KR101347684B1

KR101347684B1 - Laminate for display protection

Info

Publication number: KR101347684B1
Application number: KR1020120115742A
Authority: KR
Inventors: 전승호; 박창규; 박종; 이종성
Original assignee: 주식회사 폴리사이언텍
Priority date: 2012-10-18
Filing date: 2012-10-18
Publication date: 2014-01-06

Abstract

The present invention relates to a laminate comprising: a base layer consisting of a polycarbonate-based resin (A); and a skin layer consisting of one selected from a copolymer resin (B) of crosslinkable monomers including (matte) acrylic ester and a fluorine structure and a ring-shaped polyolefin resin (C) including a hydrophilic group or a mixture (D) thereof or a protective plate for a display including the same. The present invention exhibits excellent transparency, impact resistance, wet-proof properties and scratch resistance and is usefully used in display fields such as a display for a personal digital assistant and the like by having excellent flexure protection properties.

Description

Laminates for Display Protection {LAMINATE FOR DISPLAY PROTECTION}

The present invention relates to a laminate that can be used as a display protection plate such as a display window of a portable information terminal having excellent transparency, impact resistance, moisture resistance and scratch resistance, as well as excellent bending resistance.

With the advent of smartphones such as Galaxy and iPhone, the adoption of tempered glass such as Corning's product name Gorilla and Asahi Glass's product name Dragon trial has increased significantly in the display protection market, while its impact resistance and moisture resistance are inferior, but excellent transparency and scratch resistance. Double-sided hard-coated single-layered acrylic resin sheet and scratch resistance are poor, but double-sided hard-coated single-layered polycarbonate resin sheet with excellent transparency, impact resistance and moisture resistance is used for smartphone, feature phone, navigation, MP-3, It is rapidly contracting in the display protection market such as PMP, game consoles and cameras.

This is because the operation principle of the smartphone is related to the use of the capacitive method based on the touch screen panel and the relatively large screen. Tempered glass is adopted in consideration of the constant touch, the smoothness of the large screen, and the dimensional stability. It seems to be.

However, the tempered glass is heavy, poor workability and expensive, has a big disadvantage is actively developing a display protection plate to replace it. In general, display protection plates require scratch resistance of at least H before hard coating, and final display protection plates, which have undergone hard coating, require products of 4H or more, preferably 5H or more. For example, original molded polycarbonate resins only. Silver transparency, impact resistance, moisture resistance, heat resistance, etc. are very good, but unfortunately the pencil hardness is 2B ~ B, so scratch resistance is very poor, even if hard coating, it is only H ~ 2H level with the current technology. It is used only as a protector and cannot be used as an advanced display protector like a smartphone.

Similarly, a disc made of conventional acrylic resin, which is a copolymer resin with polymethyl methacrylate homopolymer or other acrylic monomer, comonomer such as styrene and other vinyl monomer, has excellent transparency and scratch resistance at the level of 2H to 4H. Although it is excellent, there is a problem inferior in terms of impact resistance, moisture resistance and heat resistance. Examples of prior art developments to improve this include copolymers of styrene and maleic anhydride (Japanese Patent Publication No. 1983-40970), copolymers of α-methyl styrene and maleic anhydride (Japanese Patent Publication No. 1992-300907), styrene And copolymers with maleic anhydride (Japanese Patent Laid-Open No. 1992-227613), copolymers with α-methyl styrene, styrene and maleic anhydride (Japanese Patent Laid-Open No. 1986-271313) have been proposed, but copolymers with maleic anhydride have been proposed. Has problems of stability during molding, problems such as decomposition or gel formation due to high molding processing temperature, and other copolymers with styrene and maleimide monomers (Korean Patent Application No. 10-2005-0037739), Many research and development cases have been reported, including copolymers of isobonyl methacrylate substituted with alkyl groups at 5,5,6 and alpha-substituted vinyl monomers (Korean Patent Application No. 10-2005-0055481). However, the quality improvement in terms of impact resistance, moisture resistance, and heat resistance is not sufficient, and thus, an original plate (or a hard coating layer) made of these acrylic resins alone is insufficient to be used as a display protection plate, especially as a high-end display protection plate. .

In particular, as the demand for long-term reliability of electric and telecommunication products has been strengthened, high temperature and humidity resistance is required to allow only a dimensional change of less than 0.02% after standing at 85 ° C, 85% RH, and 72 hours even in the case of a display protection plate. The market for acrylic resin protective plates, which were mainly used as windows of the film, is shrinking even more due to lack of moisture resistance.

As a result, research on multilayered laminates using two or more resins instead of a single resin attracted great attention. As a development example, a conventional polycarbonate-based resin having excellent transparency, impact resistance, and moisture resistance was used as a base material. As a skin layer raw material exposed to scratches and having excellent transparency and scratch resistance, a copolymer of methyl methacrylate and styrene (Japanese Patent Application No. 2008-207050), a copolymer of methyl methacrylate and acrylic acid ester (Korean patent) Application of 10-2009-7009932, etc.), developed a product that double-sided hard-coated laminate of two-layer structure manufactured by co-extrusion using conventional acrylic resin to protect some smartphones thanks to the light and low cost advantages compared to tempered glass As it is applied to resin plates, the market is rapidly growing rapidly.

However, the laminated body having a two-layer structure consisting of a base layer made of a double-sided hard-coated polycarbonate resin and a skin layer made of a conventional acrylic resin has a glass transition temperature of 140 to 155 ° C. The thermal properties such as glass transition temperature are significantly different from the conventional acrylic resin having a temperature of 110 ~ 120 ℃, and curvature occurs seriously in the laminate molding cooling process. Both edges are treated as defective products, resulting in a significant cost increase due to a significant decrease in yield, and even products shipped as good products also suffer from additional surface warpage during hard coating and printing drying processes. There is a serious problem that can be solved dramatically, not only has excellent bending resistance, but also There is an urgent need for the emergence of a new display protection plate manufacturing technology with a high degree of transparency, impact resistance, moisture resistance and scratch resistance.

Japanese Patent Laid-Open No. 1983-40970 Japanese Patent Laid-Open No. 1992-300907 Japanese Patent Laid-Open No. 1992-227613 Japanese Patent Laid-Open No. 1986-271313 Republic of Korea Patent Application No. 2005-0037739 Republic of Korea Patent Application No.2005-0055481 Japanese Patent Application No. 2008-207050 Republic of Korea Patent Application No.2009-7009932

SUMMARY OF THE INVENTION An object of the present invention is to provide a display protective plate such as a laminate having excellent transparency, impact resistance, moisture resistance, and scratch resistance, as well as excellent bending preventing characteristics, or a display window of a portable information terminal including such a laminate. Considering the problems in the prior art, a two-layered hard-coated polycarbonate-based resin (substrate layer) / copolymer of methyl methacrylate and styrene or a copolymer of methyl methacrylate and acrylic ester (skin layer) The laminate had a good transparency, impact resistance, and scratch resistance, but the thermal properties such as glass transition temperature between the base layer and skin layer resins were largely different, causing large area smoothness due to warpage to be greatly damaged. Although the skin layer is small in view, the acrylic resin is slightly inferior in moisture resistance and needs to be improved in view of the recently enhanced moisture resistance reliability requirements. The present inventors use a polycarbonate-based resin having excellent transparency, impact resistance and moisture resistance as a base layer, and in selecting a new skin layer material, it has properties that can be extruded once, and has excellent transparency and surface characteristics (contact angle, etc.) It is similar to the resin and does not cause layer separation after co-extrusion, and has low saturation absorption rate compared with the conventional acrylic resin to improve moisture resistance, high surface hardness, excellent scratch resistance, and above all, glass transition between the base layer and the skin layer resin. In the search for a resin having a low temperature difference, a copolymer resin of a (meth) acrylic acid ester and a crosslinkable monomer containing a fluorene structure, a cyclic polyolefin resin with appropriate conditions, and a mixture thereof may be very suitable as a material for a new skin layer. Focusing on the fact that it can be carried out with intensive research and development to complete the present invention It became.

The object of the present invention comprises a copolymer resin (B) and a hydrophilic group of a crosslinkable monomer comprising a base layer and a (meth) acrylic acid ester and a fluorene structure of the polycarbonate resin (A) The present invention has been completed by providing a display protective plate such as a laminate including a skin layer composed of one or a mixture (D) selected from the cyclic polyolefin resin (C) or a display window of a portable information terminal including the laminate. .

In order to solve the above problems, the present invention is a substrate layer made of a polycarbonate resin (A); And a copolymer resin (B) of a crosslinkable monomer having a (meth) acrylic acid ester and a fluorene structure and a cyclic polyolefin-based resin (C) including a hydrophilic group, or a mixture thereof (D). It is an object of the present invention to provide a laminate comprising a skin layer, or a protective plate for a display including the same.

In the laminate of the present invention, a skin layer may be laminated on one or both surfaces of the base layer, wherein the (meth) acrylic acid ester has an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. It may be any one or more selected from the group consisting of alkyl acrylates, glycidyl (meth) acrylates, preferably the alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate It is one or more selected from the group consisting of acrylate, butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, more preferably the alkyl methacrylate Is methyl methacrylate, and the alkyl acrylate is methyl acrylate, ethyl acrylate, It is at least one selected from the group consisting of ropil acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate sayikeu may be.

In addition, in the present invention, the crosslinkable monomer including the fluorene structure may be a compound of Formula 1 below.

[Formula 1]

(In Chemical Formula 1, R ₁ is carbon number 1 To alkyl groups of 8 to 8, R ₂ represents a hydrogen atom or a methyl group)

In the copolymer resin (B) of the (meth) acrylic acid ester and the crosslinkable monomer including the fluorene structure, the content of the crosslinkable monomer including the fluorene structure may be 1 to 20% by weight.

In the present invention, the hydrophilic group of the cyclic polyolefin-based resin (C) containing the hydrophilic group is hydroxyl group, ester group, organic acid group, organic acid salt group, organic acid anhydride group, amine group, ammonium group, cyano group, acetate group, ether group, epoxy group, It may be at least one selected from the group consisting of halogen groups, preferably at least one of the following formula (2) to (7).

(2)

(Ra and Rb in the formula (2) is the same or different, any one of a hydroxyl group, ester group, organic acid group, organic acid salt group, organic acid anhydride group, amine group, ammonium group, cyano group, acetate group ether group, epoxy group, halogen group, Ra and Rb may combine with each other to form a ring, where l is 0 or an integer of 1 or more, and m is an integer ranging from 1 to 2,000.)

(3)

(In Formula 3, Rc and Rd are the same or different, any one of a hydroxyl group, ester group, organic acid group, organic acid salt group, organic acid anhydride group, amine group, ammonium group, cyano group, acetate group ether group, epoxy group, halogen group, Rc and Rd may be bonded to each other to form a ring, p is an integer of 0 or more than 1, q and r are integers in the range of 1 to 2,000, and the molar ratio of q: r is a ratio of 0.01 to 0.99: 0.99 to 0.01. Have.)

[Chemical Formula 4]

(In Formula 4, R is an alkyl group having 1 to 20 carbon atoms, n is an integer ranging from 1 to 2,000.)

