-butyl-4 , 4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butyl) Peroxy) -3,3,5-trimethylcyclohexane, t-butyl peroxybenzoate, benzoyl peroxide, t-butyl peroxyacetate, methyl Ethyl ketone peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, methyl ethyl ketone peroxide 2,5-dimethylhexyl-2,5-bisperoxybenzoate, t-butyl hydroperoxide, p-menthane hydroperoxide, p-chlorobenzoyl peroxide, hydroxyheptyl peroxide, chlorohexanone peroxide, octanoyl Peroxide, decanoyl peroxide, lauroyl peroxide, cumyl peroxy octoate, succinic peroxide, acetyl peroxide, t-butyl peroxy (2-ethylhexanoate), m-toluoyl peroxide -Oxide, t-butylperoxyisobutylene, 2,4-dichlorobenzoyl peroxide and the like.

  The first composition 11 may further contain an ultraviolet absorber, a light stabilizer, an antioxidant and the like in order to increase the durability of the first layer 3.

  The solvent is not particularly limited as long as it is a solvent that dissolves at least one of the monomer, oligomer and polymer having a polymerizable double bond and the compound represented by the general formula (1). Specific examples of the solvent include alcohol solvents such as methanol, ethanol, n-propanol and isopropanol, ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethyl ether, benzene, toluene, n-hexane and the like. Hydrocarbon solvents, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, and ester solvents such as ethyl acetate and butyl acetate. Only 1 type may be used for a solvent and 2 or more types may be mixed and used for it. Among these, a low boiling point solvent is preferable because the volatilization of the solvent is easy. As the low boiling point solvent, it is preferable to use an alcohol solvent such as methanol, ethanol, n-propanol, or isopropanol.

(Second composition)
In the present invention, the second composition 12 for forming the second layer 4 includes a polymer having a repeating unit represented by the following general formula (2).

In the general formula (2), R ⁴ is a linear alkylene oxide chain having 2 to 12 carbon atoms, a branched alkylene oxide chain having 3 to 12 carbon atoms, or a cycloalkylene oxide chain having 5 to 15 carbon atoms. Indicates. A linear alkylene oxide chain having 2 to 12 carbon atoms, a branched alkylene oxide chain having 3 to 12 carbon atoms, and a cycloalkylene oxide chain having 5 to 8 carbon atoms are each subjected to ring-opening polymerization of a cyclic ether group. It is preferable to obtain it. R ⁴ is more preferably a linear alkylene oxide chain having 2 to 10 carbon atoms, a branched alkylene oxide chain having 3 to 10 carbon atoms, or a cycloalkylene oxide chain having 5 to 12 carbon atoms, More preferably, it is a linear alkylene oxide chain having 2 to 6 carbon atoms or a cycloalkylene oxide chain having 5 to 8 carbon atoms. Three R < ⁵ > shows a C1-C8 alkyl group or hydrogen each independently. It is preferable that three R < ⁵ > is a C1-C6 alkyl group each independently.

  The polymer preferably has a weight average molecular weight in terms of styrene measured by gel permeation chromatography (GPC) of 500 to 10000, more preferably 600 to 5000, and still more preferably 1000 to 2300. . When the weight average molecular weight is in the above preferred range, the adhesion between the first layer 3 and the second layer 4 is further improved. Although the measuring method of the weight average molecular weight using a gel permeation chromatography is not specifically limited, For example, the following method is mentioned. Gel permeation chromatography measuring device (Waters, 2690), UV detector (Waters, UV Waters 2487), two columns connected in series (Showa Denko, Shodex LF-804), calibration Standard polystyrene is used for the measurement as a sample. In this method, 50 μL of 0.1% by mass of the polymer / THF solution passed through a filter having a pore diameter of 0.45 μm is injected into the column as a sample, and measurement is performed at a flow rate of 1 mL / min and 40 ° C.

R ⁴ is a polymer having a repeating unit represented by the above general formula (2), which is a linear alkylene oxide chain having 2 to 12 carbon atoms or a branched alkylene oxide chain having 3 to 12 carbon atoms. Examples of the structure include the following general formulas (2b) and (2c):

The structure represented by these is preferable. In the general formulas (2b) and (2c), R ²¹ represents an alkylene group or an organic group having an ether bond, and R ²² represents an organic group having an oxygen, an alkylene group or an ether bond. In the general formula ^(2b), the total number of carbon atoms of ^{R 21} and ^{R 22} is 1 to 11. In the general formula ^(2c), the carbon number of ^{R 21} is 1 to 11. The organic group having an alkylene group and an ether bond may be linear or branched. Examples of the organic group having an ether bond include an alkylene oxide group. The alkylene group and the organic group having an ether bond may have a substituent. Examples of the substituent include halogen and hydroxy group. ^{Also, R 23} represents an alkyl group or hydrogen having 1 to 8 carbon atoms independently.

