JP6985126B2 - Laminates, coating agents, and methods for manufacturing laminates - Google Patents

Description

The present invention relates to a laminate, a coating agent, and a method for producing the laminate.

In various technical fields, a coating film covering the base material may be provided for the purpose of protecting the base material. In the field of electronic devices, the market for touch panels that input data by directly touching the display screen with a pen or finger as an input device to an information terminal is increasing, and a transparent protective layer or the like is provided on the surface of the touch panel. Be done. In addition, the surface of plastic parts used in automobiles, home appliances, and the like may be provided with functions such as designability, slipperiness, and stain resistance by a coating film.

Usually, a coating agent is used to form the coating film. As a material for a coating agent, urethane (meth) acrylate is known as a material that can be cured by active energy rays and can form a film having excellent mechanical properties (for example, Patent Document 1 below). See).

Japanese Unexamined Patent Publication No. 2012-36290

By the way, the coating film provided on a base material such as a touch panel and plastic parts for automobiles and home appliances, which are often touched by humans, is easily contaminated by human sebum and cosmetics. Patent Document 1 describes that a cured product of a curable composition exhibits chemical resistance to ethanol, hydrochloric acid and sodium hydroxide. However, according to the studies by the present inventors, it has been found that even the curable composition of Patent Document 1 does not have sufficient chemical resistance to cosmetics such as sunscreen cream.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a coating agent capable of forming a layer having excellent chemical resistance, a laminate having excellent chemical resistance, and a method for producing the same. do.

As a result of diligent research to achieve the above object, the present inventors have used a polycarbonate-based resin obtained by reacting a polycarbonate polyol having a specific skeleton, a polyisocyanate-based compound, and a polyol having a specific functional group. It was found that the cured resin layer formed in the above-mentioned material exhibits excellent chemical resistance to cosmetics such as sunscreen cream, and the present invention was completed based on this finding.

The present invention comprises a base material and a cured resin layer containing a cured product of the resin composition provided on the base material, and the resin composition comprises at least the following component (A) and the following (B). Provided is a laminate containing a polycarbonate-based resin obtained by reacting a component and the following component (C).
(A) Component: Polycarbonate polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom (B) Component: Polyisocyanate compound (C) Ingredients: (meth) acryloyl group-containing polyol having at least one (meth) acryloyl group and two or more hydroxyl groups in the molecule

The laminate of the present invention can have excellent chemical resistance by providing the cured resin layer.

The polycarbonate-based resin may have a divalent organic group represented by the following chemical formula (A-1).

The cured resin layer may further contain inorganic fine particles.

The polycarbonate-based resin may be at least a resin obtained by reacting the reaction products of the component (A) and the component (B) with the component (C).

The present invention also provides a coating agent containing a polycarbonate-based resin obtained by reacting at least the above component (A), the above component (B) and the above component (C).

According to the coating agent of the present invention, a layer having excellent chemical resistance can be formed on the substrate.

The polycarbonate-based resin may have a divalent organic group represented by the following chemical formula (A-1).

The coating agent of the present invention may further contain inorganic fine particles.

The polycarbonate-based resin may be at least a resin obtained by reacting the reaction products of the component (A) and the component (B) with the component (C).

The present invention also includes a step of providing a resin composition layer on a substrate and a step of curing the resin composition layer to form a cured resin composition layer, and the resin composition layer is at least described above (A). ), A method for producing a laminated body, which comprises a polycarbonate-based resin obtained by reacting the above-mentioned component (B) and the above-mentioned (C) component.

According to the method for producing a laminate of the present invention, a laminate having excellent chemical resistance can be produced.

The resin composition layer may further contain inorganic fine particles.

In the method for producing a laminate of the present invention, the resin composition layer further containing inorganic fine particles has a step of applying the resin composition on a substrate to form a coating film and spraying the inorganic fine particles onto the coating film. It may be formed through a process.

The polycarbonate-based resin may be at least a resin obtained by reacting the reaction products of the component (A) and the component (B) with the component (C).

According to the present invention, it is possible to provide a coating agent capable of forming a layer having excellent chemical resistance, a laminate having excellent chemical resistance, and a method for producing the same.

It is a schematic sectional drawing which shows one Embodiment of the laminated body which concerns on this invention. It is a schematic sectional drawing which shows another embodiment of the laminated body which concerns on this invention. It is a process drawing which shows typically one Embodiment of the manufacturing method of the laminated body which concerns on this invention. It is a process drawing which shows another embodiment of the manufacturing method of the laminated body which concerns on this invention schematically. It is a process drawing which shows another embodiment of the manufacturing method of the laminated body which concerns on this invention schematically. It is a process drawing which shows another embodiment of the manufacturing method of the laminated body which concerns on this invention schematically.

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

As used herein, "(meth) acrylate" means "acrylate" or its corresponding "methacrylate", "(meth) acrylic acid", "(meth) acrylic acid ester", "(meth) acryloyl". It is also synonymous with.

(Laminated body)
FIG. 1 is a schematic cross-sectional view showing an embodiment of the laminated body according to the present invention. The laminate 100 shown in FIG. 1 includes a base material 2 and a resin cured product layer (sometimes referred to as a “protective layer” or a “protective film”) 5 provided on the base material 2. The cured resin layer 5 is a layer containing a cured product 3 of a resin composition containing the polycarbonate-based resin according to the present invention (hereinafter, may be referred to as “polycarbonate-based resin composition of the present embodiment”).

FIG. 2 is a schematic cross-sectional view showing another embodiment of the laminated body according to the present invention. The laminate 110 shown in FIG. 2 includes a base material 2 and a resin cured product layer 6 provided on the base material 2, and the resin cured product layer 6 contains inorganic fine particles 4 and a polycarbonate-based material according to the present invention. It is a layer containing a cured product 3 of a resin composition containing a resin (sometimes referred to as a “particle-containing resin cured product layer”).

The material constituting the base material 2 is not particularly limited, but may be, for example, a resin used as a base material such as an optical hard coat film or a resin window. Materials constituting the base material 2 include polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polycarbonate resins; acrylic resins such as polymethylmethacrylate; polyethylene, polypropylene, polymethylpentene, and alicyclic resin. Polyolefin-based resins such as structure-containing polymers; cellulose resins such as cellophane, diacetyl cellulose resin, triacetyl cellulose resin, and acetyl cellulose butyrate resin; polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, etc. Vinyl-based resin; polystyrene resin; polysulfone resin; polyether ether ketone resin; polyether sulfone resin; polyetherimide resin; polyimide resin; fluororesin; polyamide resin; epoxy resin; polyurethane resin and the like.

Among the above materials, polyester-based resins, acrylic-based resins, and polyolefin-based resins are preferable for optical film applications such as surface protection films for touch panels and various displays from the viewpoint of transparency, impact resistance, and economy. Polyolefin-based resins containing an alicyclic structure and fluororesins are preferable as applications that require heat resistance. Polycarbonate-based resins are preferable for vehicle window glass applications from the viewpoint of transparency and impact resistance.

The polycarbonate-based resin according to the present invention comprises a polycarbonate polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom, and at least one in the molecule. It is a polycarbonate-based resin obtained by reacting a (meth) acryloyl group-containing polyol having two (meth) acryloyl groups and two or more hydroxyl groups with a polyisocyanate-based compound. Here, the "polycarbonate" is a compound having two or more carbonate groups in the molecule. The "alicyclic skeleton" is a structure in which carbon atoms are cyclically bonded, excluding an aromatic ring.

When the polycarbonate resin has an alicyclic skeleton, the carbon number of the alicyclic skeleton is preferably 3 to 18 and more preferably 3 to 10 from the viewpoint of chemical resistance. Examples of the alicyclic skeleton include cycloalkylene groups such as a cyclopropylene group, a cyclohexylene group, and a cyclodecanylene group.

When the polycarbonate resin has a skeleton in which at least one carbon atom of the alicyclic skeleton is substituted with an oxygen atom, a nitrogen atom or a sulfur atom, the carbon number of the skeleton is 3 to 18 from the viewpoint of chemical resistance. Is preferable, and 3 to 6 are more preferable. Examples of the skeleton include a divalent organic group represented by the following chemical formula (A-1).

The polycarbonate-based resin is, for example, a polycarbonate polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom (hereinafter, “(A)). (Also referred to as “component”), (B) a polyisocyanate compound (hereinafter, also referred to as “(B) component”), (C) at least one (meth) acryloyl group and two or more hydroxyl groups in the molecule. A resin (hereinafter, also referred to as “polycarbonate-based resin”) obtained by reacting with a (meth) acryloyl group-containing polyol (hereinafter, also referred to as “component (C)”) having the above can be used.