[Chemical Formula 5]

(In Formula 5, R is an alkyl group having 1 to 20 carbon atoms, p and q are integers in the range of 1 to 2,000, the molar ratio of p: q has a ratio of 0.01 to 0.99: 0.99 to 0.01.)

[Chemical Formula 6]

(In Formula 6, R is an alkyl group having 1 to 20 carbon atoms, M is any one of metal ions selected from alkali metals, alkaline earth metals, transition metals, p, q and r are independently of each other of 1 to 2,000 And a molar ratio of p: q: r is available in the range of 0.01 to 0.99, respectively.)

[Formula 7]

In Formula 7, n is an integer of 1 to 20, X is any one of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, p and q are integers in the range of 1 to 2,000, and the molar ratio of p: q is 0.01 to 0.99. : It has a ratio of 0.99 to 0.01.)

In addition, in the present invention, the surface characteristics of the resin constituting the skin layer may be in the range of 50 ° to 90 ° based on the contact angle, and preferably in the range of 60 ° to 80 °.

The weight average molecular weight of the resin constituting the skin layer of the present invention is in the range of 30,000 to 100,000, more preferably in the range of 50,000 to 80,000. Tg when the glass transition temperature of the polycarbonate-based resin (A) forming the base layer is Tg (A) and the glass transition temperature of the resin (B, C or D) forming the skin layer is Tg (B, C or D). The difference between (A) and Tg (B, C or D) is 20 ° C. or less, preferably 15 ° C. or less.

In the present invention, the base layer and the skin layer may be laminated by coextrusion molding, and the resin constituting the skin layer may be a copolymer resin (B) of a crosslinkable monomer comprising a (meth) acrylic acid ester and a fluorene structure. Cyclic polyolefin-based resin (C) containing a hydrophilic group may be composed of a mixture (D) of 10/90 to 90/10% by weight.

In addition, in the present invention, the thickness of the base layer may be 70 to 97% of the total, and the thickness of the skin layer may be 3 to 30%, and the UV absorber may be 0.005 to 3 wt% in addition to the resin of the base layer or / and the skin layer. It may be contained. In addition, the resin of the base layer or / and skin layer may further contain one or more selected from the group consisting of a release agent, processing aids, lubricants, antioxidants, colorants, light diffusing agents, flame retardants, antistatic agents and dyes. .

The present invention also relates to a protective plate for a display comprising the above laminate. The protective plate may further comprise a hard coat layer on the surface of the base layer or / and the skin layer, it is preferable that the total thickness of the protective plate is 0.3 ~ 1.5 mm. In addition, the display may preferably be a protective plate for protecting a panel of a portable information terminal.

The laminate of the multi-layer structure according to the present invention has a two-layer structure composed of a base layer 10 and a one-side skin layer 20 as shown in Fig. 1 (a) and as shown in Fig. 1 (b). The three layer structure comprised from the base material layer 10 and the double-sided skin layer 20 is included.

The display protective plate of the multi-layer structure according to the present invention has a three-layer structure consisting of a base layer 10, one side skin layer 20 and one side hard coating layer 30 exposed, as shown in Figure 2 (a), As shown in FIG. 2 (b), a four-layer structure composed of a base layer 10, one side skin layer 20, and a double-sided hard coating layer 30, and a base layer as shown in FIG. 10), the four-layer structure consisting of the one-sided hard coating layer 30 exposed to the double-sided skin layer 20 and the substrate layer 10, the double-sided skin layer 20, and both sides as shown in Figure 2 (d) It includes a five-layer structure consisting of a hard coating layer (30).

In the present invention, as the polycarbonate resin (A), for example, a polymer obtained by reacting at least one divalent phenol and at least one carbonylating agent by an interfacial polycondensation method, a melt transesterification method, or the like, and a carbonate prepolymer may be used as a solid phase transesterification method. The polymer etc. which are obtained by superposing | polymerizing the polymer obtained by superposition | polymerization by the cyclic | annular and cyclic carbonate compound by a ring-opening polymerization method, etc. are mentioned. Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane and bis {(4-hydroxy-3,5- Dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) Propane (commonly known as bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2 , 2-bis {(4-hydroxy-3,5-dibromo) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis { (4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2- Bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2, 2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxy Cifetyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9 , 9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α'-bis (4-hydroxyphenyl) -o -Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1, 3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'- Dihydroxy diphenyl sulfide, 4,4'- dihydroxy diphenyl ketone, 4,4'- dihydroxy diphenyl ether, 4,4'- dihydroxy diphenyl ester, and the like. Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) - 3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 Dihydric phenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene alone, or It is preferable to use 2 or more types, and especially the homopolymer of bisphenol A, the copolymer of bisphenol A, and 1, 1-bis (4-hydroxyphenyl) -3, 3, 5- trimethyl cyclohexane, 2,2 with bisphenol A Of at least one divalent phenol selected from the group consisting of -bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene Copolymers are preferred. Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, and haloformates such as dihaloformates of dihydric phenol.

In the present invention, the molecular weight of the polycarbonate-based resin (A) is in the range of 1.0 to 15.0, preferably based on the melt index (300 ° C., 1.2 Kg), from the viewpoint that the laminate can be produced by conventional extrusion molding. Is preferably in the range of 5.0 to 10.0. You may add various additives, such as a ultraviolet absorber, a mold release agent, a processing aid, a lubricating agent, antioxidant, a coloring agent, a light diffusing agent, a flame retardant, an antistatic agent, and a salt pigment, generally used to polycarbonate resin (A).

In the copolymer resin (B) of the (meth) acrylic acid ester and the fluorene structure-containing crosslinkable monomer according to the present invention, the (meth) acrylic acid ester may be methyl methacrylate, ethyl methacrylate, propyl methacrylate, Alkyl methacrylates having 1 to 20 carbon atoms such as butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, lauryl methacrylate and stearyl methacrylate, methyl acrylate and ethyl acryl Alkyl acrylates having 1 to 20 carbon atoms, glycidyl (meth) such as acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, lauryl acrylate and stearyl acrylate Acrylate etc. are mentioned, Among these, methyl methacrylate is the most preferable.

In the copolymer resin (B) of the (meth) acrylic acid ester according to the present invention with a crosslinkable monomer containing a fluorene structure, the fluorene structure-containing crosslinkable monomer is a compound represented by the following formula (1), and specific examples thereof include Gas chemical company, brand names OGSOL Grade EA-0200, EA-F5003, EA-F5503, EA-F5510 are mentioned.

[Formula 1]

In the present invention, the surface properties of the copolymer resin (B) of the (meth) acrylic acid ester with the fluorene structure-containing crosslinkable monomer are generally 65 ° to 75 ° with a contact angle of the polycarbonate-based resin (B), which is a raw material for the base layer. Considering the level, it is preferable that the contact angle is in the range of 50 to 90 °, preferably in the range of 60 ° to 80 °. If the contact angle is less than 50 ° or more than 90 °, there is a fear of layer separation after coextrusion.

In the present invention, the glass transition temperature of the polycarbonate-based resin (A) is Tg (A), and the glass transition temperature of the copolymer resin (B) of the (meth) acrylic acid ester with the fluorene structure-containing crosslinkable monomer is Tg ( In the case of B), the difference between Tg (A) and Tg (B) is preferably 20 ° C. or lower, preferably 15 ° C. or lower. When the difference exceeds 20 ° C., there is a high possibility that the warpage prevention property becomes poor. The glass transition temperature of the copolymer resin (B) of the (meth) acrylic acid ester and the fluorene structure-containing crosslinkable monomer is 130 in view of the fact that the glass transition temperature of the polycarbonate resin (A) is usually 140 to 155 ° C. It is preferable that the range of ~ 165 ℃, preferably in the range of 135 ~ 160 ℃, but more accurate criterion is to measure the glass transition temperature of the base layer resin when any one of the polycarbonate resin (A) is selected as the base layer resin It is possible to secure excellent anti-bending properties desired to select a copolymer resin (B) of the (meth) acrylic acid ester for a skin layer and a fluorene structure-containing crosslinkable monomer having a difference of 20 ° C. or less.

In the present invention, in the copolymer resin (B) of the (meth) acrylic acid ester and the crosslinkable monomer containing a fluorene structure, the content of the crosslinkable monomer containing a fluorene structure is 1 to 20% by weight, preferably 3-15 weight% is preferable. When the content of the crosslinkable monomer including the fluorene structure is less than 1% by weight, the difference from the Tg (A) of the base layer exceeds 20 ° C, so that a desired anti-bending effect cannot be expected. If the content exceeds 20% by weight, the lipophilic properties are so great that the contact angle exceeds 90 °, so that there is a high risk of delamination.

Looking at a more specific example of the method for producing a copolymer resin (B) of the (meth) acrylic acid ester and the fluorene structure-containing crosslinkable monomer according to the present invention, for example, as described in Korean Patent Application No. 10-2010-0120223 It can be prepared by conventional bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization by using a composition in which an initiator and a chain transfer agent are added to (meth) acrylic acid ester and fluorene structure-containing crosslinkable monomers such as acrylate. In order to minimize the contamination caused by block polymerization or suspension polymerization is preferred.

The initiators include ketone peroxide, peroxy ketal, hyperoxide, dialkyl peroxide, diacryl peroxide, peroxyester, peroxy dicarbonate, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexane Peroxide, acetylacetone peroxide, 1,1-dibutylperoxy-3,3,5-trimethylcyclohexane, 1,1-dibutylperoxycyclohexane, 2,2-di-butylperoxybutane, 2 , 2,4-trimethylpentyl-2-hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-di- (t-butyl peroxy) hexane, t-butylcumyl peroxide, di-t -Butyl peroxide, tris- (t-butylperoxy) triazine, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane or di-t-butylperoxyhexahydrotere Organic peroxides such as phthalate or azobisisobutylonitrile, 1,1-azobis (cyclohexane-1-carbonitrile), azodi-t-octane-2-sa Azo compounds such as iano-2-propyl azoformamide, dimethyl-2,2-azobis (2-methylpropionate) and 2,2-azobis (2-hydroxymethylpropionitrile) are suitable. It is preferable that the addition amount is used in 0.01 thru | or 0.1 weight part with respect to 100 weight part of monomer total amounts, such as a (meth) acrylic acid ester and a fluorene structure containing crosslinkable monomer. If the content is less than 0.01 parts by weight, there is a problem that the polymerization rate is lowered. If the content is more than 0.1 parts by weight, the desired molecular weight cannot be obtained and the reactor is difficult to heat.

The chain transfer agent controls the fluidity of the resin by controlling the molecular weight of the copolymer resin (B) of the (meth) acrylic acid ester with the fluorene structure-containing crosslinkable monomer, and suppresses the crosslinking reaction of the fluorene structure-containing crosslinkable monomer. The chain transfer agent that can be used includes isopropyl mercaptan, normal butyl mercaptan, tertiary-butyl mercaptan, normal-amyl mercaptan, normal having 1 to 12 carbon atoms of an alkyl group and having one thiol functional group. Alkyl mercaptans such as octyl mercaptan, normal-dodecyl mercaptan or polythiol mercaptans having two or more thiol functional groups are suitable. The addition amount is 0.1-5.0 weight part, Preferably it is 0.2-1.0 weight part with respect to 100 weight part of monomer total amounts, such as (meth) acrylic acid ester and a fluorene structure containing crosslinkable monomer. When the amount is lower than 0.1 part by weight, the molecular weight becomes large and sufficient fluidity cannot be secured. When the amount is lower than 5.0 part by weight, the molecular weight is too small to effectively express physical properties.