  When the linear alkylene oxide chain has 2 to 12 carbon atoms, the adhesion between the first layer 3 and the second layer 4 is further improved. The linear alkylene oxide chain preferably has 3 to 10 carbon atoms. When the branched alkylene oxide chain has 3 to 12 carbon atoms, the adhesion between the first layer 3 and the second layer 4 is further improved. More preferably, the branched alkylene oxide chain has 3 to 10 carbon atoms. When R23 is an alkyl group, sufficient scratch resistance can be obtained if the number of carbon atoms is 1 or more, and sufficient adhesion between the first layer and the second layer can be obtained if it is 8 or less. And durability is improved.

Examples of the structure of the polymer having a repeating unit represented by the above general formula (2) in which R ⁴ is a cycloalkylene oxide chain having 5 to 15 carbon atoms include, for example, the following general formulas (2d) to (2g) :

The structure represented by these is preferable. In the general formulas (2d) to (2g), R ²⁴ represents an alkylene group or an organic group having an ether bond, and R ²⁵ represents an organic group having an oxygen, an alkylene group or an ether bond. The alkylene group and the organic group having an ether bond may be linear or branched. The alkylene group and the organic group having an ether bond may have a substituent. Examples of the substituent include halogen and hydroxy group. Examples of the organic group having an ether bond include an alkylene oxide group. Ring A ₁ represents a cycloalkylene ring of 3-membered ring to six-membered ring. In the general formula (2d), the total number of carbon atoms of R ²⁴ , R ²⁵ and ring A ₁ is 5-15. In the general formula ^(2e), the total number of carbon atoms of ^{R 24} and ring _{A 1} is a 5 to 15. In the general formula ^(2f), the total number of carbon atoms of ^{R 25} and ring _{A 1} is a 5 to 15. In the general formula (2 g), the number of carbon atoms of ring _{A 1} is 3 to 10. Moreover, R < ²⁶ > shows a C1-C8 alkyl group or hydrogen each independently. When the cycloalkylene oxide chain has 5 to 15 carbon atoms, the adhesion between the first layer 3 and the second layer 4 is further improved. The number of carbon atoms in the cycloalkylene oxide chain is more preferably 5-12, and still more preferably 3-8. When R ²⁶ is an alkyl group, sufficient scratch resistance is obtained if the number of carbon atoms is 1 or more, and if the number of carbon atoms is 8 or less, sufficient adhesion between the first layer and the second layer is obtained. And durability is improved.

  The polymer having a repeating unit represented by the general formula (2) is preferably an alkoxysilane polymer, and can be obtained by ring-opening polymerization of an alkoxysilane having a cyclic ether group in the presence of a catalyst. preferable. In the present invention, the cyclic ether group refers to a cyclic organic group having an ether bond. The cyclic ether group is usually a hydrocarbon group having a 3- to 6-membered ring structure and having an ether bond in the ring structure. Among them, a 3-membered or 4-membered cyclic ether group having a large ring strain energy and high reactivity is preferable, and a 3-membered cyclic ether group is more preferable.

  Specific examples of the cyclic ether group include, for example, a glycid in which an oxyglycidyl group having 4 or less carbon atoms such as β-glycidoxyethyl group, γ-glycidoxypropyl group, and γ-glycidoxybutyl group is bonded. Xyalkyl group, glycidyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ- (3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycycloheptyl) ethyl group, β- ( C5-C8 cycloalkyl having an oxirane group such as 3,4-epoxycyclohexyl) propyl group, β- (3,4-epoxycyclohexyl) butyl group, β- (3,4-epoxycyclohexyl) pentyl group And an alkyl group substituted with a group. Among these, an oxyglycidyl group is bonded to an alkyl group having 1 to 3 carbon atoms such as a β-glycidoxyethyl group, a γ-glycidoxypropyl group, and a β- (3,4-epoxycyclohexyl) ethyl group. An alkyl group having 3 or less carbon atoms substituted with a cycloalkyl group having 5 to 8 carbon atoms having a glycidoxyalkyl group or an oxirane group is preferable.