The polycarbonate-based resin is, for example, a component (A), a component (C), and, if necessary, a polyol other than the above-mentioned (A) component and (C) component (hereinafter, also referred to as “(E) component”. A polyol component containing (.), A polyisocyanate compound such as (B) component, and a (meth) acrylic acid ester compound having one hydroxyl group in the molecule (hereinafter, also referred to as "(d1) component"). It may be a polyurethane resin having a (meth) acryloyl group obtained by reacting with).

The double bond equivalent of the polycarbonate resin is preferably 150 to 4000 g / eq from the viewpoint of chemical resistance. Here, the double bond equivalent is defined by the following formula and is a measure of the amount of polymerizable double bond contained in the molecule.
Double bond equivalent = total mass of raw materials constituting the polycarbonate resin / total number of moles of (meth) acryloyl group contained in the polycarbonate resin

In polycarbonate-based resin, (A) the ratio of the sum of the number of moles M _C of the hydroxyl groups of the number of moles M _A and the component (C) of the hydroxyl groups of components, the number of moles M _B of the isocyanate groups of component (B) (M _A + _M C) :( _{M B),} from the viewpoint of chemical resistance, 1: 0.3 to 1: 3 preferably 1: 0.4 to 1: 2.2 are more preferred.

When the component (E) is used in the polycarbonate resin according to the present invention, the blending amount of the component (E) in the reaction system is the total mass of the component (A) and the component (E) from the viewpoint of chemical resistance. As a reference, 0 to 50% by mass is preferable, 0 to 30% by mass is more preferable, and 0 to 10% by mass is further preferable.

Hereinafter, the above-mentioned (A) component, (B) component, (C) component, (d1) component and (E) component will be described in order.

The component (A) is a polycarbonate polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom. Here, the "polycarbonate polyol" is a compound having two or more carbonate groups and two or more hydroxyl groups in the molecule.

The average hydroxyl value of the component (A) is preferably 50 to 250 mgKOH / g, more preferably 90 to 200 mgKOH / g, from the viewpoint of chemical resistance.

When the component (A) has an alicyclic skeleton, the carbon number of the alicyclic skeleton is preferably 3 to 18 and more preferably 3 to 10 from the viewpoint of chemical resistance. Examples of the alicyclic skeleton include cycloalkylene groups such as a cyclopropylene group, a cyclohexylene group, and a cyclodecanylene group.

When the component (A) has a skeleton in which at least one carbon atom of the alicyclic skeleton is substituted with an oxygen atom, a nitrogen atom or a sulfur atom, the carbon number of the skeleton is 3 to 3 from the viewpoint of chemical resistance. 18 is preferable, and 3 to 6 are more preferable. Examples of the skeleton include a divalent organic group represented by the following chemical formula (A-1).

The component (A) is, for example, a polyol having a skeleton in which at least one carbon atom of the (a1) alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom (hereinafter, "(a1)). It may be a compound obtained by a conventionally known reaction between a "component") and a carbonic acid derivative. The component (A) is obtained by a conventionally known reaction of a mixture of the component (a1) and a polyol (a2) other than the above component (a1) (hereinafter, also referred to as "component (a2)") with a carbonic acid derivative. It may be a compound to be used.

The component (a1) is a polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom. Here, the "polyol" is a compound having two or more hydroxyl groups in the molecule.

When the component (a1) has an alicyclic skeleton, the carbon number of the alicyclic skeleton is preferably 3 to 18 and more preferably 3 to 10 from the viewpoint of chemical resistance. Examples of the alicyclic skeleton include cycloalkylene groups such as a cyclopropylene group, a cyclohexylene group, and a cyclodecanylene group.

When the component (a1) has a skeleton in which at least one carbon atom of the alicyclic skeleton is substituted with an oxygen atom, a nitrogen atom or a sulfur atom, the carbon number of the skeleton is 3 to 3 from the viewpoint of chemical resistance. 18 is preferable, and 3 to 6 are more preferable. Examples of the skeleton include a divalent organic group represented by the following chemical formula (A-1).

As the component (a1), for example, a compound represented by the following chemical formula (A-2) such as isosorbide, isomannide, isoidide; a diol compound of cycloalkane such as cyclohexanedimethanol and cyclopropanedimethanol; hydrogenated bisphenol A, Hydrogenated bisphenol compounds such as hydrogenated bisphenol F; tricyclodecanedimethanol and the like can be mentioned. Among these, the compound represented by the chemical formula (A-2) is preferable from the viewpoint of chemical resistance. The compound represented by the chemical formula (A-2) may be a single stereoisomer or a mixture of different stereoisomers. (A1) As the component, one kind may be used alone or two or more kinds may be used in combination.

The component (a2) is a polyol other than the above component (a1). That is, the component (a2) is a polyol having no skeleton in which at least one carbon atom of the alicyclic skeleton and the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom.

Examples of the component (a2) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,3-butanediol, and 1,4-butanediol. 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, Aliper diols such as 2-methyl-1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol; aromatic diols such as bisphenol A; glycerin, trimethylolpropane, Examples thereof include polyhydric alcohols such as pentaerythritol. These can be used alone or in combination of two or more.

Examples of the carbonic acid derivative include diphenyl carbonate, dimethyl carbonate, diethyl carbonate, diethylene carbonate, phosgene and the like.

As the component (A), a commercially available product can also be used. Examples of commercially available products include isosorbide polycarbonate diols such as BENEBiOL HS0840B (manufactured by Mitsubishi Chemical Corporation) and BENEBiOL HS0850 (manufactured by Mitsubishi Chemical Corporation); Examples thereof include cyclohexanedimethanol-based polycarbonate diols such as (manufactured by Ube Industries), ETERNACOLL UM90 (1/3) (manufactured by Ube Industries), and ETERNACOLL UC100 (manufactured by Ube Industries).

The component (B) is a polyisocyanate compound. Here, the "polyisocyanate" is a compound having two or more isocyanate groups in the molecule. The polyisocyanate compound may be a derivative or a modified product of polyisocyanate. The component (B) is urethane-bonded with the hydroxyl groups of the components (A) and (C) to form a polyurethane prepolymer, whereby the physical properties of the resin and the like can be variously modified. Examples of the component (B) include low molecular weight polyisocyanates such as aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates, isocyanurates of these polyisocyanates, trione bodies of these polyisocyanates, and these. Examples thereof include derivatives and modified compounds of polyisocyanate. Among these, diisocyanate having two isocyanate groups in the molecule is preferable.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, tetramethylene diisocyanate, 1,2-butylenediocyanate, 2,3-butylenediocyanate, 1,3-butylenediocyanate, hexamethylene diisocyanate, and penta. Alibo diisocyanates such as methylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate; lysine ester triisocyanate, 1,4,8-triisocyanatooctane, 1,6,11-triisosia Molecules such as natoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane Examples thereof include aliphatic polyisocyanates having three or more isocyanate groups.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentanediisocyanate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (also known as:: Isophoron diisocyanate), 4,4'-methylenebis (cyclohexylisocyanate), 2,4'-methylenebis (cyclohexylisocyanate), methyl-2,6-cyclohexanediisocyanate, 1,3- or 1,4-bis (isocyanatomethyl) Alicyclic diisocyanates such as cyclohexane; 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2,5-bisisocyanatomethyl-bicyclo [2.2.1] heptane, 2 , 6-bisisocyanatomethyl-bicyclo [2.2.1] heptane, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2.2.1] heptane, 2 -(3-Isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -Vicyclo [2.2.1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane, 6- ( 2-Isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2.2.1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2 -(3-Isocyanatopropyl) -bicyclo [2.2.1] -heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2. 2.1] Examples thereof include alicyclic polyisocyanates having three or more isocyanate groups in a molecule such as heptane.

Examples of the aromatic polyisocyanate include m-phenylenedi isocyanate, p-phenylenedi isocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalenedi isocyanate, 2,4'-or 4,4'-diphenylmethane diisocyanate or Aromatic diisocyanates such as the mixture, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidin diisocyanate, 4,4'-diphenyl ether diisocyanate; triphenylmethane-4,4', 4 ''-In the molecule of triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanate toluene, 4,4'-diphenylmethane-2,2', 5,5'-tetraisocyanate, etc. Aromatic polyisocyanates having three or more isocyanate groups can be mentioned.

Examples of the polyisocyanate derivative include isocyanurate ring-containing polyisocyanates such as the above-mentioned polyisocyanate dimer and the above-mentioned polyisocyanate trimmer; polyisocyanate having a biuret bond; polyisocyanate having an allophanate bond; carbon dioxide gas and the above-mentioned polyisocyanate simple substance. Polyisocyanates having a 2,4,6-oxadiazine trione ring obtained by reaction with a meter; polyisocyanates having a carbodiimide bond; polymethylene polyphenyl polyisocyanates and the like can be mentioned.