In the present invention, the molecular weight of the copolymer (B) of the (meth) acrylic acid ester with the fluorene structure-containing crosslinkable monomer is preferably a weight average molecular weight from the viewpoint that the laminate can be produced by ordinary extrusion molding. Is preferably in the range of 30,000 to 100,000, preferably in the range of 50,000 to 80,000. Copolymers of (meth) acrylic acid esters with fluorene structure-containing crosslinkable monomers (B) generally include ultraviolet absorbers, mold release agents, processing aids, lubricants, antioxidants, colorants, light diffusing agents, flame retardants, and antistatic agents. You may add various additives, such as salt pigment.

In the present invention, as the hydrophilic group of the cyclic polyolefin-based resin (C) containing the hydrophilic group, hydroxyl group, ester group, organic acid group, organic acid salt group, organic acid anhydride group, amine group, ammonium group, cyano group, acetate group ether group, epoxy group, halogen And a hydroxyl group, an ester group, an organic acid group, an organic acid salt group, and the like are preferable, and specific examples thereof are as shown in Chemical Formulas 2, 3, 4, 5, 6, 7, and the like.

(2)

(3)

[Chemical Formula 4]

(In Formula 4, R is an alkyl group having 1 to 20 carbon atoms. N is an integer ranging from 1 to 2,000.)

[Chemical Formula 5]

[Chemical Formula 6]

[Formula 7]

More specifically introducing the method of obtaining the cyclic polyolefin-based resin (C) containing a hydrophilic group according to the present invention, for example, the cyclic polyolefin-based resin containing a hydrophilic group according to the formula (2) is obtained by ring-opening metathesis polymerization, for example registered in Korea Patent No. 10-2009-0883765, Bielawski CW, Grubbs RH. Living Ring-opening metathesis polymerization. Prog Polym Sci, Vol. 32 , 1 (2007), Trimmer, MS. Commercial Applications of Ruthenium Olefin Metathesis Catalysts in Polymer Synthesis. In Handbook of Metathesis; Grubbs, RH, Ed. Wiley-VCH, Vol. 3 , 407 (2003) and the like, the cyclic olefin monomer is a catalyst consisting of a halide, nitrate or acetylacetone compound and a reducing agent of a metal selected from ruthenium, rhodium, palladium, osmium, indium, platinum and the like, or titanium, palladium Can be obtained by ring-opening metathesis polymerization in the presence of a catalyst such as a halide or acetylacetone compound and an organoaluminum compound of a metal selected from zirconium, molybdenum and the like, and optionally further hydrogenation. , F4520, D4531F, D4532 and the like.

Cyclic polyolefin-based resins containing a hydrophilic group according to formula (3) are obtained by addition polymerization, for example, Korean Patent Registration No. 10-1999-0231173, Japanese Patent Publication No. 1986-221206, Japanese Patent Publication No. 1989-106, Japanese Patent Publication As described in 1990-145213, Japanese Patent Laid-Open No. 1990-173112, Japanese Patent Laid-Open No. 1991-234716, Japanese Patent Laid-Open No. 199-320258 and the like, a cyclic olefin monomer is a transition metal catalyst such as zirconium, titanium, hafnium, or cyclopentadie. Obtained as a cyclic olefin homopolymer by addition polymerization in the presence of a metalocene catalyst which is a catalyst composed of a transition metal compound containing a ligand having an enyl skeleton, an organoaluminum oxy compound, and an organoaluminum compound to be blended as necessary, and is also obtained as a cyclic olefin homopolymer. The above cyclic olefin monomers and linear olefin monomers such as ethylene, propylene, butene, etc. It can be obtained by addition polymerization in the presence of a catalyst, a metalocene catalyst and the like.

Cyclic polyolefin-based resins containing a hydrophilic group according to the formula (4) is a norbornene carboxylic acid alkyl ester homopolymer or copolymer, for example J. Polym. Sci. Polym. Norbornene carboxylic acid methyl ester, norbornene carboxylic acid ethyl ester, norbornene carboxylic acid n-propyl ester, norbornene carboxylic acid iso as described in Chem., Vol 45 , 30422 (2007) -Propyl ester, norbornene carboxylic acid n-butyl ester, norbornene carboxylic acid t-butyl ester, norbornene carboxylic acid n-pentyl ester, norbornene carboxylic acid n-hexyl ester, norbornene N-carboxylic acid cyclohexyl ester, norbornene carboxylic acid n-heptyl ester, norbornene carboxylic acid 1,4-dimethylpentyl ester, norbornene carboxylic acid n-octyl ester, norbornene carboxylic acid C1-C20 alkyl groups, such as 2-ethylhexyl ester, norbornene carboxylic acid myristyl ester, norbornene carboxylic acid palmityl ester, and norbornene carboxylic acid stearyl ester A paradigm complex-based catalyst having various norbornene carboxylic acid alkyl esters. Norbornene carboxylic acid alkyl ester homopolymer or alkyl group having one alkyl group by solvent polymerization in a solvent such as saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene under a catalyst such as a nickel composite system It may be obtained in the form of two or more norbornene carboxylic acid alkylester copolymers.

The cyclic polyolefin resin containing a hydrophilic group according to the formula (5) is a norbornene carboxylic acid alkyl ester homopolymer or copolymer of a cyclic polyolefin resin containing a hydrophilic group according to the formula (3) tetrahydrofuran, dibutyl ether, dimeth Ethers such as oxyethane, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform, tetrachloroethylene, ethyl acetate, n-butyl acetate, iso-butyl acetate It may be obtained by dissolving in an organic solvent such as saturated carboxylic acid esters such as methyl propionate and the like, followed by partial hydrolysis in solution by adding an aqueous solution such as hydrochloric acid or sulfuric acid.

The cyclic polyolefin resin containing a hydrophilic group according to Formula 6 is a norbornene carboxylic acid alkyl ester-norbornene which is a cyclic polyolefin resin containing a hydrophilic group according to Formula 4 as described in Korean Patent Registration No. 10-1147197. The carboxylic acid copolymer may be a metal such as alkali metal ions such as lithium ions, sodium ions and potassium ions, alkaline earth metal ions such as magnesium ions, calcium ions and barium ions, transition metal ions such as nickel ions, copper ions and zinc ions. Can be obtained by partial or complete neutralization with ions.

In addition, the cyclic polyolefin-based resin containing a hydrophilic group according to the formula (7) is as described in detail, such as in Japanese Patent Application No. 2004-138946, Korean Patent Application No. 10-2011-0017531, etc. Diisobutylaluminum, pentenyldiethylaluminum, pentenyldiisobutylaluminum, hexenyldiisobutylaluminum, hexenyldiethylaluminum, octenyldiisobutylaluminum, octenyldiethylaluminum, dekenyldiisobutylaluminum, dodekenyldiiso The norbornene-alkenyldialkylaluminum copolymer obtained by copolymerizing an alkenyldialkylaluminum compound such as butylaluminum and undekenyldiisobutylaluminum in the presence of a catalyst such as a metalocene catalyst or a half-methrosene catalyst is used for oxygen, peroxide, Hydrolysis of Dialkyl Aluminum Groups in Contact with Carbon Dioxide, Sulfur Trioxide, etc. By the response it can be obtained.

In the present invention, the surface properties of the cyclic polyolefin-based resin (C) containing the hydrophilic group are preferably in the range of 50 to 90 °, and preferably in the range of 60 to 80 °. If the contact angle is less than 50 ° or more than 90 °, there is a fear of layer separation after coextrusion.

In the present invention, when the glass transition temperature of the cyclic polyolefin-based resin (C) containing the hydrophilic group is Tg (C), the difference between Tg (A) and Tg (C) is 20 ° C or lower, preferably 15 ° C or lower. desirable. When the difference exceeds 20 ° C., there is a high possibility that the warpage prevention property becomes poor.

In the present invention, the molecular weight of the cyclic polyolefin-based resin (C) containing the hydrophilic group is preferably in the range of 30,000 to 100,000, preferably 50,000, in view of the fact that the laminate can be produced by conventional extrusion molding. ~ 80,000 range is good. To the cyclic polyolefin-based resin (C) containing a hydrophilic group, various additives such as ultraviolet absorbers, mold release agents, processing aids, lubricants, antioxidants, colorants, light diffusing agents, flame retardants, antistatic agents and salt pigments may be added. .

It should be noted that in the present invention, the copolymer resin (B) of the (meth) acrylic acid ester with the fluorene structure-containing crosslinkable monomer is advantageous in that the fluorene structure itself increases the heat resistance and rigidity due to its three-dimensional characteristic, Increasing the glass transition temperature, high hardness, the scratch resistance is induced, and the lipophilic characteristics are also improved, and the moisture resistance is partially improved. The moisture resistance is somewhat less than that of the cyclic polyolefin-based resin (C) containing a hydrophilic group.

On the other hand, the cyclic polyolefin resin (C) containing a hydrophilic group is basically a polyolefin having high lipophilic properties and thus has a low saturation moisture content, so it has excellent moisture resistance, but scratch resistance is a copolymer of a (meth) acrylic acid ester with a crosslinking monomer containing a fluorene structure. There is a side inferior to resin (B).

Therefore, in view of complementing the advantages and disadvantages of the two resins (B) and (C), the polycarbonate-based resin (A) is used as a raw material of the base layer, and the (meth) acrylic acid ester and the Multi-layer obtained by coextrusion from 10/90 to 90/10 (wt%) mixture (D) of copolymer resin (B) and cyclic polyolefin resin (C) containing a hydrophilic group as a raw material of one side or both sides skin layer It is highly desirable to use a laminate of structures as a display protection plate.

In the present invention, the copolymer resin (B) of the (meth) acrylic acid ester with the fluorene structure-containing crosslinkable monomer and the cyclic polyolefin-based resin (C) containing a hydrophilic group (10%) to 90/10 (wt%) The surface property of the mixture (D) is preferably in the range of 50 ° to 90 °, preferably 60 ° to 80 °, based on the contact angle. If the contact angle is less than 50 ° or more than 90 °, there is a fear of layer separation after coextrusion.

In the present invention, the glass transition temperature of the polycarbonate-based resin (A) is Tg (A) and the cyclic polyolefin containing a copolymer resin (B) of a (meth) acrylic acid ester and a fluorene structure-containing crosslinkable monomer and a hydrophilic group. When the glass transition temperature of the mixture (D) of 10/90 to 90/10 (wt%) with the resin (C) is Tg (D), the difference between Tg (A) and Tg (D) is 20 ° C or less. 15 degrees C or less is preferable. When the difference exceeds 20 ° C., there is a high possibility that the warpage prevention property becomes poor. In particular, a mixture of two resins may cause two or three glass transition temperatures rather than one. If all of the above conditions are not met, there is a high possibility that the anti-bending properties will be poor.