  The alkoxysilane polymer is preferably obtained by ring-opening polymerization of γ-glycidoxyalkyltrialkoxysilane represented by the following general formula (4). Thereby, the adhesiveness of the 2nd layer 4 and the 1st layer 3 is improved more.

In the general formula ^{(4), R 10} represents an alkylene group having 1 to 9 carbon atoms. R ¹⁰ is preferably an alkylene group having 1 to 4 carbon atoms. Three R < ¹¹ > shows a C1-C8 alkyl group each independently.

  Specific examples of the γ-glycidoxyalkyltrialkoxysilane represented by the general formula (4) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and γ-glycidoxy. Propyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2,3-epoxypropyltrimethoxysilane, 2,3-epoxy Examples include propyltriethoxysilane. As the alkoxysilane containing a cyclic ether group, only one type may be used, or two or more types may be used.

  In addition, the polymer having the repeating unit represented by the general formula (2) includes γ-glycidoxyalkyltrialkoxysilane represented by the general formula (4) and 3-glycidoxypropyl (methyl). Dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3-epoxypropyl (phenyl) dimethoxysilane and other alkoxysilanes. May be.

  The catalyst used for the ring-opening polymerization of the cyclic ether group is preferably an organometallic compound. Examples of the catalyst that can be used include metal alkoxide compounds of metals such as Ti, Al, Zr, and Sn, metal chelate compounds, metal ester compounds, and metal silicate compounds. Examples of the metal alkoxide compound include aluminum trimethoxide, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum triisobutoxide, aluminum tri-sec-butoxide. Aluminum alkoxide such as aluminum tri-tert-butoxide, tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-tert-butyl titanate, tetra-n-hexyl titanate , Titanium alkoxides such as tetraisooctyl titanate and tetra-n-lauryl titanate, tetraethyl zirconate, La-n-propyl zirconate, tetraisopropyl zirconate, tetra-n-butyl zirconate, tetra-sec-butyl zirconate, tetra-tert-butyl zirconate, tetra-n-pentyl zirconate, tetra-tert-pentyl Examples include zirconium alkoxides such as zirconate, tetra-tert-hexyl zirconate, tetra-n-heptyl zirconate, tetra-tert-octyl zirconate and tetra-n-stearyl zirconate, and tin alkoxides such as dibutyltin dibutoxide. .

  Examples of metal chelate compounds include tris (ethyl acetoacetate) aluminum, tris (isopropyl acetate) aluminum, tris (n-butyl acetoacetate) aluminum, isopropoxybis (ethyl acetoacetate) aluminum, and tris (acetylacetonato) aluminum. , Tris (proponylacetonato) aluminum, diisopropoxypropionylacetonatoaluminum, acetiacetonato bis (propionylacetonato) aluminum, acetylacetonatoaluminum di-sec-butyrate, methyl acetoacetate aluminum sec-butyrate, di (methyl Acetoacetate) ・ mono-tert-butylate, diisopropoxyethyl acetoacetate aluminum, monoacetyl Aluminum chelate compounds such as acetona bis (ethyl acetoacetate) aluminum, titanium chelate compounds such as diisopropoxy bis (ethyl acetoacetate) titanium, diisopropoxy bis (acetylacetonato) titanium, tetrakis (acetylacetonato) Zirconium chelate compounds such as zirconium and tributoxy (acetylacetonato) zirconium, and dibutyltin bis (acetylacetonate).

  Examples of the metal ester compound include titanium ester compounds such as polyhydroxytitanium stearate, zirconium ester compounds such as tributoxyzirconium stearate, dibutyltin diacetate, dibutyltin di (2-ethylhexylate), and dibenzyltin diester. (2-ethylhexylate), dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin distearate, dibutyltin diisooctylmalate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin distearate, etc. .

  Examples of the metal silicate compound include dibutyltin bistrimethoxysilicate, dibutyltin bistriethoxysilicate, dioctyltin bistrimethoxysilicate, and dioctyltin bistriethoxysilicate.

  Moreover, it is necessary to make the 2nd composition in this invention contain the at least 1 sort (s) of metal alkoxide compound chosen from Ti, Al, Zr, and Sn. The metal alkoxide compound acts as a catalyst for ring-opening polymerization of the compound containing the cyclic ether group represented by the general formula (1) constituting the first layer at the interface between the first layer and the second layer, By further polymerizing to the terminal residue of the alkoxysilane polymer represented by the general formula (2) constituting the second layer, the interfacial adhesion between the first layer and the second layer is enhanced. If at least one metal alkoxide compound selected from Ti, Al, Zr and Sn is used when producing the polymer represented by the general formula (2), it is not necessary to add further, and it can be used as it is. effective.