As the modified product of the polyisocyanate, for example, the above-mentioned polyisocyanate or the derivative of the polyisocyanate and the polyol or the polyamine are used so that the isocyanate group of the polyisocyanate is more than the hydroxyl group of the polyol or the amino group of the polyamine. Examples thereof include a polyol-modified product and a polyamine-modified product obtained by reacting at an equivalent ratio; blocked isocyanate in which isocyanate is sealed with methyl ethyl ketone oxime, dimethylpyrazole, diethyl malonate, caprolactam, phenol and the like.

Among these, from the viewpoint of reducing yellowing due to light, the aliphatic polyisocyanate includes hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4- or 2, and 2,4-trimethylhexamethylene diisocyanate, and alicyclic. Group polyisocyanates include 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate), and 4,4'-methylenebis (cyclohexyl). Isocyanate) and 2,4'-methylene bis (cyclohexamethylene diisocyanate) are preferred. These can be used alone or in combination of two or more.

The component (C) is a (meth) acryloyl group-containing polyol having at least one (meth) acryloyl group and two or more hydroxyl groups in the molecule.

The inventors consider the reason why the laminate according to the present embodiment is excellent in chemical resistance as follows. That is, if the polycarbonate polyol resin obtained by reacting at least the component (A), the component (B) and the component (C) by having the component (C) having two or more hydroxyl groups in the molecule is only the terminal of the molecule. However, it is possible to have an acryloyl group as a cross-linking point inside the molecule. As a result, the cured product of the resin composition containing the polycarbonate polyol resin of the present embodiment has a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom. It is considered that it was possible to have a high cross-linking density while sufficiently containing it, and it was possible to impart excellent chemical resistance.

［式（Ｃ−１）中、Ｒ^１１及びＲ^１２は、それぞれ独立に水素原子、メチル基、又はエチル基を表し、Ｒ^１３は、水素原子、又はメチル基を表し、Ｙ^１１及びＬ^１１は、それぞれ独立に炭素原子、酸素原子及び水素原子からなる２価の有機基を表す。］ The component (C) preferably has a partial structure represented by the following formula (C-1).

[In formula (C-1), R ¹¹ and R ¹² independently represent a hydrogen atom, a methyl group, or an ethyl group, R ¹³ represents a hydrogen atom, or a methyl group, and Y ¹¹ and L ^{11 represent a hydrogen atom or a methyl group, respectively.} Represents a divalent organic group consisting of a carbon atom, an oxygen atom and a hydrogen atom, respectively. ]

Examples of the component (C) include pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth). (Meta) acrylate of polyhydric alcohol such as acrylate and glycerin mono (meth) acrylate; Reaction product of 2 molecules of (meth) acrylic acid and 1 molecule of 1,6-hexanediol diglycidyl ether (Nagase Chemtech) "DA-212"), a reaction product of two molecules of epoxy (meth) acrylic acid and one molecule of neopentyl glycol diglycidyl ether, two molecules of (meth) acrylic acid and one molecule of bisphenol A diglycidyl ether. Reaction product with (for example, "DA-250" manufactured by Nagase Chemtech), reaction product of two molecules of (meth) acrylic acid and diglycidyl ether of propylene oxide adduct of bisphenol A, and two molecules (meth). ) Reaction product of acrylic acid and 1 molecule of diglycidyl phthalate (for example, "DA-721" manufactured by Nagase Chemtech), 2 molecules of (meth) acrylic acid and 1 molecule of polyethylene glycol diglycidyl ether Reaction product (for example, "DM-811", "DM-832", "DM-851" manufactured by Nagase Chemtech Co., Ltd.) Reaction formation of two molecules of (meth) acrylic acid and one molecule of polypropylene glycol diglycidyl ether. Reaction product of (meth) acrylic acid and polyol diglycidyl ether; reaction product of 3 molecules of (meth) acrylic acid and 1 molecule of glycerin triglycidyl ether (for example, "DA-" manufactured by Nagase Chemtech Co., Ltd. 314 "), additions of glycidyl (meth) acrylate and (meth) acrylic acid, and the like. Among these, from the viewpoint of reactivity, a reaction product of pentaerythritol di (meth) acrylate, two molecules of (meth) acrylic acid and one molecule of 1,6-hexanediol diglycidyl ether, and two molecules of (meth). ) A reaction product of acrylic acid and one molecule of bisphenol A diglycidyl ether is preferred.

As used herein, the reaction product refers to the product produced by the reaction.

Examples of the reaction product of two molecules of (meth) acrylic acid and one molecule of 1,6-hexanediol diglycidyl ether include compounds represented by the following chemical formula (C-2).

Examples of the reaction product of two molecules of (meth) acrylic acid and one molecule of bisphenol A diglycidyl ether include compounds represented by the following chemical formula (C-3).

The component (d1) is a (meth) acrylic acid ester compound having one hydroxyl group in the molecule. Examples of the component (d1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth). Compounds represented by the following general formula (d-1) such as acrylates; (meth) acrylates of polyhydric alcohols such as pentaerythritol tri (meth) acrylates and dipentaerythritol penta (meth) acrylates; 2-hydroxyethyl (meth) ) Caprolactone-modified 2-hydroxyethyl (meth) acrylate obtained by adding lactone to acrylate by a known method can be mentioned. Among these, from the viewpoint of reactivity, the following formula (d-1), R ¹ is a hydrogen atom, n is 1 to 5 compounds, and (meth) acrylates of polyhydric alcohols are preferable, and 2- Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate are more preferable.

［式（ｄ−１）中、Ｒ^１は水素原子又はメチル基を表し、Ａ^１Ｏは炭素数２〜４のアルキレンオキシ基を表し、ｎは１〜２０の整数を表す。なお、ｎは、炭素数２〜４のアルキレンオキサイドの平均付加モル数を意味する。］

[In the formula (d-1), R ¹ represents a hydrogen atom or a methyl group, A ¹ O represents an alkyleneoxy group having 2 to 4 carbon atoms, and n represents an integer of 1 to 20. Note that n means the average number of moles of alkylene oxide having 2 to 4 carbon atoms. ]

The component (E) is a polyol other than the above components (A) and (C). That is, the component (E) is a polycarbonate polyol having an alicyclic skeleton and a polycarbonate polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom, and at least in the molecule. It is a polyol other than a (meth) acryloyl group-containing polyol having one (meth) acryloyl group and two or more hydroxyl groups. The component (E) does not have, for example, a polyether polyol, a polyester polyol, and a skeleton in which at least one carbon atom of the alicyclic skeleton and the alicyclic skeleton is substituted with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples include polycarbonate polyols.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

Examples of the polyester polyol include a reaction between a low molecular weight polyol and / or a polyether polyol and a dibasic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or an acid component of an anhydride thereof. Products include.

Examples of the polycarbonate polyol having no skeleton in which at least one carbon atom of the alicyclic skeleton and the alicyclic skeleton is substituted with an oxygen atom or a nitrogen atom or a sulfur atom include 1,3-propanediol and 1,4. -Butandiol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl Examples thereof include compounds obtained by a conventionally known reaction between a polyol such as -1,8-octanediol and 1,10-decanediol and a carbonic acid derivative such as diphenyl carbonate, dimethyl carbonate, diethyl carbonate, diethylene carbonate and phosgen. ..

Examples of the component (E) other than the above include a polyol having an alicyclic structure such as cyclohexanedimethanol, hydrogenated bisphenol A, hydrogenated bisphenol F, and tricyclodecanedimethanol, and an alicyclic such as isosorbide, isomannide, and isoidide. Polyol having a skeleton in which at least one carbon atom of the formula structure is substituted with an oxygen atom; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,3 -Butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8 Glycos such as -octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-propanediol; glycerin, trimethylolpropane, Polyhydric alcohols such as pentaerythritol; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; novolaks such as phenol novolac and cresol novolac. These can be used alone or in combination of two or more.

The polycarbonate-based resin according to the present invention can be produced by a known method.

The order in which the component (A), the component (B), and the component (C), and the components (d1) and (E) to be blended as necessary are reacted is not particularly limited, and for example, all of them. The components may be reacted together, the predetermined components may be reacted with each other, and then the remaining components may be reacted, or the predetermined components may be divided and reacted. From the viewpoint of improving chemical resistance, it is preferable to react at least the component (C) with the reaction products of the components (A) and (B). That is, it is preferable to obtain a reaction product obtained by reacting at least the component (A) and the component (B), and to react the reaction product with the component (C).