In the present invention, the copolymer resin (B) of the (meth) acrylic acid ester with the fluorene structure-containing crosslinkable monomer and the cyclic polyolefin-based resin (C) containing a hydrophilic group (10%) to 90/10 (wt%) The molecular weight of the mixture (D) is preferably in the range of 30,000 to 100,000, preferably 50,000 to 80,000, in view of the fact that the laminate can be produced by ordinary extrusion molding.

The multi-layered resin sheet of two or three layers according to the present invention is produced by the following coextrusion. That is, one main extruder which extrudes the polycarbonate resin (A) which is a raw material of a base material layer, the copolymer resin (B) of (meth) acrylic acid ester which is a raw material of a skin layer, and a fluorene structure containing crosslinkable monomer, It consists of one or two sub-extruders which extrude one or more selected from the group consisting of cyclic polyolefin-based resins (C) containing hydrophilic groups, and mixtures (D) thereof. That is adopted. The temperature of the main extruder is usually 230 ~ 290 ℃, preferably 240 ~ 280 ℃, more than 80 ℃ compared to the glass transition temperature of the polycarbonate resin (A), the temperature conditions of the sub-extruder also (meth) acrylic acid ester and fluorene 80 ° C to 140 ° C higher than one glass transition temperature selected from the group consisting of a copolymer resin (B) with a structure-containing crosslinkable monomer, a cyclic polyolefin-based resin (C) containing a hydrophilic group, and a mixture (D) thereof It is preferable to process at temperature conditions. Moreover, in order to remove the foreign material in resin, it is preferable to provide a polymer filter upstream from the dice | dies of an extruder.

As a method of laminating two kinds of molten resins, well-known methods, such as a multi-manifold system and a feed block system, can be used. In the case of a multi-manifold die, the molten resin laminated in the die is molded into a laminate shape inside the die, and then flows into a mirror-molded molding roll (polishing roll) to form a bank. The laminate-shaped molded product is subjected to mirror finishing and cooling during the passage of the forming cooling roll to form a laminated body having a multilayer structure of two layers of a skin layer / base layer structure or a three layer structure of a skin layer / base layer / skin layer. In addition, the molten resin laminated in the feed block is introduced into a laminate molding die such as a T die and molded into a laminate, and then surface finish and cooling are performed with a forming cooling roll to form a laminate. Moreover, as temperature of die | dye, it is 250-320 degreeC normally, Preferably it is 270-300 degreeC, and as a shaping | molding cooling roll temperature, it is 100-190 degreeC normally, Preferably it is 110-180 degreeC. When only one sub-extruder is used, the copolymer resin (B) of the same (meth) acrylic acid ester and the crosslinking monomer containing a fluorene structure, the cyclic polyolefin resin (C) containing a hydrophilic group, and a mixture thereof (D) Two-layer laminate of skin layer / substrate layer forming skin layer as one selected from the group consisting of can be formed, and when using two sub-extruders, the skin layer has different (meth) acrylic acid ester and fluorene structure-containing crosslinkable monomer Of a three-layer structure of a skin layer / base layer / skin layer each formed of one selected from the group consisting of a copolymer resin (B), a cyclic polyolefin resin (C) containing a hydrophilic group, and a mixture (D) thereof. The laminate can be molded.

The display protective plate according to the present invention preferably has a thickness configuration in which the thickness of the base layer is 70 to 97% and the thickness of the skin layer is 3 to 30%. If the thickness of the base layer is less than 70%, it is difficult to secure the desired impact resistance, and if the thickness of the skin layer is less than 3%, it may be difficult to secure the desired scratch resistance.

In the present invention, in order to exhibit excellent weather resistance over a long period of time, it is preferable that at least one ultraviolet absorber is contained in 0.005 to 3% by weight in the raw material resin of the base layer and the skin layer. If the UV absorber content is less than 0.005% by weight, it is difficult to secure desired weather resistance, and if it exceeds 3% by weight, scratch resistance may be deteriorated. As said ultraviolet absorber, a benzotriazole type, a benzophenone type, a salicylic acid phenyl ester type, a triazine type ultraviolet absorber etc. are mentioned, for example. As said benzotriazole type ultraviolet absorber, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3, 5-bis ((alpha), (alpha) '-dimethyl benzyl) ) Phenyl] -2H-benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetra Methylene butyl) -6- (2H-benzotriazol-2-yl) phenol]. As said benzophenone type ultraviolet absorber, 2-hydroxy-4- octoxy benzophenone, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxy-4'- chlor benzophenone, for example. And 2,2-dihydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4,4'-dimethoxybenzophenone and the like. As said salicylic acid phenyl ester type ultraviolet absorber, p-tert- butylphenyl salicylic acid ester etc. are mentioned, for example. As said triazine ultraviolet absorber, it is 2, 4- diphenyl-6- (2-hydroxy-4- methoxyphenyl) -1,3, 5- triazine, 2, 4- diphenyl-6, for example. -(2-hydroxy-4-ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-tri Azine, 2,4-diphenyl- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxy Phenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl- 6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3 , 5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy Oxy-4-butoxyethoxy) -1,3,5-triazine etc. are mentioned. The ultraviolet absorber contained in the polycarbonate resin layer and the ultraviolet absorber contained in the acrylic resin layer may be the same as or different from each other. The ultraviolet absorber in this invention is not limited to the ultraviolet absorber illustrated above, and contains various well-known ultraviolet absorbers.

In order for the protective plate according to the present invention to be more suitably used for display protection, it is preferable that a hard coat layer is further included on the surface of the base layer and / or the skin layer to improve scratch resistance. In particular, a hard coating layer is necessary on the surface of the skin layer, but the substrate layer also has a high probability of being scratched during various subsequent processes such as during transportation, hard coating operation, and printing process, and thus a hard coating layer is realistically required.

The curable coating composition used to form the hard coat layer contains at least one curable compound that improves scratch resistance as an essential component, and a curing catalyst, conductive particles, solvent, leveling agent, stabilizer, antioxidant, It contains a coloring agent and the like.

Examples of the curable compound include an acrylate compound, a urethane acrylate compound, an epoxy acrylate compound, a carboxyl group-modified epoxy acrylate compound, a polyester acrylate compound, a copolymerized acrylate compound, an alicyclic epoxy resin, and glycidyl ether epoxy. Resins, vinyl ether compounds, oxetane compounds, and the like, and among these, radically polymerizable curable compounds such as polyfunctional acrylate compounds, polyfunctional urethane acrylate compounds, and polyfunctional epoxy acrylate compounds, alkoxysilanes, alkylalkoxysilanes, and the like. The thermal polymerization curable compound of is preferable. These curable compounds are preferably compounds which are cured by irradiating energy rays such as electron beams, radiation, ultraviolet rays or the like, and compounds which are cured by heating, and as specific examples, "NK hard M101" (urethane acrylate type) of Shin-Nakamura Chemical Industries, "NK ester A-TMM-3L" (pentaerythritol triacrylate), "NK ester A-TMMT" (pentaerythritol tetraacrylate), "NK ester A-9530" (dipentaerythritol pentaacrylate) And "NK ester A-DPH" (Dipentaerythritol hexaacrylate), "KAYARAD DPCA" (Dipentaerythritol hexaacrylate) from Nippon Kayaku, Sanofco's "Novcocure 200" series, Dainippon "Unidict" series of the ink chemical industry, etc. are mentioned.

When hardening curable coating composition with an ultraviolet-ray, it is preferable to use 1 or more types of photoinitiators as a curing catalyst. As said photoinitiator, benzyl, benzophenone, its derivative (s), thioxanthones, benzyl dimethyl ketals, (alpha)-hydroxyalkyl phenones, hydroxy ketones, aminoalkyl phenones, acylphosphine oxide, etc. are mentioned, for example. And more specifically, "IRGACURE 651", "IRGACURE 184", "IRGACURE 500", "IRGACURE 1000", "IRGACURE 2959", "DAROCUR 1173", "IRGACURE 907" of Ciba-Speculsity-Chemicals, IRGACURE series and DAROCUR series, such as "IRGACURE 369", "IRGACURE 1700", "IRGACURE 1800", "IRGACURE 819", "IRGACURE 784", Nippon Kayaku's "KAYACURE ITX", "KAYACURE DETX-S", "KAYACURE KAYACURE series, such as BP-100 "," KAYACUREBMS ", and" KAYACURE 2-EAQ ", etc. are mentioned, The usage-amount of a photoinitiator is 0.1-5 weight part normally with respect to 100 weight part of curable compounds.

The hard coat layer obtained by containing the conductive particles in the curable coating composition has antistatic properties. Examples of the conductive particles include antimony-tin composite oxide, tin oxide containing phosphorus, antimony oxide, antimony-zinc composite oxide, and oxidation. Inorganic particles such as titanium and indium-tin composite oxide (ITO) are preferable, and the average particle diameter of the conductive particles is preferably fine nanoparticles in the range of 1 to 100 nm in terms of transparency damage prevention. Content of electroconductive particle is 2-50 weight part normally with respect to 100 weight part of curable compounds, Preferably it is 3-20 weight part. Although there exists a tendency for the antistatic property of a hard coat layer to improve that there are many content of electroconductive particle, when there is too much content of electroconductive particle, transparency may fall.

The curable coating composition may contain one or more leveling agents. As the leveling agent, silicone oil is preferable. Examples of silicone oils include dimethyl silicone oil, phenylmethyl silicone oil, alkyl aralkyl modified silicone oil, fluoro silicone oil, polyether modified silicone oil, fatty acid ester modified silicone oil, methylhydrogen silicone oil, silanol group-containing silicone oil, Alkoxy group containing silicone oil, phenol group containing silicone oil, methacryl modified silicone oil, amino modified silicone oil, carboxylic acid modified silicone oil, carbinol modified silicone oil, epoxy modified silicone oil, mercapto modified silicone oil, fluorine modified silicone Oils, polyether modified silicone oils, and the like, and more specific examples thereof include "SH200-100cs", "SH28PA", "SH29PA", "SH30PA", "ST83PA", "ST80PA", and "ST97PA" of Toray Dow Corning Silicone. And "ST86PA", BYK's "BYK-302", "BYK-307", "BYK-320" and "BYK-330", and the like. Content of a leveling agent is 0.01-5 weight part normally with respect to 100 weight part of curable compounds.

As a coating method of the curable coating composition which forms a hard coat layer, a bar coating method, the microgravure coating method, the roll coating method, the flow coating method, the dip coating method, the spin coating method, the die coating method, the spray coating method, etc. are mentioned, for example. In addition, hardening of a hard coat layer can be performed by irradiation of an energy beam or heating according to the kind of curable coating composition.

The thickness of the laminate according to the present invention is somewhat different depending on the use and there is no particular limitation, but when used as a mobile phone window, such as smart phones, feature phones, the total thickness is 0.3 ~ 1.5 ㎜ range is better and more preferably in the range of 0.7 ~ 1.0 ㎜ It is preferable.