  As the metal alkoxide compound in the present invention, titanium tetramethoxide, titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium t-butoxide, aluminum trimethoxide, Aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, aluminum tri-sec-butoxide, aluminum tri-t-butoxide, zirconium tetramethoxide, zirconium tetraethoxide, Zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium n-tetrabutoxide, zirconium tetra-t-butoxide, tin dibutyl oxide, 'S butyl hydroperoxide, and the like.

  Among these catalysts, aluminum alkoxide is preferable from the balance of reactivity and storage stability, and aluminum tri-sec-butoxide is more preferable. These catalysts may use only 1 type and may use 2 or more types. The amount of the catalyst used for the ring-opening polymerization is not particularly limited, but is preferably 0.01 to 0.5 times the molar equivalent of the cyclic ether group, and 0.02 to 0.4. Double molar equivalents are more preferred.

  From the viewpoint of sufficiently thermosetting the second composition, the content of the polymer having the repeating unit represented by the general formula (2) in the solid content of the second composition is 40% by mass to 40% by mass. It is preferably in the range of 95% by mass, and more preferably in the range of 50% by mass to 80% by mass.

  In the second composition, in addition to the essential components, other alkoxysilanes represented by, for example, the following general formula (5) can be contained within a range not deteriorating the performance in the present invention.

Here, R ^c represents a polymerizable or non-polymerizable organic group having 1 to 30 carbon atoms, and R ^d represents an alkyl group having 1 to 6 carbon atoms. m is an integer of 0-3.

  Examples of the alkoxysilane represented by the general formula (5) include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isopropyltrimethoxysilane, and isobutyl. Trimethoxysilane, cyclohexyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, vinyltrimethoxysilane, vinyltri Ethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxy Propyltriethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Examples thereof include methoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, and 3aminopropyltriethoxysilane.

  Curing of the second composition is performed by hydrolysis and condensation of alkoxysilane by heating as described above. Thereby, according to this invention, the 2nd layer excellent in abrasion resistance can be formed.

(Other components that can be added to the first and second compositions)
In order to apply | coat uniformly, a 1st composition can be used by diluting with a solvent. Examples of the solvent include organic solvents. Only one type of solvent may be used, or two types may be used. Specific examples of the organic solvent include ethanol solvents such as ethanol, 1-propanol, 2-propanol, 1-butanol, t-butanol and 1-methoxy-2-ethanol, ethyl acetate, propyl acetate, butyl acetate and the like. Examples include ester solvents, ketone solvents such as methyl ethyl ketone, ethyl butyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbon solvents such as toluene and xylene, and petroleum solvents such as petroleum ether and petroleum naphtha.

  Also in the second composition, an organic solvent can be used as in the first composition. The second composition may be a composition using water as a solvent. When the main solvent of the second composition is water, an organic solvent may be appropriately added as necessary, such as the viscosity of the composition, the wettability with the first layer, and the leveling property. The organic solvent that can be added must be soluble in water, for example, alcohol solvents such as ethanol, 1-propanol, 2-propanol, 1-butanol, t-butanol, 1-methoxy-2-ethanol, etc. Is suitable.

  The first and second compositions may contain a leveling agent, a thixotropic agent, a dispersant, a flame retardant, a colorant, an ultraviolet absorber, an antioxidant, and the like as necessary.

  In the present invention, when both the first layer 3 and the second layer 4 contain an alkylene oxide chain, the affinity of the first layer 3 and the second layer 4 is increased, and the adhesion is improved. Can be further enhanced.

(Manufacturing method of the laminated body 1)
Hereinafter, an example of a method for manufacturing the laminate 1 will be described more specifically with reference to the drawings.

  As shown in FIG. 2A, the first composition 11 is applied to the surface 2 a of the resin substrate 2 to form a layer of the first composition 11.

  Thereafter, as shown in FIG. 2B, the first composition 11 is cured. The first composition 11 may contain a polymerization initiator as described later. Here, the case where the 1st composition 11 contains an active energy ray polymerization initiator is demonstrated, for example. By irradiating the first composition 11 with active energy rays, the first composition 11 is cured and the first layer 3 is formed. Specifically, when active energy rays are irradiated to the first composition 11, the active energy ray polymerization initiator is decomposed to generate radicals. This radical reacts with the polymerizable double bond to initiate the polymerization reaction, and the polymerization reaction of the polyfunctional (meth) acrylate proceeds. As a result, the first composition 11 is cured to form the first layer 3.