In the present specification, unless otherwise specified, or unless there is a clear contradiction in the context, at least the component (A), the component (B), and the component (C) are reacted to mean the component (A). Not only the component (B) and the component (C), and if necessary, all of the other components are reacted at the same time, but also the component (A), the component (B), and other components as needed. The reaction product to be reacted is obtained, and then the obtained reaction product is reacted with the component (C) and, if necessary, other components, the component (C), the component (B) and necessary. It comprises reacting the other components accordingly to obtain a reaction product, followed by reacting the obtained reaction product, the component (A) and, if necessary, the other components. Further, in the case of a reaction product of the component (A) and the component (B), a reaction product obtained by further reacting a component other than the component (A) and the component (B) is also included.

The ends of the polycarbonate-based resin obtained by reacting the component (A), the component (B), the component (C), and, if necessary, the component (d1) are the component (A), the component (B), and (C). Either the component or the component (d1) may be used, but from the viewpoint of chemical resistance, the terminals are the component (A) and the component (C), the component (A) and the component (d1), and the component (B) and (C). ) Component, (B) component and (d1) component, (C) component alone (that is, (C) component and (C) component), (d1) component alone (that is, (d1) component and (d1) component), ( The C) component and the (d1) component are preferable, and the (C) component alone, the (d1) component alone, and the (C) component and the (d1) component are more preferable.

The polycarbonate-based resin whose terminal is the component (C) alone, the component (d1) alone, or the component (C) and the component (d1) is, for example, the component (A) and, if necessary, the component (C) and (B). In the presence of a catalyst and, if necessary, a polymerization inhibitor, the hydroxyl group of the component (A) and the hydroxyl group of the component (C) added as needed are 75% or more of the isocyanate group of the component (B). The reaction is carried out under the conditions of 70 to 90 ° C. until the reaction is carried out, and then the component (C) and, if necessary, the component (d1) are further added to remain at 60 to 90 ° C. in the presence of a catalyst and a polymerization inhibitor. It can be produced by reacting until the isocyanate concentration becomes a specified concentration or less.

The polycarbonate resin having a terminal (A) and (C) component, (A) component and (d1) component, or a combination of (A) component and (C) component and (d1) component is, for example, (A). ) Component and, if necessary, component (C) and component (B), in the presence of a catalyst and, if necessary, a polymerization inhibitor, the hydroxyl group of component (A) and the component (C), if necessary. The hydroxyl group of (B) is reacted under the condition of 70 to 90 ° C. until it reacts with the isocyanate group of the component (B) by 75% or more, and then the components (A), (C) and (d1) are further added. It can be produced by reacting at 60 to 90 ° C. in the presence of a catalyst and a polymerization inhibitor until the residual isocyanate concentration becomes a specified concentration or less.

The polycarbonate-based resin whose terminal is a combination of the component (B), the component (C), and the component (d1), or a combination of the component (C), the component (d1), and the component (A) is, for example, (A). The component and, if necessary, the component (C) and the component (B) of the component (C) to which the hydroxyl group of the component (A) and the component (C), if necessary, were added in the presence of a catalyst and, if necessary, a polymerization inhibitor. The hydroxyl group is reacted under the condition of 70 to 90 ° C. until it reacts with the isocyanate group of the component (B) by 75% or more, and then the component (C) and, if necessary, the components (d1) and (A) are further added. It can be produced by adding it and reacting it at 60 to 90 ° C. in the presence of a catalyst and a polymerization inhibitor until the residual isocyanate concentration becomes a specified concentration or less.

The polycarbonate-based resin whose terminal is the component (A) alone or the component (B) and the component (A) is, for example, a component (B), a component (C) and, if necessary, a component (A). From 70 to 70 until the hydroxyl group of the component (C) and the hydroxyl group of the component (A) added as needed react with the isocyanate group of the component (B) by 75% or more in the presence of a catalyst and, if necessary, a polymerization inhibitor. The reaction is carried out under the condition of 90 ° C., and then the component (A) is further added and reacted at 60 to 90 ° C. at 60 to 90 ° C. until the residual isocyanate concentration becomes the specified concentration or less in the presence of a catalyst and a polymerization inhibitor. Can be manufactured.

Examples of the catalyst used for producing the polycarbonate-based resin include amine-based catalysts such as triethylamine, N-ethylmorpholine, and triethylenediamine; tin-based catalysts such as trimethyltinlaurate and dibutyltindilaurate; titanium-based, zinc-based, and bismuth. Examples thereof include known urethane polymerization catalysts typified by organic metal salts such as bismuth-based compounds such as tris (2-ethylhexanoate). These can be used alone or in combination of two or more.

Examples of the polymerization inhibitor used for producing the polycarbonate resin include phenols such as hydroquinone, hydroquinone monoethyl ether and dibutylhydroxytoluene; amines such as phenothiazine and diphenylamine; copper salts such as copper dibutyldithiocarbamate; manganese acetate. Manganese salts such as; nitro compounds; nitroso compounds and the like. These can be used alone or in combination of two or more. Of these, phenols are preferable as the polymerization inhibitor.

From the viewpoint of chemical resistance, the polycarbonate resin of the present embodiment preferably has a urethane bond equivalent of 120 to 1200 g / eq, and more preferably 200 to 1200 g / eq. Here, the urethane bond equivalent is defined by the following formula and serves as a measure of the urethane bond amount contained in the molecule.
Urethane bond equivalent = total mass of raw materials constituting the polycarbonate resin / total number of moles of urethane bond contained in the polycarbonate resin

The polycarbonate-based resin composition of the present embodiment contains the above-mentioned polycarbonate-based resin according to the present invention.

If necessary, a photopolymerization initiator may be added to the polycarbonate-based resin composition of the present embodiment. The type of the photopolymerization initiator is not particularly limited, and known ones can be used. Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, benzoin isopropyl ether, benzophenone and the like. These can be used alone or in combination of two or more.

When the photopolymerization initiator is used, the amount added thereof is preferably 1 to 10% by mass, preferably 3 to 5% by mass, based on the mass of the polycarbonate-based resin according to the present invention in the polycarbonate-based resin composition of the present embodiment. % Is more preferable.

The polycarbonate-based resin composition of the present embodiment further comprises, if necessary, a solvent, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an acrylate compound, a light stabilizer, an ultraviolet absorber, a catalyst, and the like. It can contain a thermal polymerization initiator, a polymerization inhibitor, a silicone defoaming agent, a leveling agent, a thickener, an anti-dripping agent, various additives for organic / inorganic pigments / dyes, additive aids and the like.

Examples of the solvent include aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, octane, isooctane and decane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, cumene and ethylbenzene. Solvents; diethyl ether, diisopropyl ether, methyl-tert-butyl ether, methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tetrahydrofuran, 1 , 3-dioxane, 1,4-dioxane and other ether solvents; dimethyl ketone, ethyl methyl ketone, diethyl ketone, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, cyclohexanone and other ketone solvents; dimethyl carbonate, diethyl carbonate, ethylene Carbonate ester solvents such as carbonate; methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, cyclohexanol, diacetone alcohol, 3-methoxy-3-methyl-1-butanol, ethylene Alcohol-based solvents such as glycol and propylene glycol; ester-based solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, propylene glycol monomethyl ether acetate and 3-methoxy-3-methyl-1-butyl acetate; Nitrile solvents such as acetonitrile, aliphatic amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, alkoxy-N-isopropyl-propionamide, hydroxyalkylamide; N-methyl-2-pyrrolidone, N -Alicyclic amide solvent such as ethyl-pyrrolidone; methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (Meta) acrylate, Isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate , Cyclohexyl (meth) Alkyl (meth) acrylates such as acrylates, phenyl (meth) acrylates, benzyl (meth) acrylates, isobornyl (meth) acrylates, dicyclopentanyl (meth) acrylates, dicyclopentenyl (meth) acrylates, and dicyclopentenyloxyethyl (meth) acrylates. Meta) Acrylate; Aromatic vinyls such as styrene, 2-methylstyrene, t-butylstyrene, chlorstyrene, vinylanisole, vinylnaphthalene, divinylbenzene; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and Unsaturated carboxylic acids such as these anhydrides; vinyl esters such as vinyl acetate and vinyl propionate; vinylidene halides such as vinylidene chloride and vinylidene fluoride; N, N-dimethylaminoethyl (meth) acrylates, N, Aminoalkyl (meth) such as N-diethylaminoethyl (methacrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dibutylaminoethyl (meth) acrylate). ) Acrylates; unsaturated sulfonic acids such as styrene sulfonic acid and sodium styrene sulfonic acid; 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, acrylonitrile, metaacrylonitrile, vinyl chloride, Ethylene, propylene, isoprene, butadiene, chloroprene, vinylpyrrolidone, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) Acrylate, 2- (2'-hydroxy-5'-methacryloyloxye. Tyrphenyl) -2H-benzotriazole and the like; examples of the polyfunctional (meth) acrylic monomer include ethylene glycol di (meth) acrylate, dicyclopentenyldi (meth) acrylate, triethylene glycol diacrylate, and tetraethylene glycol di (meth). ) Acrylate, bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.02,6] decane (also referred to as "tricyclodecanediyldimethylene di (meth) acrylate"), tris (2-hydroxyethyl) Isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide. (Hereinafter referred to as "EO") Modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as "PO") Modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone Modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate , PO-modified hydrogenated bisphenol A di (meth) acrylate, EO-modified bisphenol F di (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, acrylic monomer such as component (d1); water and the like. These can be used alone or in combination of two or more.