Cyclic polyolefin-based resin comprising a copolymer resin (B) and a hydrophilic group of a base layer of the polycarbonate-based resin (A) according to the present invention and a crosslinkable monomer containing a (meth) acrylic acid ester and a fluorene structure ( The laminate including the skin layer of one or a mixture (D) selected from C) is excellent in transparency, impact resistance, moisture resistance and scratch resistance, and has excellent bending prevention properties. It is expected to be very useful for display fields such as display windows.

Cyclic polyolefin-based resin comprising a copolymer resin (B) and a hydrophilic group of a base layer of the polycarbonate-based resin (A) according to the present invention and a crosslinkable monomer containing a (meth) acrylic acid ester and a fluorene structure ( The laminate comprising the skin layer of one or a mixture (D) selected from C) and the display protective plate comprising such laminate are excellent in transparency, impact resistance, moisture resistance and scratch resistance as well as excellent warpage prevention. As it has characteristics, it is expected to be very useful for display field such as display window of portable information terminal.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure explaining the laminated body of the multilayered structure which consists of a base material layer and one or both skin layers in accordance with an aspect of the present invention.
2 is a view illustrating a display protective plate of various forms of a multi-layer structure composed of a base layer, a single-sided or double-sided skin layer, and a hard coating layer according to an embodiment of the present invention.

Through the following examples will be described in more detail the present invention. The following examples are merely examples and are not limited to the examples.

The glass transition temperature, weight average molecular weight, contact angle, transparency, impact resistance, moisture resistance, scratch resistance, anti-bending properties and weather resistance of the resin and laminate samples prepared according to the following Examples and Comparative Examples were evaluated as follows. .

(Glass transition temperature)

The glass transition temperature (Tg, ° C) for the sample was measured by heating at a rate of 10 ° C / min in DSC (Differential Scanning Calorimeter, TA).

(Weight average molecular weight)

GPC (gel permeation chromatography, Waters) measured the weight average molecular weight of the sample under the conditions of Shodex KF series column, measurement temperature 40 ℃, flow rate 1.0 mL / min.

(Contact angle)

The contact angle of the sample was measured by using a contact angle meter (model G-1, Erma).

(Transparency)

Transparency was evaluated by measuring the light transmittance (%) for the laminate samples according to ASTM D1003.

(Impact resistance)

A 59 mm X 59 mm laminate sample was fixed to a circular holder of 50 mm Φ, and a 22.2 mm diameter, 225 g steel ball was dropped at a height of 3.3 cm to measure the energy (J) when cracking occurred. The impact resistance was evaluated by the evaluation criteria shown in Table 1.

division ◎ (excellent) (Good) △ (Normal) X (bad)
Energy when cracking (J)
0.25 or more 0.20 or more
Less than 0.25 0.10 or more
Less than 0.20
Less than 0.10

(Moisture resistance)

100 mm X 100 mm laminate samples were placed in a thermo-hygrostat and placed at 85 ° C., 85% RH for 72 hours, and the average values of dimensional change (%) in MD and TD directions were measured to evaluate moisture resistance according to the evaluation criteria shown in Table 2. .

division ◎ (excellent) (Good) △ (Normal) X (bad)
Dimensional change ratio (%)
Less than 0.02 0.02 or more
Less than 0.03 0.03 or more
Less than 0.05
0.05 or more

(Scratch resistance)

The pencil hardness of the laminate sample was measured according to KS M 15184 to evaluate scratch resistance.

(Bending prevention characteristic)

The warpage against the full width of the laminate sample having a width of 1,200 mm was measured based on KS B 5224, and the maximum warp (mm) value was measured.

division ◎ (excellent) (Good) △ (Normal) X (bad)
Bending value (mm)
Less than 0.20 0.20 or more
Less than 0.30 0.30 or more
Less than 0.40
0.40 or more

(Weather resistance)

The initial yellowness (YI ₀ ) was measured on the UV-VIS spectrometer on the obtained laminate sample, and the yellowness (YI ₅₀₀ ) after 500 hours after the laminate sample was mounted on the weather-O-meter again. The weather resistance was evaluated by measuring the difference (ΔYI). The smaller the value of ΔYI, the better the weather resistance.

Example 1

First, as one of the polycarbonate resins (A), polycarbonate resin (melt index (300 ° C, 1.2Kg) 6.0, glass transition temperature 145 ° C, contact angle 70 °) (Bayer MaterialScience, trade name Makrolon, grade 3107, PC-A1) Was prepared as a raw material of the substrate layer.

Methyl methacrylate and bisaryl fluorene copolymer resin (PA-B1) are prepared as a raw material of the skin layer as one of the copolymer resins (B) of the (meth) acrylic acid ester and the crosslinkable monomer having a fluorene structure. Specifically, azobis was used as an initiator with respect to 100 parts by weight of a mixture of 97% by weight of methyl methacrylate and 3% by weight of bisaryl fluorene (OGSOL EA-F5003 having a viscosity of 2,000 mPas of Osaka gas chemical). 0.1 part by weight of isobutylonitrile, 0.5 part by weight of normal octyl mercaptan as a chain transfer agent, 200 parts by weight of water, and 0.3 part by weight of a polyvinyl alcohol aqueous solution as a suspension were added to the reactor, and the reaction temperature was 80 minutes at 80 ° C. After the polymerization, in order to remove residual monomer, additional polymerization was performed at 110 ° C. for 30 minutes to obtain a bead copolymer resin, and then washed in a dehydrator. The final resin sample was obtained by drying for 24 hours. The obtained methyl methacrylate and bisaryl fluorene copolymer resin (PA-B1) were analyzed and found to have a weight average molecular weight of 75,000, a glass transition temperature of 130 ° C., and a contact angle of 69 °. . In this case, the difference between the glass transition temperature of the polycarbonate-based resin (A) of the base material layer and the glass transition temperature of the methyl methacrylate and the bisaryl fluorene copolymer resin (PA-B1) of the skin layer is 15 ° C.

A two-layer laminate molding machine was provided with one main extruder having a barrel diameter of 65 mm and a screw L / D = 35 and one sub extruder having a barrel diameter of 32 mm and a screw L / D = 32. The main extruder was set at 250 ° C., polycarbonate-based resin (PC-A1) was added as a raw material of the base layer, the sub extruder was set at 235 ° C., and methyl methacrylate and bisaryl fluorene copolymer were used as raw materials for the skin layer. After the resin (PA-B1) was added, it was melt-extruded and cooled to obtain a laminate having a skin layer / base layer (50 μm / 950 μm) thickness and a two-layer structure having a final thickness of 1.0 mm. The transparency and impact resistance of the specimen were obtained. , Moisture resistance, scratch resistance and bending resistance were evaluated and the results are shown in Table 4.

Example 2

The monomer mixture was prepared in the same manner as in Example 1 except that 94% by weight of methyl methacrylate and 6% by weight of bisaryl fluorene (OGSOL EA-F5003, 2,000 mPas of Osaka Gas Chemical Co., Ltd.) were used. Thus, methyl methacrylate and bisaryl fluorene copolymer resin (PA-B2), which were raw materials for the skin layer having a weight average molecular weight of 77,000, a glass transition temperature of 141 ° C. and a contact angle of 73 °, were obtained. In this case, the difference between the glass transition temperature of the polycarbonate-based resin (A), which is the raw material of the base material layer, and the glass transition temperature of methyl methacrylate and the bisaryl fluorene copolymer resin (PA-B2), which is the raw material of the skin layer, is 4 ℃.

The polycarbonate-based resin (PC-A1) was used as a raw material for the base material layer, and was carried out in the same manner as in Example 1, where the skin layer / base layer (50 μm / 950 μm) thickness configuration and the final thickness of 1.0 mm two-layer laminate The transparency, impact resistance, moisture resistance, scratch resistance and bending resistance characteristics of the specimens were evaluated and the results are shown in Table 4.

Example 3

Except for using the monomer mixture obtained by mixing 89% by weight of methyl methacrylate, 3% by weight of methyl acrylate, and 8% by weight of bisaryl fluorene (OGSOL EA-F5003 having a viscosity of 2,000 mPas from Osaka Gas Chemical) In the same manner as in Example 1, methyl methacrylate-methyl acrylate-bisaryl fluorene copolymer resin (PA-B3), which is a raw material for the skin layer having a weight average molecular weight of 81,000, a glass transition temperature of 154 ° C., and a contact angle of 79 °, was prepared. Got it. In this case, the glass transition temperature of the polycarbonate-based resin (A), which is the raw material of the base material layer, and the glass transition temperature of the methyl methacrylate-methylacrylate-bisaryl fluorene copolymer resin (PA-B3), which is the raw material of the skin layer, The difference is 9 ° C. The polycarbonate-based resin (PC-A1) was used as a raw material for the base material layer, and was carried out in the same manner as in Example 1, where the skin layer / base layer (50 μm / 950 μm) thickness configuration and the final thickness of 1.0 mm two-layer laminate The transparency, impact resistance, moisture resistance, scratch resistance and bending resistance characteristics of the specimens were evaluated and the results are shown in Table 4.

Example 4

In the monomer mixture, 83% by weight of methyl methacrylate, 3% by weight of butyl acrylate, and 14% by weight of bisaryl fluorene (OGSOL EA-F5003 with 2,000 mPas of viscosity from Osaka Gas Chemical) were used. In the same manner as in Example 1, methylmethacrylate-butylacrylate-bisarylfluoroene copolymer resin (PA-B4), which is a raw material for the skin layer having a weight average molecular weight of 84,500, a glass transition temperature of 167 ° C and a contact angle of 83 °, was prepared. Got it. In this case, the glass transition temperature of the polycarbonate-based resin (A), which is the raw material of the base material layer, and the glass transition temperature of the methyl methacrylate-butylacrylate-bisaryl fluorene copolymer resin (PA-B4), which is the raw material of the skin layer, The difference is 22 ° C. The polycarbonate-based resin (PC-A1) was used as a raw material for the base material layer, and was carried out in the same manner as in Example 1, where the skin layer / base layer (50 μm / 950 μm) thickness configuration and the final thickness of 1.0 mm two-layer laminate The transparency, impact resistance, moisture resistance, scratch resistance and bending resistance characteristics of the specimens were evaluated and the results are shown in Table 4.

Example 5

Polycarbonate resin (Styron, trade name Caliber 201-6, PC) having a melt index (300 ° C., 1.2 Kg) 6.0, a glass transition temperature of 152 ° C., and a contact angle of 72 °, which is one of the polycarbonate resins (A). -A2) was prepared, and the methyl methacrylate-butyl acrylate-bisaryl fluorene copolymer resin (PA-B4) was prepared as a raw material for the skin layer. In this case, the glass transition temperature of the polycarbonate-based resin (PC-A2), which is the raw material of the base material layer, and the glass transition of the methyl methacrylate-butylacrylate-bisarylfluoroene copolymer resin (PA-B4), which is the raw material of the skin layer. The difference with temperature is 7 degreeC. Except for using the polycarbonate-based resin (PC-A2) as the raw material of the base material layer, the same procedure as in Example 4 was carried out to provide a skin layer / base layer (50 μm / 950 μm) thickness structure and a final two-layer structure having a final thickness of 1.0 mm. The laminate was obtained and evaluated for transparency, impact resistance, moisture resistance, scratch resistance and anti-bending properties for the specimens and the results are shown in Table 4.