  Ultraviolet rays, electron beams, α rays, β rays, γ rays, X rays, infrared rays, visible rays, or the like can be used as active energy rays that are irradiated when the first composition 11 is cured. Among these active energy rays, ultraviolet rays or electron beams are preferable because they are excellent in curability and hardened products are hardly deteriorated.

In order to cure the first composition 11 by ultraviolet irradiation, various ultraviolet irradiation apparatuses can be used. As the light source, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or the like can be used. The irradiation energy of ultraviolet rays ^is preferably in the range of ^{10mJ / cm 2 ~10,000mJ / cm 2} , more preferably in the range of ^{100mJ / cm 2 ~5,000mJ / cm 2} . When the irradiation energy of ultraviolet rays is too low, the first composition 11 is hard to be cured, and the scratch resistance of the surface layer including the first layer 3 and the first layer 3 and the second layer 4 is lowered. , The adhesion tends to deteriorate. When the irradiation energy of ultraviolet rays is too high, the surface layer including the first layer 3 and the first layer 3 and the second layer 4 deteriorates, or the first layer 3 and the first layer 3 and the second layer 4 The transparency of the surface layer including the layer 4 may be reduced.

  In order to cure the first composition 11 by electron beam irradiation, various electron beam irradiation apparatuses can be used. The irradiation energy of the electron beam is preferably in the range of 0.5 Mrad to 20 Mrad, and more preferably in the range of 1.0 Mrad to 10 Mrad. If the electron beam irradiation energy is too low, the first composition 11 is difficult to cure, and the scratch resistance of the surface layer including the first layer 3 and the first layer 3 tends to be low. When the electron beam irradiation energy is too high, the surface layer including the first layer 3 and the first layer 3 deteriorates, or the transparency of the surface layer including the first layer 3 and the first layer 3 decreases. Sometimes.

  Further, the curing of the first composition may be achieved by heating. In this case, it is preferable that the first composition 11 contains the above-described thermal decomposition polymerization initiator. About heating temperature, what is necessary is just to be more than the decomposition temperature of a thermal decomposition type polymerization initiator.

  Next, as shown in FIG. 2 (c), the second composition is applied to the surface 3b opposite to the one surface 3a laminated on the resin base material 2 of the cured first layer 3. A layer of the second composition 12 is formed.

  The cured state of the first layer 3 when forming the layer of the second composition 12 may be at least as long as the interlayer between the first layer 3 and the layer of the second composition 12 is not disturbed. However, if the curing of the first layer 3 is sufficiently advanced, the scratch resistance of the surface layer of the obtained laminate 1 is increased. Therefore, it is preferable that it is fully cured.

  Next, the layer of the 2nd composition 12 is hardened by heating, and the 2nd layer 4 is formed. By this heating, the silanol group or alkoxy group contained in the second composition 12 undergoes condensation polymerization, and the second composition 12 is cured to form the second layer 4. Along with the formation of the second layer 4, at least one metal alkoxide compound selected from Ti, Al, Zr and Sn described above is included, so that the general formula (1) on the surface of the first layer 3 is included. A cyclic ether group of an alkoxysilane having a cyclic ether group represented by the formula (2) undergoes a ring-opening reaction, and the terminal group of the polymer having a repeating unit represented by the general formula (2) of the second layer, Since it binds to an unreacted cyclic ether group, the adhesion between the first layer and the second layer is improved. Furthermore, the alkoxy group of the alkoxysilane compound represented by the general formula (1) of the first layer and the alkoxy group of the polymer represented by the general formula (2) contained in the second layer or the alkoxy group are hydrolyzed. A stronger interfacial adhesion can be obtained when the silanol group produced by decomposition is bonded by a dealcoholization or dehydration condensation reaction.

  The heating temperature is preferably as close as possible to the upper limit of the heat resistance of the resin substrate 2 and is preferably in the range of 80 ° C to 130 ° C. When the heating temperature is within this range, the adhesion between the first layer 3 and the second layer 4 is enhanced. Moreover, the hardness of the 2nd layer 4 becomes high and the abrasion resistance of the laminated body 1 can be improved.

  The method for applying the first composition 11 and the second composition 12 for constituting the laminate 1 is not particularly limited. For example, a spray coating method, a flow coating method, a spin coating method, a bar coating method, a dip method, or the like. A coating method, a roll coating method, or the like can be used.