The inorganic fine particles 4 are not particularly limited. Examples of the inorganic fine particles 4 include mica, synthetic mica, silica, alumina, calcium oxide, titania, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / tin oxide), and ATO (indium oxide / tin oxide). (Antimon oxide / tin oxide), tin oxide, indium oxide, cadmium oxide, antimonium oxide, diamond and the like can be mentioned. These can be used alone or in combination of two or more. Among these, from the viewpoint of scratch resistance, silica, alumina, calcium oxide, titania, zinc oxide, zinc oxide, magnesium fluoride, ITO (indium oxide / tin oxide), ATO (antimonium oxide / tin oxide), tin oxide , Indium oxide, cadmium oxide, and diamond are preferred.

The content of the inorganic fine particles 4 in the particle-containing cured resin layer 6 is preferably 0.001 to 70% by mass, preferably 0.005 to 50% by mass, based on the dry mass of the particle-containing cured resin layer 6. % Is more preferable. When the content of the inorganic fine particles 4 is within the above range, the particle-containing resin cured product layer 6 can have a more excellent scratch-preventing effect.

The average particle size of the inorganic fine particles 4 is preferably 5 to 300 nm, more preferably 10 to 200 nm as the primary particle size. When the average particle size of the inorganic fine particles 4 is within the above range, the particle-containing resin cured product layer 6 can have better surface smoothness and better scratch prevention effect.

(Coating agent)
The coating agent of the present embodiment contains the polycarbonate-based resin according to the present invention. The coating agent may be a one-agent type or a two-agent type of a first agent containing a polycarbonate-based resin according to the present invention and a second agent containing a polymerization initiator. When it contains inorganic fine particles, it may be a two-agent type of a first agent containing a polycarbonate-based resin according to the present invention and a second agent containing inorganic fine particles.

The content of the polycarbonate resin according to the present invention in the coating agent of the present embodiment is preferably 3 to 99% by mass based on the total amount of the coating agent.

The coating agent may be a solvent, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an acrylate compound, a light stabilizer, an ultraviolet absorber, a catalyst, a thermal / photopolymerization initiator, or a polymerization agent, if necessary. It can contain a banning agent, a silicone defoaming agent, a leveling agent, a thickener, a precipitation inhibitor, an anti-dripping agent, a flame retardant, various additives for organic / inorganic pigments / dyes, additive aids and the like.

As the solvent, the same solvent as that used for the above-mentioned polycarbonate resin composition can be used. The solvent used for the coating agent includes a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an ester solvent such as ethyl acetate, n-butyl acetate and isobutyl acetate, and a nitrile such as acetonitrile from the viewpoint of adhesion to the substrate. Acrylic monomers containing a solvent, the component (d1), and the like are preferable. In the coating agent of the present embodiment, the component (C) can be used as a part of the solvent.

The content of the solvent in the coating agent is not limited because it depends on the desired physical properties. The content of the solvent is, for example, preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the resin component (component forming a solid content) in the coating agent, and is 40 to 300 parts by mass from the viewpoint of coating suitability. Is more preferable.

The method for producing the coating agent is not particularly limited. The coating agent can be produced, for example, by adding and dispersing the polycarbonate-based resin composition of the present embodiment to a solvent. Examples of the method for dispersing the polycarbonate-based resin composition and the inorganic fine particles when they are contained include conventionally known mixing and dispersing methods. In order to more reliably disperse the polycarbonate-based resin composition and the inorganic fine particles, it is preferable to carry out the dispersion treatment using a disperser. Dispersers include, for example, two rolls, three rolls, bead mills, ball mills, sand mills, pebble mills, ultrasonic mills, sand grinders, seg barrier trimers, planetary stirrers, high speed impeller dispersers, high speed stone mills, high speed impacts. Examples include mills, kneaders, homogenizers, ultrasonic dispersers, and the like.

The coating agent of the present embodiment forms a protective film for a touch panel; a protective film for a protective sheet for a touch panel; a protective film for a window glass for an automobile, an interior / exterior material and a wheel; a window glass for a house, an interior / exterior. It can be suitably used for forming a protective film for materials, floor materials, toilet bowls and kitchen equipment; for forming a protective film for optical information media such as plastic lenses, solar cell modules and DVDs. The protective film has excellent chemical resistance (for example, UV absorbers, preservatives, emulsifiers, solvents and UV absorbers contained in cosmetics such as liquid foundations, makeup bases, concealers, sunscreen creams, beauty essences, milky lotions, and hand creams. It can have chemical resistance to oils and fats).

(Manufacturing method of laminated body)
FIG. 3 is a process diagram showing an embodiment of the method for manufacturing a laminated body according to the present invention. The method for producing the laminate 100 shown in FIG. 3 is a step of forming the resin composition layer 15 of the polycarbonate-based resin composition 13 of the present embodiment containing the polycarbonate-based resin according to the present invention on the base material 2. FIG. 3A) and a step of curing the resin composition layer 15 (FIG. 3B).

The resin composition layer 15 can be formed, for example, by applying the coating agent of the present embodiment to the base material 2.

The method of applying the coating agent is not particularly limited. The coating method can be appropriately selected according to the shape of the base material 2. Examples of the coating method include a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, a roller coating method and the like. Among these, the dip coating method, the flow coating method, and the spray coating method, which are easy to deal with complicated shapes, are preferable.

The thickness of the coating film of the coating agent can be set so that the thickness of the resin composition layer after drying is 0.1 to 50 μm.

The resin composition layer 15 can be cured by polymerizing and solidifying the resin component in the resin composition layer 15. The curing of the resin composition layer 15 is performed, for example, by heating the resin composition layer 15 as necessary to remove the volatile solvent contained in the resin composition layer 15, and then UV (ultraviolet rays) and EB. It can be performed by irradiating active energy rays L such as (electron beam), infrared rays, visible rays, X-rays, electron beams, α rays, β rays, and γ rays. As the active energy ray L, it is preferable to use EB or UV from the viewpoint of equipment cost and productivity. As the light source of the active energy ray L, a UV lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an Ar laser, a He-Cd laser, a solid state laser, a xenon lamp, and a high frequency induced mercury. Lamps, LED lamps, sunlight and the like are preferable. The irradiation amount of the active energy ray L can be appropriately selected according to the type of the active energy ray L. For example, in the case of EB irradiation, 1 to 10 Mad is preferable. Further, in the case of UV irradiation, 50 to 5,000 mJ / cm ² is preferable. The atmosphere of the resin composition layer 15 at the time of curing includes an inert gas such as air, nitrogen, and argon. The active energy ray L may be irradiated in a closed space between the film or glass and the metal mold.

FIGS. 4, 5 and 6 are process diagrams showing another embodiment of the method for manufacturing a laminate according to the present invention. FIG. 4 is a process diagram showing another embodiment of the method for manufacturing a laminated body according to the present invention. The method for producing the laminate 110 shown in FIG. 4 is a resin composition comprising the polycarbonate-based resin composition 13 of the present embodiment containing the polycarbonate-based resin according to the present invention and the inorganic fine particles 4 on the base material 2. A step of forming a material layer (sometimes referred to as a “particle-containing resin composition layer”) 16 (FIG. 4 (a)) and a step of curing the particle-containing resin composition layer 16 (FIG. 4 (b)). , Equipped with.

FIG. 5 shows a step of forming the particle-containing resin composition layer on the substrate, and FIG. 6 shows a step of curing the particle-containing resin composition layer. In the method for producing the laminate 120 shown in FIGS. 5 and 6, a coating liquid containing the polycarbonate-based resin according to the present invention (for example, the polycarbonate-based resin composition of the present embodiment) is applied onto the base material 2. A step of forming a coating film (FIG. 5A) and a step of spraying the inorganic fine particles 4 onto the coating film to form a resin composition layer (sometimes referred to as a “particle-containing resin composition layer”) 17. (FIG. 5 (b)) and a step of curing the particle-containing resin composition layer 17 (FIG. 6 (a)).

In the laminated body 120, the inorganic fine particles 4 can be unevenly distributed on the side opposite to the base material 2 of the resin cured product layer (sometimes referred to as “particle-containing resin cured product layer”) 7. As a result, the adhesion between the particle-containing cured resin layer 7 and the base material 2 can be improved while improving the scratch resistance of the cured resin layer 7. Further, as compared with the case of the laminated body 110 shown in FIG. 2, the amount of the inorganic fine particles 4 used can be reduced, which has an advantage of being more economical.