Example 6

A three-layer laminate molding machine was equipped with one main extruder having a barrel diameter of 65 mm and a screw L / D = 35 and two sub extruders having a barrel diameter of 32 mm and a screw L / D = 32. The polycarbonate-based resin (PC-A2) is used as a raw material for the base layer, and methyl methacrylate and bisaryl fluorene copolymer resin (PA-B1) are used as raw materials for the skin layer. A three-layer laminate with a thickness composition of 50 / m / 900μm / 50μm / base layer and a final thickness of 1.0mm was obtained, and the transparency, impact resistance, moisture resistance, scratch resistance, and warpage resistance characteristics of the specimen were evaluated. And the results are shown in Table 4.

Comparative Example 1

In the two-layer laminate molding machine used in Example 1, only the same polycarbonate-based resin (PC-A1) was added to the main extruder and the sub-extruder and melt-extruded to obtain a laminate having a single layer structure having a thickness of 1.0 mm, and the transparency of the specimen. , Impact resistance, scratch resistance and bending resistance characteristics were evaluated and the results are shown in Table 4.

Comparative Example 2

Except using only methyl methacrylate and bisaryl fluorene copolymer resin (PA-B1), it carried out similarly to the comparative example 1, and obtained the laminated body of 1.0 mm thickness single layer structure. Scratchability and anti-bending characteristics were evaluated and the results are shown in Table 4.

Comparative Example 3

Polycarbonate-based resin (PC-A1) was prepared as a raw material for the base material layer, and a polymethyl methacrylate resin (Kuraray, Grade HR-S, PA) having a weight average molecular weight of 81,000 and a glass transition temperature of 111 ° C was used as a raw material for the skin layer. -B2) was prepared. . In this case, the difference between the glass transition temperature of polycarbonate-based resin (PC-A1), which is a raw material of the base material layer, and the glass transition temperature of polymethyl methacrylate resin (PA-B5), which is a raw material of the skin layer, is 34 ° C. The same procedure as in Example 1 was carried out to obtain a laminate having a skin layer / substrate layer (50 μm / 950 μm) thickness configuration and a final thickness of 1.0 mm, and the transparency, impact resistance, moisture resistance, and scratch resistance of the specimen. The properties and anti-bending properties were evaluated and the results are shown in Table 4 (physical properties of the laminate obtained according to Examples 1 to 6 and Comparative Examples 1 to 3).

division Laminate Layer Composition and Resin Properties
Layered
Resin Light transmittance
(%)
Impact resistance
Moisture resistance Scratch resistance Bending prevention
characteristic Exposed surface If
Example 1
Second floor Skin layer (exposed surface) PA-B1
91
◎
4H
2B
◎ Base layer (the back side) PC-A1
Example 2
Second floor Skin layer (exposed surface) PA-B2
91
◎
4H
2B
◎ Base layer (the back side) PC-A1
Example 3
Second floor Skin layer (exposed surface) PA-B3
91
◎
◎
5H
2B
◎ Base layer (the back side) PC-A1
Example 4
Second floor Skin layer (exposed surface) PA-B4
91
◎
◎
5H
2B Base layer (the back side) PC-A1
Example 5
Second floor Skin layer (exposed surface) PA-B1
91
◎
◎
5H
B
◎ Base layer (the back side) PC-A2
Example 6
3rd Floor Skin layer (exposed surface) PA-B1
91
◎
◎
5H
5H
◎ Substrate layer PC-A2 Skin layer (the back) PA-B1 Comparative Example 1 fault PC-A1 90 ◎ ◎ 2B 2B ◎ Comparative Example 2 fault PA-B1 92 X △ 4H 4H ◎
Comparative Example 3
Second floor Skin layer (exposed surface) PA-B5
91
◎
△
4H
2B
X Base layer (the back side) PC-A1

Example 7

Cyclic polyolefin resin containing a hydrophilic group, a cyclic polyolefin resin containing an ester group having a melt index of 35 (g / 10 minutes, 260 ° C, 98N), a glass transition temperature of 145 ° C, and a contact angle of 77 ° (JSR Arton D4532, COP-C1 ) Was prepared as a raw material of the skin layer, and the polycarbonate-based resin (PC-A1) was prepared as a raw material of the base layer. In this case, the difference between the glass transition temperature of the polycarbonate-based resin (PC-A1) as the raw material of the base layer and the glass transition temperature of the cyclic polyolefin-based resin (COP-C1) containing the ester group as the raw material of the skin layer is 0 ° C. . The same procedure as in Example 1 was carried out to obtain a laminate having a skin layer / substrate layer (50 μm / 950 μm) thickness configuration and a final thickness of 1.0 mm, and the transparency, impact resistance, moisture resistance, and scratch resistance of the specimen. And anti-bending properties were evaluated and the results are shown in Table 5.

Example 8

Cyclic polyolefin resin containing a hydrophilic group, a cyclic polyolefin resin containing an ester group having a melt index of 14 (g / 10 min, 260 ° C., 98 N), a glass transition temperature of 160 ° C., and a contact angle of 82 ° (JSR Arton D4520, COP-C2 ) Was prepared as a raw material of the skin layer, and the polycarbonate-based resin (PC-A1) was prepared as a raw material of the base layer. In this case, the difference between the glass transition temperature of the polycarbonate resin (PC-A1), which is the raw material of the base material layer, and the glass transition temperature of the cyclic polyolefin resin (COP-C2) containing the ester group, which is the raw material of the skin layer, is 15 ° C. . The same procedure as in Example 1 was carried out to obtain a laminate having a skin layer / substrate layer (50 μm / 950 μm) thickness configuration and a final thickness of 1.0 mm, and the transparency, impact resistance, moisture resistance, and scratch resistance of the specimen. And anti-bending properties were evaluated and the results are shown in Table 5.

Example 9

Cyclic polyolefin-based resin containing a hydrophilic group, norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester copolymer (COP-C3) having a weight average molecular weight of 75,000, a glass transition temperature of 148 ° C and a contact angle of 75 °. Was prepared as a raw material of the skin layer, the production method is as follows. First, 7.0 Kg of paradigm (II) acetate, 6.2 Kg of tricyclohexylphosphine, and 100 L of solvent chlorobenzene were added to the catalyst production tank, followed by stirring. Thereafter, 20Kg of phenylcarbenicit tetrakis (pentafluorophenyl) borate was added thereto, followed by stirring to prepare a paradigm complex catalyst solution. Meanwhile, 1,100 kg of norbornene carboxylic acid methyl ester, 4,200 kg of norbornene carboxylic acid n-hexyl ester, and 5,000 L of solvent toluene were added to a reactor equipped with a stirrer, followed by stirring. After the polymerization, the polymerization was carried out while stirring at 100 ° C. for 12 hours. After the completion of the polymerization, the resulting resin was precipitated in about 4,000 L methyl alcohol, filtered, and then vacuum dried for 12 hours. In addition, the polycarbonate-based resin (PC-A1) was prepared as a raw material of the base layer. In this case, the glass transition temperature of the polycarbonate resin (PC-A1), which is a raw material of the base material layer, and the norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester copolymer (COP-, which is a raw material of the skin layer). The difference from the glass transition temperature of C3) is 3 ° C. The same procedure as in Example 1 was carried out to obtain a laminate having a skin layer / substrate layer (50 μm / 950 μm) thickness configuration and a final thickness of 1.0 mm, and the transparency, impact resistance, moisture resistance, and scratch resistance of the specimen. And anti-bending properties were evaluated and the results are shown in Table 5.

Example 10

Cyclic polyolefin-based resin containing a hydrophilic group, norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl having a weight average molecular weight of 85,000, a glass transition temperature of 152 ° C, a contact angle of 62 ° and a carboxylic acid group content of 3.7% by weight. An ester-norbornene carboxylic acid copolymer (COP-C4) was prepared as a raw material for the skin layer, which was obtained as the norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester copolymer (COP). -C3) Dissolve 1,000 Kg in 2,000 L of tetrahydrofuran / water (9/1, volume ratio) mixed solvent, add 400 L of hydrochloric acid, and proceed with partial hydrolysis while stirring at 50 ° C for 10 hours to obtain methyl alcohol. It precipitated, filtered, and obtained by vacuum drying for 12 hours. Furthermore, polycarbonate resin (PC-A1) was prepared as a raw material of the base material layer. In this case, the glass transition temperature of the polycarbonate-based resin (PC-A1), which is a raw material of the base material layer, and the norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carr which is a raw material of the skin layer. The difference from the glass transition temperature of the acid copolymer (COP-C4) is 7 ° C. The same procedure as in Example 1 was carried out to obtain a laminate having a skin layer / substrate layer (50 μm / 950 μm) thickness configuration and a final thickness of 1.0 mm, and the transparency, impact resistance, moisture resistance, and scratch resistance of the specimen. And anti-bending properties were evaluated and the results are shown in Table 5.

Example 11

Cyclic polyolefin-based resin containing a hydrophilic group, norbornene carboxylic acid methyl ester having a weight average molecular weight of 91,000, a glass transition temperature of 155 ° C, a contact angle of 60 °, a carboxylic acid group content of 1.4% by weight, and a zinc carboxylic acid group content of 3.2% by weight. -Norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid-norbornene carboxylic acid zinc salt copolymer (COP-C5) was prepared as a raw material of the skin layer, which is obtained norbornene carboxyl 1,000 Kg of acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid copolymer (COP-C4) is dissolved in 2,000 L of a solvent of tetrahydrofuran / water (9/1) and zinc acetate 120 Kg. After the addition, the mixture was subjected to partial neutralization reaction at 50 ° C. for 20 hours to precipitate, and the resulting resin was precipitated, filtered and then vacuum dried for 12 hours. In addition, the polycarbonate-based resin (PC-A1) was prepared as a raw material of the base layer. In this case, the glass transition temperature of the polycarbonate-based resin (PC-A1), which is a raw material of the base material layer, and the norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carr which is a raw material of the skin layer. The difference with the glass transition temperature of the acid-norbornene carboxylic acid zinc salt copolymer (COP-C5) is 10 degreeC. The same procedure as in Example 5 was carried out to obtain a laminate having a skin layer / substrate layer / skin layer (50 μm / 900 μm / 50 μm) thickness and a three-layer structure having a final thickness of 1.0 mm. The transparency, impact resistance, and resistance to the specimen were obtained. Wetness, scratch resistance and anti-bending properties were evaluated and the results are shown in Table 5.