(Examples and Comparative Examples)
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

  The raw materials shown in Table 1 were mixed at the blending ratios shown in Table 3 to prepare first compositions used in Examples 1 to 8 and Comparative Examples 1 to 4, respectively.

  Moreover, 2nd composition AD was prepared with the compounding ratio of Table 3 using the raw material of Table 2. Specifically, the second compositions A to D were produced as follows.

(Second composition A)
118.2 g (0.5 mol) of γ-glycidoxypropyltrimethoxysilane (GPTS) was mixed with 24.6 g (0.1 mol) of aluminum tri-sec butoxide (ASB) and distilled water according to Table 3. By vigorously stirring, a cloudy solution was obtained. This solution was stirred in a water bath at 60 ° C. for 30 minutes to cause ring-opening polymerization of the epoxy group of GPTS to obtain a colorless and transparent composition. It was 1200 when the weight average molecular weight of the obtained ring-opening polymer of GPTS was measured by gel permeation chromatography (GPC). A specific method for measuring the weight average molecular weight is as follows. Gel permeation chromatography measuring device (Waters, 2690), UV detector (Waters, UV Waters 2487), two columns connected in series (Showa Denko, Shodex LF-804), calibration Standard polystyrene was used for measurement as a sample. As a sample, 0.1% by mass of a polymer / THF solution 50 μL passed through a filter having a pore diameter of 0.45 μm was injected into the column, and the measurement was performed at a flow rate of 1 mL / min and 40 ° C. The composition was cooled to room temperature, 8.8 g of 10% nitric acid was added dropwise, then 20.8 g (0.1 mol) of tetraethoxysilane (TEOS) was added dropwise, and the mixture was stirred at room temperature for 2 hours to form a coating composition. Product A was obtained. To this coating composition A, 0.5 g of a polyether-modified siloxane (BYK346 manufactured by Big Chemie) was added as a leveling agent to obtain a second composition A having a solid content concentration of 25%. Incidentally, the solid content concentration, GPTS is ring-opening polymerization, addition and molecular weight 167.24 of the molecular formula _R-SiO 1.5 when combined hydrolysis and condensation _{(R = C 6 H 11 O} 2), ASB hydrolysis Molecular weight 50.98 of molecular formula AlO _1.5 when condensed, molecular weight 600.09 of molecular formula SiO ₂ when TEOS is hydrolyzed / condensed, molecular formula HSiO _1.5 when MeDESH is hydrolyzed / condensed Using a molecular weight of 60.13, the theoretical solid weight calculated from the molar ratio was divided by the weight of all added raw materials.

(Second composition B)
Except for using 123.2 g (0.5 mol) of 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane (EPC6-ETS) instead of γ-glycidoxypropyltrimethoxysilane (GPTS), In the same manner as the second composition A, a second composition B having a solid content concentration of 25% was prepared. The weight average molecular weight of the obtained EPC6-ETS ring-opening polymer was 1500 by gel permeation chromatography (GPC). The molecular formula of hydrolysis-condensation product of a (EPC6-ETS) _{is, R-SiO 1.5 (R =} C 8 H 12 O 1), the molecular weight was calculated solid concentration as 176.27.

(Second composition C)
A second composition C having a solid content concentration of 25% was produced in the same manner as the second composition A, except that tetraethoxysilane (TEOS) was changed to 10.4 g (0.05 mol).

(Second composition D)
The solid content was the same as in the second composition A except that 68.1 g (0.5 mol) of methyltrimethoxysilane (MeTS) was used instead of γ-glycidoxypropyltrimethoxysilane (GPTS). A second composition D having a concentration of 25% was prepared. The molecular formula of hydrolytic condensate of _{(PhTS), R-SiO 1.5} (R = CH 3), the molecular weight was calculated solid concentration as 67.1.

(Examples 1-8 and Comparative Examples 1-4)
A commercially available colorless and transparent polycarbonate plate (length 10 cm × width 10 cm × thickness 4 mm) was prepared. On this polycarbonate board, the 1st composition of the mixing | blending shown in Table 3 was apply | coated uniformly using the spin coater, respectively, and the layer of the 1st composition was formed. The layer of the first composition was dried at room temperature (25 ° C.) for 10 minutes. Thereafter, the first composition layer was cured by irradiating the first composition layer with ultraviolet rays so that the irradiation energy was 1,000 mJ / cm ² with a 3 kW high-pressure mercury lamp in a nitrogen atmosphere. .