In the present embodiment, the cured resin layer preferably contains inorganic fine particles in a proportion of 0.0001 to 70% by mass, preferably 0.0005 to 50% by mass, based on the total amount of the cured resin layer. It is more preferable to contain it.

The method of applying the polycarbonate-based resin composition in the case of producing the laminate 110 or 120 may be the same as the method of applying the above-mentioned coating agent. Further, the method of curing the particle-containing resin composition layers 16 and 17 may be the same as the case of curing the resin composition layer 15 described above. As a method of spraying the inorganic fine particles 4 in the case of producing the laminate 120, for example, the inorganic fine particles 4 may be sprayed as they are, or the inorganic fine particles 4 may be dispersed in a solvent and sprayed. The solvent is not particularly limited, and examples thereof include water, methyl ethyl ketone, and methyl isobutyl ketone. Spraying can be performed using a normal sprayer or the like.

The thickness of the coating film can be 0.1 to 150 μm.

As another method for producing the laminate according to the present invention, the material forming the base material 2 and the coating agent may be laminated by coextrusion, or each may be extruded to form a single-layer sheet. , They may be bonded by dry lamination, thermal lamination or the like.

The thickness of the cured resin layers 5, 6 and 7 is preferably about 0.1 to 50 μm, more preferably 1 to 30 μm from the viewpoint of chemical resistance.

In the laminates 100, 110 and 120, only one layer of the cured resin layer (protective layer) 5, 6 and 7 of the cured product 3 of the polycarbonate resin composition of the present embodiment is formed on the base material 2. Either the so-called one-coat type, which is composed of the primer layer forming the lower layer and the resin cured product layers 5, 6 and 7, can be selected. As the resin forming the primer layer (lower layer), a urethane resin composed of various blocked isocyanate components and a polyol component; acrylic resin; polyester resin; epoxy resin; melamine resin; amino resin; polyester acrylate, urethane acrylate, epoxy acrylate, phosphazenic acrylate. , Various polyfunctional acrylates such as melamine acrylate and amino acrylate can be mentioned. These can be used alone or in combination of two or more. Among these, acrylic resin and urethane acrylate are preferable. These can be either applied to an unreacted state and then subjected to a predetermined reaction to form a cured resin, or directly applied to the reacted resin to form a cured resin layer. The latter is usually applied by dissolving the resin in a solvent to make a solution, and then the solvent is removed. Also, in the former case, it is common to use a solvent.

The laminate according to the present invention is, for example, a touch panel provided with a protective film, a protective sheet for a touch panel, a window glass for an automobile provided with a protective film, an interior / exterior material or a wheel, a window glass for a house provided with a protective film, and an interior / exterior material. It can be applied as an optical information medium such as a floor material, a toilet bowl and kitchen equipment, a plastic lens provided with a protective film, a solar cell module, and a DVD. The protective film has excellent chemical resistance (for example, UV absorbers, preservatives, emulsifiers, solvents and UV absorbers contained in cosmetics such as liquid foundations, makeup bases, concealers, sunscreen creams, beauty essences, milky lotions, and hand creams. It can have chemical resistance to oils and fats).

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to these Examples.

<Polycarbonate resin raw material>
The following components were prepared as raw materials for the polycarbonate resin.

(A) Ingredients-PCD1: Isosorbide-based polycarbonate diol (trade name: BENEBiOL HS0840B, manufactured by Mitsubishi Chemical Corporation, hydroxyl value: 140.3 mgKOH / g, number average molecular weight: 800)
-PCD2: Cyclohexanedimethanol-based polycarbonate diol (trade name: ETERNACOLL UM90 (3/1), manufactured by Ube Industries, hydroxyl group value: 124.7 mgKOH / g, number average molecular weight: 900)
PCD3: Isosorbide-based polycarbonate diol (trade name: BENEBiOL HS0850, manufactured by Mitsubishi Chemical Corporation, hydroxyl value: 140.3 mgKOH / g, number average molecular weight: 800)

(B) Component-isophorone diisocyanate (molecular weight: 222)
Hexamethylene diisocyanate (molecular weight: 168)

(C) Component-A reaction product of two molecules of acrylic acid and one molecule of 1,6-hexanediol diglycidyl ether (trade name: DA-212, manufactured by Nagase Chemtech, molecular weight 374).
-A reaction product of two molecules of acrylic acid and one molecule of bisphenol A diglycidyl ether (trade name: DA-250, manufactured by Nagase Chemtech, molecular weight 484).

(D1) Component-2-Hydroxyethyl acrylate (molecular weight: 116)
-Pentaerythritol triacrylate (molecular weight: 298)

(E) Component-PCD4: Polyhexamethylene carbonate diol (hydroxyl value: 112.2 mgKOH / g, number average molecular weight: 1000)
-PTMG: Polytetramethylene glycol (hydroxyl value: 172.6 mgKOH / g, number average molecular weight 650)

<Inorganic fine particles>
The following inorganic fine particles were prepared.
-NanoDia: (Product name: V-diamond, manufactured by Vision Development, average particle size: 200 nm)
-Silica: (Product name: MEK-ST-ZL, manufactured by Nissan Chemical Industries, Ltd., average particle size: 83 nm, methyl ethyl ketone dispersion type, silica content 30% by mass)

<Synthesis of polycarbonate resin>
[Synthesis Example 1]
160.6 g of PCD1, 89.2 g of isophorone diisocyanate, 62.5 g of methyl ethyl ketone as a urethane reaction catalyst in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a blow tube for a mixed gas of nitrogen and oxygen. 0.05 g of bismastris (2-ethylhexanoate) was added and reacted at 80 to 90 ° C. for 1 hour to obtain a urethane prepolymer having a free isocyanate group content of 5.4% by mass. After cooling to 60 ° C., 0.4 g of hydroquinone monomethyl ether, 0.05 g of bismastris (2-ethylhexanoate) and 37.6 g of methyl ethyl ketone are added as polymerization inhibitors, and 150.2 g of DA-212 is added dropwise to 70. The reaction was carried out at ~ 90 ° C. for 3 hours to obtain a polyurethane acrylate-based polycarbonate resin composition containing 20% by mass of methyl ethyl ketone, that is, the resin component concentration of the resin composition was 80% by mass. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the components (A) and (E) used as raw materials was 100% by mass (that is, the blending amount of the component (E) was 0% by mass). .. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.5: was 1.0. The double bond equivalent of the obtained polycarbonate resin is 498 g / eq.

[Synthesis Example 2]
160.6 g of PCD1, 150.2 g of DA-212, 89.2 g of isophorone diisocyanate, and methyl ethyl ketone in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a blow tube for a mixed gas of nitrogen and oxygen. Add 100.0 g, 0.4 g of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.05 g of bismastris (2-ethylhexanoate) as a urethane reaction catalyst, and react at 70 to 90 ° C. for 3 hours to contain a free isocyanate group. Was 0.0% by mass, and a polyurethane acrylate-based polycarbonate resin composition having a resin component concentration of 80% by mass, which contained 20% by mass of methyl ethyl ketone, was obtained. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 100% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.5: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 498 g / eq.

[Synthesis Example 3]
155.7 g of PCD2, 76.8 g of isophorone diisocyanate, 58.1 g of methyl ethyl ketone, as a urethane reaction catalyst in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a blow tube for a mixed gas of nitrogen and oxygen. 0.05 g of bismastris (2-ethylhexanoate) was added and reacted at 80 to 90 ° C. for 1 hour to obtain a urethane prepolymer having a free isocyanate group content of 5.0% by mass. After cooling to 60 ° C., 0.4 g of hydroquinone monomethyl ether, 0.05 g of bismastris (2-ethylhexanoate) and 41.9 g of methyl ethyl ketone are added as polymerization inhibitors, and 167.5 g of DA-250 is added dropwise to 70. The reaction was carried out at ~ 90 ° C. for 3 hours to obtain a polyurethane acrylate-based polycarbonate resin composition containing 20% by mass of methyl ethyl ketone, that is, the resin component concentration of the resin composition was 80% by mass. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 100% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.5: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 578 g / eq.

[Synthesis Example 4]
255.6 g of PCD3, 67.1 g of hexamethylene diisocyanate, 80.7 g of methyl ethyl ketone, urethane in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a blow tube for a mixed gas of nitrogen and oxygen. 0.06 g of bismastris (2-ethylhexanoate) was added as a reaction catalyst and reacted at 80 to 90 ° C. for 2 hours to obtain a urethane prepolymer having a free isocyanate group content of 5.0% by mass. After cooling to 60 ° C., 0.4 g of hydroquinone monomethyl ether, 0.06 g of bismastris (2-ethylhexanoate) and 19.3 g of methyl ethyl ketone were added as polymerization inhibitors, and 77.3 g of DA-250 was added dropwise to 70. The reaction was carried out at ~ 90 ° C. for 3 hours to obtain a polyurethane acrylate-based polycarbonate resin composition containing 20% by mass of methyl ethyl ketone, that is, the resin component concentration of the resin composition was 80% by mass. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 100% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.2: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 1252 g / eq.