Example 12

Cyclic polyolefin-based resin containing a hydrophilic group, which has a weight average molecular weight of 97,000, a glass transition temperature of 150 ° C, a contact angle of 69 °, and a hydroxyl content of 1.1% by weight of norbornene-1-hexene copolymer (COP-C6) as a raw material for the skin layer. This prepared a norbornene and hexenyl diisobutylaluminum as first monomer. 250L of toluene was added to a 500L reactor equipped with a stirrer, and then 250 mmol of [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ], a catalyst, 250 mmol of [t-BuNSiMe ₂ Flu], and 50 mol% of norbornene as a monomer. And a comonomer of hexenyl diisobutylaluminum 50 mol% was added to the reactor and the polymerization was carried out for 2 hours while maintaining the reaction temperature at 40 ℃ to obtain a norbornene-hexenyldiisobutylaluminum copolymer. 15 L of dry oxygen was slowly injected at room temperature for 2 hours to proceed with complete hydrolysis of the diisobutylaluminum group contained in the hexenyl diisobutylaluminum compound unit, precipitated in methanol, filtered and washed with methanol several times. It was obtained by drying under reduced pressure at 60 ° C. for 8 hours. In addition, the polycarbonate-based resin (PC-A1) was prepared as a raw material for the substrate layer, and a COP-C2 resin was prepared as an exposed surface material in the skin layer, and a COP-C6 resin was prepared as a back material. In this case, the difference between the glass transition temperature of the polycarbonate resin (PC-A1), which is the raw material of the base material layer, and the glass transition temperature of the cyclic polyolefin resin (COP-C2) containing the ester group, which is one of the raw materials of the skin layer, is 15 And the difference between the glass transition temperature of the norbornene-1-hexene copolymer (COP-C6) containing 1.1% by weight of a hydroxyl group is 5 ° C. The same procedure as in Example 5 was carried out to obtain a laminate having a skin layer / substrate layer / skin layer (50 μm / 900 μm / 50 μm) thickness and a three-layer structure having a final thickness of 1.0 mm. The transparency, impact resistance, and resistance to the specimen were obtained. Wetness, scratch resistance and anti-bending properties were evaluated and the results are shown in Table 5.

Comparative Example 4

Except using only cyclic polyolefin resin (JSR Arton D4520, COP-C1) containing ester group, the same procedure as in Comparative Example 1 was carried out to obtain a laminate having a single-layer structure having a thickness of 1.0 mm. The transparency, impact resistance, and resistance to the specimen were obtained. Wetness, scratch resistance and anti-bending properties were evaluated and the results are shown in Table 5 (physical properties of the laminate obtained according to Examples 7 to 12 and Comparative Example 4).

division Laminate Layer Composition and Resin Properties Layered Resin Light transmittance
(%) Impact resistance Moisture resistance Scratch resistance Bending prevention
characteristic Exposed surface If Example 7 Second floor Skin layer (exposed surface) COP-C1 91 ◎ ◎ H 2B ◎ Base layer (the back side) PC-A1 Example 8 Second floor Skin layer (exposed surface) COP-C2 91 ◎ ◎ 2H 2B ◎ Base layer (the back side) PC-A1 Example 9 Second floor Skin layer (exposed surface) COP-C3 91 ◎ ◎ H 2B ◎ Base layer (the back side) PC-A1 Example 10 Second floor Skin layer (exposed surface) COP-C4 91 ◎ ◎ H 2B ◎ Base layer (the back side) PC-A1 Example 11 3rd Floor Skin layer (exposed surface) COP-C5 92 ◎ ◎ H H ◎ Substrate layer PC-A1 Skin layer (the back) COP-C5 Example 12 3rd Floor Skin layer (exposed surface) COP-C2 92 ◎ ◎ 2H H ◎ Substrate layer PC-A1 Skin layer (the back) COP-C6 Comparative Example 4 fault COP-C1 92 △ ◎ H H ◎

Example 13

First, a cyclic polyolefin-based resin (COP-C1) containing the methyl methacrylate, bisaryl fluorene copolymer resin (PA-B1) and an ester group was prepared as a raw material for the skin layer. Methyl methacrylate, bisaryl fluorene copolymer resin (PA-B1), and a cyclic polyolefin resin (COP-C1) containing an ester group, using the polycarbonate-based resin (PC-A1) as a base material A skin layer / base layer (50 μm / 950 μm) thickness was constructed in the same manner as in Example 1 except that 70/30 (wt%) mixture (D1) was used as the raw material for the skin layer. A laminate of was obtained, and the transparency, impact resistance, moisture resistance, scratch resistance, and warpage resistance characteristics of the specimens were evaluated and the results are shown in Table 6.

Example 14

Methyl methacrylate, bisaryl fluorene copolymer resin (PA-B1), and a cyclic polyolefin resin (COP-C1) containing an ester group, using the polycarbonate-based resin (PC-A1) as a base material A skin layer / base layer (50 μm / 950 μm) thickness configuration and final thickness of 1.0 mm were performed except that 50/50 (wt%) mixture (D2) was used as the skin layer raw material. A laminate of was obtained, and the transparency, impact resistance, moisture resistance, scratch resistance, and warpage resistance characteristics of the specimens were evaluated and the results are shown in Table 6.

Example 15

Methyl methacrylate, bisaryl fluorene copolymer resin (PA-B1), and a cyclic polyolefin resin (COP-C1) containing an ester group, using the polycarbonate-based resin (PC-A1) as a base material A skin layer / base layer (50 μm / 950 μm) thickness was constructed in the same manner as in Example 1, except that 30/70 (wt%) mixture (D3) was used as the material for the skin layer. The laminate was obtained, and the transparency, impact resistance, moisture resistance, scratch resistance, and warpage resistance characteristics of the specimen were evaluated, and the results are shown in Table 6 (physical properties of the laminate obtained according to Examples 13 to 15).

division Laminate Layer Composition and Resin Properties
Layered
Resin Light transmittance
(%)
Impact resistance
Moisture resistance Scratch resistance Bending prevention
characteristic Exposed surface If
Example 13
Second floor Skin layer (exposed surface) PA-B1 / COP-C1
(= 70/30)
91
◎
◎
3H
2B
◎ Base layer (the back side) PC-A1
Example 14
Second floor Skin layer (exposed surface) PA-B1 / COP-C1
(= 50/50)
91
◎
◎
2H
2B
◎ Base layer (the back side) PC-A1
Example 15
Second floor Skin layer (exposed surface) PA-B1 / COP-C1
(= 30/70)
91
◎
◎
H
2B
◎ Base layer (the back side) PC-A1

Example 16

First, a UV-curable hard coating liquid (HC-A) prepared by mixing 90 parts by weight of Daicel Scitech Co., Ltd. EB-220, 10 parts by weight of Osaka Organic Chemical Co., Ltd. .

Skin layer obtained by using polycarbonate-based resin (PC-A1) obtained in Example 2 as a raw material of the base layer and using methyl methacrylate and bisaryl fluorene copolymer resin (PA-B2) as raw materials of the skin layer. The UV curable hard coating liquid (HC-A) was applied to both sides of the two-layer structure of the substrate layer (50 μm / 950 μm) thickness configuration and the final thickness of 1.0 mm by dipping and dried at room temperature for 1 minute, followed by 45 ° C. After drying for 3 minutes in a hot air oven, the solvent was volatilized, and the coating film was irradiated with ultraviolet rays of 0.5 J / cm 2 using a 120 W high-pressure mercury lamp to cure, and a hard coating layer / skin having a double-sided hard coating layer having a thickness of 3 μm was formed. A four-layer laminate with a layer / substrate layer / hard coating layer (3μm / 50μm / 950μm / 3μm) thickness was obtained, and the transparency, impact resistance, moisture resistance, scratch resistance, and warpage resistance characteristics of the specimen were evaluated. The results are shown in Table 7.

Example 17

Skin layer obtained by using polycarbonate-based resin (PC-A1) obtained in Example 5 as a raw material of the base layer, and methyl methacrylate and bisaryl fluorene copolymer resin (PA-B1) as raw materials of the skin layer. Hard coating layer with a double-sided hard coating layer having a thickness of 3 μm, which was carried out in the same manner as in Example 12 except that the base layer / skin layer (50 μm / 900 μm / 50 μm) thick constitution and a laminate having a three-layer structure having a final thickness of 1.0 mm were used. Skin layer / substrate layer / skin layer / hard coating layer (3μm / 50μm / 900μm / 50μm / 3μm) of 5-layered laminate was obtained and the transparency, impact resistance, moisture resistance, scratch resistance and warpage of the specimen were obtained. The protection properties were evaluated and the results are shown in Table 7.

Example 18

Norbornene carboxylic acid methyl ester-norbornene carboxylic acid n-hexyl ester-norbornene carboxylic acid-nord using the polycarbonate resin (PC-A1) obtained by the said Example 10 as a raw material of a base material layer Skin layer / substrate layer / skin layer (50μm / 900μm / 50μm) thickness constitution obtained by using Bornezane carboxylic acid zinc salt copolymer (COP-C5) as raw material of skin layer, laminate of three-layer structure of final thickness 1.0mm Except for using the same as in Example 12, the hard coating layer / skin layer / base layer / skin layer / hard coating layer (3μm / 50μm / 900μm / 50μm / 3μm) thickness configuration having a double-sided hard coating layer having a thickness of 3㎛ Layered laminates were obtained and their transparency, impact resistance, moisture resistance, scratch resistance, and anti-bending properties were evaluated for the specimens and the results are shown in Table 7.

Comparative Example 5

A hard coat layer / substrate layer having a double-sided hard coat layer having a thickness of 3 μm was formed in the same manner as in Example 12, except that the polycarbonate-based resin (PC-A1) laminate having a single layer structure of 1.0 mm obtained in Comparative Example 1 was used. A three-layer laminate with a thickness of 3 μm / 1,000 μm / 3 μm was obtained, and the transparency, impact resistance, moisture resistance, scratch resistance, and anti-bending properties of the specimens were evaluated. Indicated.

Comparative Example 6

A double-sided hard having a thickness of 3 μm was carried out in the same manner as in Example 12, except that the methyl methacrylate having a single layer structure and the bisaryl fluorene copolymer resin (PA-B1) laminate obtained in Comparative Example 2 were used. A three-layer laminate with a hard coat layer, substrate layer, and hard coat layer (3 μm / 1,000 μm / 3 μm) with a coating layer was obtained, and the transparency, impact resistance, moisture resistance, scratch resistance, and warpage resistance characteristics of the specimen were obtained. It evaluated and showed the result in Table 7 (physical properties of the laminate obtained according to Examples 16-18 and Comparative Examples 5, 6).

division Laminate Layer Composition and Resin Properties Layered use
Suzy hard
Coating agent Light transmittance
(%) Impact resistance Moisture resistance Scratch resistance Bending prevention
characteristic Exposed surface If

Example 16

4th floor Hard coating layer
(Exposure side) - HC-A

91

◎

6H

H

◎ Skin layer PA-B2 - Substrate layer PC-A1 - Hard coating layer
(Back side) - HC-A

Example 17

5th floor Hard coating layer
(Exposure side) - HC-A

92

◎

6H

6H

◎ Skin layer PA-B1 - Substrate layer PC-A1 - Skin layer PA-B1 - Hard coating layer
(Back side) - HC-A

Example 18

5th floor Hard coating layer
(Exposure side) - HC-A

92

◎

◎

5H

5H

◎ Skin layer COP-C5 - Substrate layer PC-A1 - Skin layer COP-C5 - Hard coating layer
(Back side) - HC-A

Comparative Example 5

3rd Floor Hard coating layer
(Exposure side) - HC-A

90

◎

◎

H

H

◎ Substrate layer PC-A1 - Hard coating layer
(Back side) - HC-A

Comparative Example 6

3rd Floor Hard coating layer
(Exposure side) - HC-A

92

X

△

6H

6H

◎ Substrate layer PA-B1 - Hard coating layer
(Back side) - HC-A

Example 19

Methyl methacrylate and bisaryl fluorene copolymer resin (PA-B1) / Methyl methacrylate and bisaryl fluorene copolymer resin (PA-B2) using polycarbonate resin (PC-A1) as a raw material of a base material layer ) (= 50/50, weight ratio) The same procedure as in Example 1 was carried out except that the composition was used as a raw material for the skin layer. The transparency and weather resistance of the specimens were evaluated and the results are shown in Table 8.