  Next, the second composition having the composition shown in Table 3 below was uniformly applied onto the cured first composition layer using a spin coater to form a second composition layer. . The layer of the second composition was dried at room temperature (25 ° C.) for 10 minutes. The layer of the second composition was then heated in an oven at 125 ° C. for 2 hours. Thus, the 1st layer and 2nd layer as a surface layer were formed in the upper surface of a polycarbonate board, and the laminated body of Examples 1-8 and Comparative Examples 1-4 was obtained.

  Next, the following items (1) to (12) were evaluated for the laminates obtained in Examples 1 to 8 and Comparative Examples 1 to 4, respectively.

(1) Thickness of 1st layer and 2nd layer The film thickness of the 1st layer and the 2nd layer was measured using the optical film thickness meter ETA-SST made from AudioDev GmbH.

(2) Appearance The state of the surface layer of the laminate after forming the second layer was visually confirmed and evaluated according to the following evaluation criteria.

[Evaluation criteria for appearance]
○: The surface layer is colorless and uniform. Δ: The surface layer is uneven, the fluoroscopic image is distorted, or the coating film is clouded. ×: The surface layer is cracked.

(3) Evaluation of transparency Based on JIS K7136, the haze value of the polycarbonate board in which the surface layer was formed was measured with the haze meter (Tokyo Denshoku Co., Ltd. "TC-HIIIDPK"). In addition, it shows that transparency is so high that a haze value is small.

  In addition, when the haze value of the said polycarbonate plate in which the said surface layer was not formed was measured, haze value was 0.1%.

(4) Evaluation of Yellowness Yellowness ΔYI was measured with a color analyzer (“TC-1800MK-II” manufactured by Tokyo Denshoku) according to JIS K7105.

(5) Evaluation of scratch resistance According to JIS R3212, a horizontal rotating table rotating at a speed of 70 times / minute and a pair of smoothly rotating wear wheels fixed at an interval of 65 ± 3 mm. Scratch resistance was evaluated using a constructed Taber abrasion tester “Rotary Ablation Tester TS” manufactured by Toyo Seiki Co., Ltd. In addition, the wear wheel measured the haze difference ((DELTA) haze%) of the haze after a 500 cycle test and initial haze in CS-10F (type IV) and a load of 500 g.

  In addition, when the said haze difference ((DELTA) haze%) of the said polycarbonate plate in which the said surface layer was not formed was measured, haze difference was 48%.

(6) Adhesiveness Adhesiveness was evaluated as an evaluation item for durability. It is desirable that the adhesion be maintained after the following boil test. In addition to being maintained after the boil test, it is more desirable that the adhesion be maintained after the water resistance evaluation, the hot water resistance evaluation, the moisture resistance evaluation and the heat resistance evaluation described below. . According to JIS K5600-5-6, the surface layer formed on the surface of the polycarbonate plate is crossed at right angles using a cutting jig (BYK cross-cut tester PE5123, 1 mm interval × 11). A total of 100 divided bases were formed by cutting 11 vertical and horizontal cuts. After sufficiently bonding an adhesive tape (manufactured by 3M, product number: Scotch 898, width 25 mm, adhesive strength 15.75 N / 25 mm) at an angle of 45 degrees with respect to the meshes on the surface layer on which the base mesh is formed, The adhesive tape was abruptly peeled from the surface layer in the direction of 90 degrees. Of the total 100 bases, the number of bases in which the surface layer remained without peeling from the polycarbonate plate was counted.

(7) Evaluation of weather resistance Light is emitted using a super xenon weather meter (SX75 manufactured by Suga Test Instruments Co., Ltd., inner filter quartz, outer filter # 295, illuminance 180 W / cm ² (300 to 400 nm), black panel temperature 63 ° C.). Irradiation and accelerated tests were conducted. The haze value and yellowness (ΔYI) after 1000 hours of irradiation were measured.

(8) Evaluation of water resistance After immersion in distilled water at 32 ° C. for 14 days, visual inspection and visual adhesion test (6) were performed.

(9) Evaluation of hot water resistance After immersion in distilled water at 50 ° C. for 24 hours, a visual appearance inspection and an adhesion test (6) were performed.

(10) Evaluation of moisture resistance After putting a sample into a constant temperature and humidity chamber of 50 ° C. and RH 98% for 14 days, a visual appearance inspection and an adhesion test (6) above were performed.

(11) Evaluation of heat resistance After putting a sample into a thermostat at 90 ° C. for 14 days, an adhesion test of haze value, yellowness (ΔYI) and (6) was performed.