[Synthesis Example 5]
293.3 g of PCD3, 25.3 g of DA-250, 81.4 g of isophorone diisocyanate, and methyl ethyl ketone in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a blowing tube for a mixed gas of nitrogen and oxygen. Add 100.0 g, 0.4 g of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.08 g of bismastris (2-ethylhexanoate) as a urethane reaction catalyst, and react at 70 to 90 ° C. for 3 hours to contain a free isocyanate group. Was 0.0% by mass, and a polyurethane acrylate-based polycarbonate resin composition having a resin component concentration of 80% by mass, which contained 20% by mass of methyl ethyl ketone, was obtained. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 100% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.1: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 3819 g / eq.

[Synthesis Example 6]
148.6 g of PCD3, 86.2 g of PTMG, 51.4 g of DA-250, hexamethylene diisocyanate in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a blowing tube for a mixed gas of nitrogen and oxygen. 89.2 g, methyl ethyl ketone 93.8 g, hydroquinone monomethyl ether 0.4 g as a polymerization inhibitor, and bismastris (2-ethylhexanoate) 0.08 g as a urethane reaction catalyst, and the reaction was carried out at 70 to 90 ° C. for 3 hours. A urethane prepolymer having a free isocyanate group content of 1.9% by mass was obtained. After cooling to 60 ° C., 0.08 g of bismastris (2-ethylhexanoate) and 6.2 g of methyl ethyl ketone are added, 24.6 g of 2-hydroxyethyl acrylate is added dropwise, and the mixture is reacted at 70 to 90 ° C. for 3 hours. A polyurethane acrylate-based polycarbonate-based resin composition containing 20% by mass of methyl ethyl ketone, that is, having a resin component concentration of 80% by mass in the resin composition was obtained. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 63% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.0: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 942 g / eq.

[Synthesis Example 7]
78.8 g of PCD3, 36.8 g of DA-212, 49.6 g of hexamethylene diisocyanate, methyl ethyl ketone in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a blowing tube of a mixed gas of nitrogen and oxygen. 41.3 g, hydroquinone monomethyl ether 0.4 g as a polymerization inhibitor, and 0.03 g of bismastris (2-ethylhexanoate) as a urethane reaction catalyst were added and reacted at 70 to 90 ° C. for 3 hours to contain a free isocyanate group. A urethane prepolymer having an amount of 4.0% by mass was obtained. After cooling to 60 ° C., 0.03 g of bismastris (2-ethylhexanoate) and 58.7 g of methyl ethyl ketone are added, and 234.8 g of pentaerythritol triacrylate is added dropwise and reacted at 70 to 90 ° C. for 5 hours. , 20% by mass of methyl ethyl ketone, that is, a polyurethane acrylate-based polycarbonate-based resin composition having a resin component concentration of 80% by mass in the resin composition was obtained. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 100% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 2.0: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 156 g / eq.

[Synthesis Example 8]
173.9 g of PCD1, 81.3 g of DA-212, 144.8 g of isophorone diisocyanate, and methyl ethyl ketone in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a blowing tube for a mixed gas of nitrogen and oxygen. Add 100.0 g, 0.4 g of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.08 g of bismastris (2-ethylhexanoate) as a urethane reaction catalyst, and react at 70 to 90 ° C. for 3 hours to contain a free isocyanate group. Was 3.7% by mass, and a polyurethane acrylate-based polycarbonate resin composition having a resin component concentration of 80% by mass, which contained 20% by mass of methyl ethyl ketone, was obtained. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 100% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 0.7: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 920 g / eq.

[Synthesis Example 9]
99.3 g of DA-212, 88.4 g of isophorone diisocyanate, 46.9 g of methyl ethyl ketone, polymerization prohibited in a 4-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a blowing tube for a mixed gas of nitrogen and oxygen. 0.4 g of hydroquinone monomethyl ether as an agent and 0.04 g of bismastris (2-ethylhexanoate) as a urethane reaction catalyst were added and reacted at 70 to 90 ° C. for 3 hours, and the free isocyanate group content was 4.8% by mass. Urethane prepolymer was obtained. After cooling to 60 ° C., 0.04 g of bismastris (2-ethylhexanoate) and 53.1 g of methyl ethyl ketone are added, 212.3 g of PCD3 is added dropwise, and the mixture is reacted at 70 to 90 ° C. for 5 hours to react with methyl ethyl ketone 20. A polyurethane acrylate-based polycarbonate resin composition containing% by mass, that is, having a resin component concentration of 80% by mass was obtained. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 100% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.3: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 754 g / eq.

[Synthesis Example 10]
238.7 g of PCD4, 106.0 g of isophorone diisocyanate, 86.2 g of methyl ethyl ketone as a urethane reaction catalyst in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a blow-in tube for a mixed gas of nitrogen and oxygen. 0.07 g of bismastris (2-ethylhexanoate) was added and reacted at 80 to 90 ° C. for 2 hours to obtain a urethane prepolymer having a free isocyanate group content of 4.7% by mass. After cooling to 60 ° C., 0.4 g of hydroquinone monomethyl ether, 0.07 g of bismastris (2-ethylhexanoate) and 13.8 g of methyl ethyl ketone were added as polymerization inhibitors, and 55.3 g of 2-hydroxyethyl acrylate was added dropwise. The reaction was carried out at 70 to 90 ° C. for 3 hours to obtain a polyurethane acrylate-based polycarbonate resin composition containing 20% by mass of methyl ethyl ketone, that is, the resin component concentration of the resin composition was 80% by mass. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 0% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.0: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 838 g / eq.

[Synthesis Example 11]
182.5 g of PCD4, 136.5 g of DA-212, 81.0 g of isophorone diisocyanate, and methyl ethyl ketone in a four-necked flask equipped with a stirrer, a reflux cooling tube, a thermometer, and a blowing tube for a mixed gas of nitrogen and oxygen. Add 100.0 g, 0.4 g of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.08 g of bismastris (2-ethylhexanoate) as a urethane reaction catalyst, and react at 70 to 90 ° C. for 3 hours to contain a free isocyanate group. Was 0.0% by mass, and a polyurethane acrylate-based polycarbonate resin composition having a resin component concentration of 80% by mass, which contained 20% by mass of methyl ethyl ketone, was obtained. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 0% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.5: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 548 g / eq.

[Synthesis Example 12]
216.8 g of PCD1, 120.3 g of isophorone diisocyanate, 84.3 g of methyl ethyl ketone, as a urethane reaction catalyst in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a blow tube for a mixed gas of nitrogen and oxygen. 0.07 g of bismastris (2-ethylhexanoate) was added and reacted at 80 to 90 ° C. for 1 hour to obtain a urethane prepolymer having a free isocyanate group content of 5.4% by mass. After cooling to 60 ° C., 0.4 g of hydroquinone monomethyl ether, 0.07 g of bismastris (2-ethylhexanoate) and 15.7 g of methyl ethyl ketone were added as polymerization inhibitors, and 62.9 g of 2-hydroxyethyl acrylate was added dropwise. The reaction was carried out at 70 to 90 ° C. for 4 hours to obtain a polyurethane acrylate-based polycarbonate resin composition containing 20% by mass of methyl ethyl ketone, that is, the resin component concentration of the resin composition was 80% by mass. All the above reactions were carried out while blowing the above mixed gas.

The ratio of the component (A) to the total mass of the component (A) and the component (E) used as the raw material was 100% by mass. The ratio of the sum of the number of moles M _C of (A) the number of moles of components of hydroxyl M _A and the component (C) of the hydroxyl groups used as the raw material, the number of moles M _B of the isocyanate groups of component (B), (M _{a + M C) :( M B} ) = 1.0: was 1.0. The double bond equivalent of the obtained polycarbonate resin was 738 g / eq.

The amounts of the component (A), the component (B), the component (C), the component (d1) and the component (E) used in each of the above synthetic examples are shown in Tables 1 to 3. The unit of the numerical value of each component amount in Tables 1 to 3 is "g".