Example 20

First, Smithsorb 340 (Sumitomo Chemical, UVA-1), which is a benzotriazole-based ultraviolet absorber, was prepared as an ultraviolet absorber.

Addition of UVA-1 2,000ppm to polycarbonate-based resin (PC-A1) as raw material for base layer, and cyclic polyolefin-based resin (JSR Arton D4520, COP-C1) containing ester group as raw material for skin layer In the same manner as in Example 1, a skin layer / substrate layer (50 μm / 950 μm) thickness configuration and a 1.0-mm-thick two-layer laminate were obtained, and the transparency and weather resistance of the specimen were evaluated. Indicated.

Example 21

Add 5,000 ppm of UVA-1 to polycarbonate-based resin (PC-A1) as a base material, and add 3000 ppm of UVA-1 to methyl methacrylate and bisaryl fluorene copolymer resin (PA-B1). The same procedure as in Example 1 was conducted except that the skin layer was used as a raw material for the skin layer, thereby obtaining a laminate having a skin layer / base layer (50 μm / 950 μm) thickness and a two-layer structure having a thickness of 1.0 mm. The transparency and weather resistance of the specimen were obtained. Was evaluated and the results are shown in Table 8 (physical properties of the laminate obtained according to Example 19 21).

division Laminate Layer Composition, Resin and UV Absorber Properties
Layered
Resin
UV absorbers Light transmittance
(%) Weatherability YI ₀ YI ₅₀₀ △ YI
Example 19 Second floor Skin layer (exposed surface) PA-B1 / PA-B2 = 5/5 -
91
0.6
5.2
4.6 Base layer (the back side) PC-A1 -
Example 20 Second floor Skin layer (exposed surface) COP-C1 -
91
0.5
4.4
3.9 Base layer (the back side) PC-A1 UVA-1 2,000ppm
Example 21 Second floor Skin layer (exposed surface) PA-B1 UVA-1 3,000ppm
91
0.6
2.3
2.9 Base layer (the back side) PC-A1 UVA-1 5,000 ppm

Examples 1 to 6 show excellent properties in transparency, impact resistance, moisture resistance, scratch resistance, and warpage prevention properties. It can be seen that the moisture resistance and the scratch resistance of the copolymer resin (B) with the containing crosslinkable monomer increased with increasing content of the fluorene structure-containing crosslinkable monomer. In Example 4, where the difference in glass transition temperature was slightly decreased, the bending property was slightly decreased. It can be seen that the bending prevention property is excellent again because the difference is smaller. Comparing Comparative Example 3 and Examples 1 to 5, it can be seen that particularly according to the present invention, the anti-bending properties and the moisture resistance are significantly improved.

Example 7 to Example 12 using the cyclic polyolefin-based resin (C) containing a hydrophilic group as the raw material of the skin layer, the transparency, impact resistance, moisture resistance, scratch resistance and Although all of the anti-bending properties are excellent, it can be seen that the impact resistance is greatly improved as compared with the single layer laminate using only the cyclic polyolefin-based resin (C) containing the hydrophilic group of Comparative Example 4.

In Examples 1, 7, and 13 to 15, the cyclic polyolefin containing methyl methacrylate, bisaryl fluorene copolymer resin (PA-B1) and ester group in the skin layer raw material. When the composition ratio with the resin (COP-C1) is changed, if the content of methyl methacrylate and the bisaryl fluorene copolymer resin (PA-B1) is increased, the scratch resistance is improved and the ester-containing cyclic polyolefin resin (COP) It can be seen that the moisture resistance is improved when the content of -C1) is increased.

Looking at Example 17 and Example 18 it can be seen that if the hard coating layer is formed on the skin layer, scratch resistance is greatly improved while maintaining excellent transparency, impact resistance, moisture resistance, and anti-bending properties.

Looking at Examples 19 to 21, it can be seen that when the ultraviolet absorbent is prescribed to the raw material resin of the skin layer or the base layer, the weather resistance is more improved, but it has a relatively excellent weather resistance even if not prescribed.

10: substrate layer
20: skin layer
30: Hard coating layer

Claims

A base layer made of a polycarbonate resin (A); And alkyl methacrylate having an alkyl group having 1 to 20 carbon atoms, alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, glycidyl (meth) acrylates any one or more selected from the group consisting of ( A mixture of a copolymer resin (B) of a crosslinkable monomer having a meth) acrylic acid ester and a fluorene structure and a cyclic polyolefin-based resin (C) containing at least one hydrophilic group of Formulas 2 to 7 (D) Laminate comprising a skin layer consisting of
(2)

(Ra and Rb in the formula (2) is the same or different, any one of a hydroxyl group, ester group, organic acid group, organic acid salt group, organic acid anhydride group, amine group, ammonium group, cyano group, acetate group, ether group, epoxy group, halogen group , Ra and Rb may combine with each other to form a ring, where l is 0 or an integer of 1 or more, and m is an integer ranging from 1 to 2,000.)
(3)

(In Formula 3, Rc and Rd are the same or different, hydroxyl group, ester group,
It is any one of an organic acid group, an organic acid salt group, an organic acid anhydride group, an amine group, an ammonium group, a cyano group, an acetate group ether group, an epoxy group, and a halogen group, and Rc and Rd may combine with each other to form a ring. p is an integer of 0 or 1 or more, q and r are integers in the range of 1 to 2,000, and the molar ratio of q: r has a ratio of 0.01 to 0.99: 0.99 to 0.01.)
[Chemical Formula 4]

(In Formula 4, R is an alkyl group having 1 to 20 carbon atoms, n is an integer ranging from 1 to 2,000.)
[Chemical Formula 5]

(In Formula 5, R is an alkyl group having 1 to 20 carbon atoms, p and q are integers in the range of 1 to 2,000, the molar ratio of p: q has a ratio of 0.01 to 0.99: 0.99 to 0.01.)
[Chemical Formula 6]

(In Formula 6, R is an alkyl group having 1 to 20 carbon atoms, M is any one of metal ions selected from alkali metals, alkaline earth metals, transition metals, p, q and r independently of each other of 1 to 2,000 And a molar ratio of p: q: r is available in the range of 0.01 to 0.99, respectively.)
(7)

In Formula 7, n is an integer of 1 to 20, X is any one of a hydroxyl group, a carboxylic acid group, and a sulfonic acid group, p and q are integers in the range of 1 to 2,000, and the molar ratio of p: q is 0.01 to 0.99. : Has a ratio of 0.99 to 0.01.)

The laminate according to claim 1, wherein the skin layer is further laminated on both sides of the substrate layer.

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The method of claim 1 or 2, wherein the alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, lauryl Laminate, characterized in that any one or more selected from the group consisting of methacrylate, stearyl methacrylate

The laminate according to claim 4, wherein the alkyl methacrylate is methyl methacrylate.

The method of claim 1 or 2, wherein the alkyl acrylate is methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate Laminated body, characterized in that any one or more selected from the group consisting of

The laminate according to claim 1 or 2, wherein the crosslinkable monomer comprising the fluorene structure is a compound represented by the following general formula (1).
[Chemical Formula 1]

In Formula 1, R ₁ represents an alkyl group having 1 to 8 carbon atoms, and R ₂ represents a hydrogen atom or a methyl group.

The copolymer resin (B) of the crosslinkable monomer containing the (meth) acrylic acid ester and the fluorene structure, according to claim 1 or 2, wherein the content of the crosslinkable monomer containing the fluorene structure is 1 to 20 wt%. Laminate, characterized in that%

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The laminate according to claim 1 or 2, wherein the surface property of the resin constituting the skin layer is in a range of 50 ° to 90 ° based on a contact angle.

12. The laminate according to claim 11, wherein the surface property of the resin is in the range of 60 ° to 80 ° based on contact angle.

The laminate according to claim 1 or 2, wherein the weight average molecular weight of the resin forming the skin layer is in the range of 30,000 to 100,000.

The laminate according to claim 13, wherein the resin has a weight average molecular weight in the range of 50,000 to 80,000.

The glass transition temperature of the polycarbonate-based resin (A) constituting the substrate layer is Tg (A) and the glass transition temperature of the resin (D) constituting the skin layer is Tg (D). In the case where the difference between Tg (A) and Tg (D) is 20 ℃ or less laminated body

The laminate according to claim 15, wherein a difference in glass transition temperature between Tg (A) and Tg (D) is 15 ° C or less.

The laminate according to claim 1 or 2, wherein the base layer and the skin layer are laminated by coextrusion molding.

The cyclic polyolefin-based resin (C) according to claim 1 or 2, wherein the resin forming the skin layer comprises a copolymer resin (B) of a crosslinkable monomer containing a (meth) acrylic acid ester and a fluorene structure and a hydrophilic group (C). ) Is composed of 10/90 to 90/10% by weight of the mixture (D)

The laminate according to claim 1 or 2, wherein the base layer has a thickness of 70 to 97% of the whole and a skin layer of 3 to 30%.

The laminate according to claim 1 or 2, wherein the resin of the base layer or / and skin layer further contains 0.005 to 3% by weight of an ultraviolet absorber.

The resin of claim 1 or 2, wherein the resin of the base layer or the skin layer is selected from the group consisting of a releasing agent, a processing aid, a lubricant, an antioxidant, a coloring agent, a light diffusing agent, a flame retardant, an antistatic agent and a dye pigment. Laminate, characterized in that it further contains one or more

A base layer made of a polycarbonate resin (A); And alkyl methacrylate having an alkyl group having 1 to 20 carbon atoms, alkyl acrylate having an alkyl group having 1 to 20 carbon atoms, glycidyl (meth) acrylates any one or more selected from the group consisting of ( A mixture of a copolymer resin (B) of a crosslinkable monomer having a meth) acrylic acid ester and a fluorene structure and a cyclic polyolefin-based resin (C) containing at least one hydrophilic group of Formulas 2 to 7 (D) Protective plate for display comprising a laminate comprising a skin layer consisting of;

The hard coating layer of claim 22, wherein the hard coating layer comprises at least one curable coating composition, a curing catalyst, conductive particles, a solvent, a leveling agent, a stabilizer, an antioxidant, and a coloring agent on a surface of the substrate layer and / or the skin layer. Protective plate for display, characterized in that further included

23. The protective plate for display according to claim 22, wherein the total thickness of the protective plate is 0.3 to 1.5 mm.

23. The protective plate for display according to claim 22, wherein the protective plate is for protecting a panel of a portable information terminal.