(12) Boil test After dipping in hot water at 98 ° C for 30 minutes, a visual appearance inspection and an adhesion test (6) were performed.

  The evaluation results of (1) to (12) are shown in Table 4 below.

DESCRIPTION OF SYMBOLS 1 ... Laminated body 2 ... Resin base material 2a ... Surface 3 ... 1st layer 3a ... One side 3b ... Other side 4 ... 2nd layer 11 ... 1st composition 12 ... 2nd composition

Claims (9)

A resin substrate;
A first layer laminated on at least a partial region of one surface of the resin substrate;
A second layer laminated in at least a partial region of the other surface opposite to the one surface on which the resin base material of the first layer is laminated,
The first layer is a cured first composition containing at least one of a monomer, oligomer and polymer having a polymerizable double bond and an alkoxysilane compound represented by the following general formula (1). A layer obtained by

[Wherein, R ¹ is a linear alkylene oxide chain having 2 to 12 carbon atoms having a cyclic ether group, a branched alkylene oxide chain having 3 to 12 carbon atoms, or a cycloalkylene oxide having 5 to 15 carbon atoms. Represents a chain, and n represents an integer of 1 to 3. R < ² > shows a C1-C8 alkyl group or hydrogen each independently. ]
The second layer contains a polymer having a repeating unit represented by the following general formula (2) and at least one metal alkoxide compound selected from the group consisting of Ti, Al, Zr, and Sn. A laminate that is a cured product of the second composition.

[Wherein R ⁴ represents a linear alkylene oxide chain having 2 to 12 carbon atoms, a branched alkylene oxide chain having 3 to 12 carbon atoms, or a cycloalkylene oxide chain having 5 to 15 carbon atoms, Three R < ⁵ > shows a C1-C8 alkyl group or hydrogen each independently. ] R ¹ in the general formula (1) is a linear alkylene oxide chain having 2 to 6 carbon atoms or a cycloalkylene oxide chain having 5 to 8 carbon atoms having a cyclic ether group, and each R ² is The laminate according to claim 1, which is independently an alkyl group having 1 to 6 carbon atoms. R ⁴ in the general formula (2) is a linear alkylene oxide chain having 2 to 6 carbon atoms or a cycloalkylene oxide chain having 5 to 8 carbon atoms obtained by ring-opening polymerization of a cyclic ether group. Three R < ⁵ > is a C1-C6 alkyl group each independently, The laminated body of Claim 1 or 2.   The monomer, oligomer or polymer in which at least one of the monomer, oligomer and polymer having a polymerizable double bond contained in the first composition contains at least one (meth) acrylate group in the molecule The laminate according to any one of claims 1 to 3, which is a polymer. The monomer or oligomer having a polymerizable double bond contained in the first composition is a polyfunctional (meth) acrylate represented by the following general formula (3). The laminate according to Item 1.

[Wherein, R ^a represents a p-valent organic group, R ^b represents an alkylene group having 1 to 6 carbon atoms, R ^c represents a hydrogen atom or a methyl group, and R ^d represents a hydrogen atom or a methyl group. Represents a group, q represents an integer of 1 to 9, and p represents an integer of 2 or more. ]   The p-valent organic group in the general formula (3) is p-valent, an aliphatic hydrocarbon group having 2 to 40 carbon atoms, ethylene glycol residue, propylene glycol residue, diethylene glycol residue, di From propylene glycol residue, diglycerin residue, polyethylene glycol residue, polypropylene glycol residue, polyglycerin residue, erythritol residue, pentaerythritol residue, dipentaerythritol residue, isocyanuric acid residue and bisphenol A residue The laminate according to claim 5, which is an organic group selected from the group consisting of: The laminate according to claim 5 or 6, wherein R ^b in the general formula (3) is an ethylene group or a propylene group. A polymer having a repeating unit represented by the general formula (2) contained in the second composition is represented by the following general formula (4):

[Wherein, R ¹⁰ represents an alkylene group having 1 to 9 carbon atoms, and three R ¹¹ each independently represents an alkyl group having 1 to 8 carbon atoms. ]
The laminated body of any one of Claims 1-7 which is a polymer of the alkoxysilane obtained by ring-opening polymerization of (gamma) -glycidoxyalkyl trialkoxysilane represented by these. The laminate according to claim 8, wherein R ¹⁰ in the general formula (4) is an alkylene group having 1 to 4 carbon atoms.

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