(Preparation of laminated body)
[Example 1]
After diluting 100 g of the composition (composition 1) of Synthesis Example 1 with methyl ethyl ketone and adjusting the concentration of the polycarbonate resin composition to 40% by mass, 1.6 g of Irgacure 184 (manufactured by BASF Japan) as a photopolymerization initiator. Mixing gave a coating. The coating agent was applied to a polycarbonate resin plate with a bar coater so that the film thickness after drying was 10 μm. ^{Dry at 60 ° C for 10 minutes in a hot air dryer, and irradiate 500 mJ / cm 2} with an ultraviolet irradiation device (product name: EYE GRANDAGE ECS-301, manufactured by Eye Graphics, light source: metal halide) to cure the resin. A layer (protective film) was formed. A laminated body was produced by the above method.

[Example 2]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 2 (composition 2).

[Example 3]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 3 (composition 3).

[Example 4]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 4 (composition 4).

[Example 5]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 5 (composition 5).

[Example 6]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 6 (composition 6).

[Example 7]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 7 (composition 7).

[Example 8]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 8 (composition 8).

[Example 9]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 9 (composition 9).

[Comparative Example 1]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 10 (composition 10).

[Comparative Example 2]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 11 (composition 11).

[Comparative Example 3]
A laminate was prepared by the same method as in Example 1 except that the composition 1 of Example 1 was changed to the composition of Synthesis Example 12 (composition 12).

[Example 10]
After diluting 100 g of the composition (composition 1) of Synthesis Example 1 with methyl ethyl ketone and adjusting the concentration of the polycarbonate resin composition to 40% by mass, 0.08 g of nanodiamond and irgacure 184 (BASF Japan) as a photopolymerization initiator (Manufactured) was mixed in an amount of 1.6 g to obtain a coating agent. The coating agent was applied to a polycarbonate resin plate with a bar coater so that the film thickness after drying was 10 μm. ^{Dry at 60 ° C for 10 minutes in a hot air dryer, and irradiate 500 mJ / cm 2} with an ultraviolet irradiation device (product name: EYE GRANDAGE ECS-301, manufactured by Eye Graphics, light source: metal halide) to cure the resin. A layer (protective film) was formed. A laminated body was produced by the above method.

[Example 11]
A laminate was prepared by the same method as in Example 10 except that the blending amount of nanodiamond in Example 10 was changed to 0.8 g.

[Example 12]
A laminate was prepared in the same manner as in Example 10 except that 0.08 g of nanodiamond in Example 10 was changed to 34.3 g of silica.

[Example 13]
A laminate was prepared by the same method as in Example 11 except that the composition 1 of Example 11 was changed to the composition of Synthesis Example 2 (composition 2).

[Example 14]
A laminate was prepared by the same method as in Example 11 except that the composition 1 of Example 11 was changed to the composition of Synthesis Example 7 (composition 7).

[Example 15]
A laminate was prepared by the same method as in Example 11 except that the composition 1 of Example 11 was changed to the composition of Synthesis Example 8 (composition 8).

[Comparative Example 4]
A laminate was prepared by the same method as in Example 11 except that the composition 1 of Example 11 was changed to the composition of Synthesis Example 10 (composition 10).

[Comparative Example 5]
A laminate was prepared by the same method as in Example 11 except that the composition 1 of Example 11 was changed to the composition of Synthesis Example 11 (composition 11).

The amounts of the components used in each of the above Examples and Comparative Examples are shown in Tables 4 to 8. In Tables 4 to 8, the unit of each component amount is "g".

The obtained laminate was evaluated for initial adhesion, chemical resistance and scratch resistance by the methods shown below. The evaluation results are shown in Tables 4-8.

<Initial adhesion>
In accordance with JIS K5600-5-6 (1999), 11 vertical and horizontal cuts at 1 mm intervals were made in the resin cured product layer (protective film) of the produced laminate with a cutter knife to form a 100-square grid. A cellophane tape manufactured by Nichiban Co., Ltd. was attached on the grid, and the cellophane tape was peeled off. Adhesion was evaluated by the number of squares of the residual film after peeling of the cellophane tape, and the case where 95 or more sheets remained was regarded as acceptable.

<Chemical resistance>
For chemical resistance evaluation, use sunscreen cream (trade name: Neutrogena Ultra Sheer DRY-TOUCH SUNBLOCK SPF45), (trade name: Nivea SUN LIGHT FEELING SPF50), and add about 0.5 g of Neutrogena or hand cream onto the cured product. Spread it into a circle with a diameter of 1 cm, apply it, heat it in an oven at 80 ° C. for 24 hours, wipe the surface with a Kim towel, and observe the state of the coating film. Chemical resistance was evaluated according to the following criteria. Those with no change on the surface, those with transparent marks on the surface, and those with slight whitening on the surface were accepted.
◎; No change ○; There is a transparent mark on the surface △; There is a slight whitening on the surface ×; The coating film is destroyed and becomes white or swollen

<Scratch resistance>
The resin cured product layer (protective film) of the produced laminate is ^{reciprocated 20 times with a load of 1000 g / cm 2} using # 0000 steel wool, and the presence or absence of scratches on the protective film is visually checked according to the following criteria. The ones that are not easily scratched were evaluated as good.
⊚: No scratches after 20 round trips ○: Scratches occur after 10 round trips or more and less than 20 round trips △: Scratches occur after 5 round trips or more and less than 10 round trips ×: Scratches occur after 5 round trips

As is clear from the results shown in Tables 4 to 6, it was confirmed that the laminate of the present embodiment has high chemical resistance. As is clear from the results shown in Tables 7 and 8 by further blending fine particles, it was confirmed that the laminate of the present embodiment has high chemical resistance and scratch resistance.

According to the present invention, it is possible to impart high chemical resistance by laminating a cured resin layer (protective layer) on a base material such as a resin. Therefore, by applying the laminate of the present invention to, for example, window glass for automobiles, interior / exterior materials, etc., it becomes possible to replace it with a lightweight resin material, which is very useful for reducing the weight of automobiles.

2 ... Substrate, 3 ... Cured product, 4 ... Inorganic fine particles, 5 ... Resin cured product layer, 6, 7 ... Resin cured product layer (particle-containing resin cured product layer), 13 ... Polycarbonate resin composition, 15 ... Resin Composition layer, 16, 17 ... Resin composition layer (particle-containing resin composition layer), 100, 110, 120 ... Laminate, L ... Active energy ray.

Claims (10)

A base material and a resin cured product layer containing a cured product of the resin composition provided on the base material are provided.
Said resin composition, see contains at least the following component (A), the following component (B) and the following component (C), polycarbonate-based resin obtained by reacting,
A laminate in which the polycarbonate resin has a divalent organic group represented by the following chemical formula (A-1) .
(A) Component: Polycarbonate polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom (B) Component: Polyisocyanate compound (C) Ingredients: (meth) acryloyl group-containing polyol having at least one (meth) acryloyl group and two or more hydroxyl groups in the molecule

The laminate according to claim 1, wherein the cured resin layer further contains inorganic fine particles. The laminate according to claim 1 or 2 , wherein the polycarbonate-based resin is at least a resin obtained by reacting the reaction product of the component (A) and the component (B) with the component (C). body. See containing at least the following component (A), the following component (B) and the following component (C), polycarbonate-based resin obtained by reacting,
A coating agent in which the polycarbonate-based resin has a divalent organic group represented by the following chemical formula (A-1).
(A) Component: Polycarbonate polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom (B) Component: Polyisocyanate compound (C) Ingredients: (meth) acryloyl group-containing polyol having at least one (meth) acryloyl group and two or more hydroxyl groups in the molecule

The coating agent according to claim 4 , further comprising inorganic fine particles. The coating agent according to claim 5, wherein the polycarbonate-based resin is a resin obtained by reacting at least the reaction product of the component (A) and the component (B) with the component (C). A step of providing a resin composition layer on a base material and a step of curing the resin composition layer to form a cured resin composition layer are provided.
Said resin composition layer, see contains at least the following component (A), the following component (B) and the following component (C), polycarbonate-based resin obtained by reacting,
A method for producing a laminate, wherein the polycarbonate resin has a divalent organic group represented by the following chemical formula (A-1).
(A) Component: Polycarbonate polyol having a skeleton in which at least one carbon atom of the alicyclic skeleton or the alicyclic skeleton is replaced with an oxygen atom, a nitrogen atom or a sulfur atom (B) Component: Polyisocyanate compound (C) Ingredients: (meth) acryloyl group-containing polyol having at least one (meth) acryloyl group and two or more hydroxyl groups in the molecule

The method for producing a laminate according to claim 7 , wherein the resin composition layer further contains inorganic fine particles. The eighth aspect of the present invention, wherein the resin composition layer is formed through a step of applying the resin composition on the substrate to form a coating film and a step of spraying the inorganic fine particles on the coating film. The method for manufacturing a laminate according to the description. Any one of claims 7 to 9 , wherein the polycarbonate-based resin is at least a resin obtained by reacting the reaction product of the component (A) and the component (B) with the component (C). The method for manufacturing a laminate according to the section.

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