TWI652309B - Image display device - Google Patents

Abstract

The present invention provides a urethane resin composition characterized by containing a urethane resin (A) obtained by reacting a polyol (a1) and a polyisocyanate (a2), the polyol (a1) a polyhydric alcohol (a1-1) represented by the formula (1), and a polyether polyol selected from the group consisting of an aromatic polyester polyol (a1-2) and an epoxyalkyl group added to bisphenol (a1) -3) One or more polyols in the group. The urethane resin composition is excellent in film-forming property and has good adhesion to various substrates and overcoat layers, and thus can be used as a primer for various substrates. Further, since the coating film formed using the urethane resin composition has a high refractive index which can be used in the range of optical use, it can also be used for an optical film or the like.

Description

Image display device

The present invention relates to a urethane resin composition and a primer which can be used for producing an image display device such as a liquid crystal television or a touch panel.

As a urethane resin composition, a solvent-based urethane resin composition, an aqueous urethane resin composition, and a solvent-free urethane resin composition have been known, and are being used. It is used for various applications such as a molding material such as a film or a sheet, an adhesive, and a coating agent.

Further, urethane resin compositions have been studied in recent years for films or sheets which are oriented for optical use. Specific examples of the optical use include a liquid crystal display, a touch panel, and the like. A display device such as the above liquid crystal display is generally configured by laminating an optical film having an individual function. As such an optical film, an antireflection film, a retardation film, a tantalum lens sheet, or the like can be used.

As a urethane resin composition which can be used for the production of such an optical film or the like, for example, a reaction of an acid component containing an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid in a specific ratio with a diol component is known. a polyester polyol; and an aqueous polyester urethane resin obtained by reacting a polyisocyanate, containing 0.5 to 6% by weight of a pendant carboxyl group, and neutralizing the carboxyl group by ammonia or the like (for example, reference) Patent Document 1).

However, the aforementioned aqueous polyester polyurethane resin composition It is impossible to form a film which can be used for an optical use, has a high refractive index of about 1.55 to 1.65, and the like, and has a difference in refractive index due to a polyethylene terephthalate substrate which is a carrier of the optical film. A situation in which interference fringes are produced. Further, since the aqueous polyester urethane resin composition is slightly inferior in film formability, a smooth film cannot be formed.

Incidentally, the aforementioned optical use is by means of a plurality of layers. A layer of various functions is provided on the surface of the substrate to obtain an optical film having desired optical characteristics. As the base material, a substrate of various materials has been studied in view of diversification of products, and for example, a polyethylene terephthalate substrate which is generally difficult to adhere is known.

However, since the usual urethane resin composition does not have the level of adhesion that can be used for optical applications to the above-mentioned polyethylene terephthalate substrate, when the final product is used for a long period of time, This results in peeling from the polyethylene terephthalate substrate and the like.

Further, when an optical element is further produced by laminating an overcoat layer or the like different in properties from the olefin substrate, it is required to be able to form a good both for the polyethylene terephthalate substrate and the overcoat layer. The layer of adhesion, the conventional urethane resin composition is not easy to combine these properties.

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 61-36314

An object of the present invention is to provide a urethane resin having a high refractive index and a good film forming property which can be used for optical applications and having good adhesion to various substrates and overcoat layers. Composition.

The present inventors have found that it is possible to use a polyol (a1-1) represented by the formula (1) in combination with an aromatic polyester polyol (a1-2) and an alkylene oxide group. One or more of the group of the polyphenol polyols (a1-3) of bisphenol is used as a polyol used in the production of a urethane resin to solve the above problems.

That is, the present invention relates to a urethane resin composition characterized by containing a urethane resin (A) obtained by reacting a polyol (a1) and a polyisocyanate (a2), the polyol (a1) comprising a polyol (a1-1) represented by the formula (1), and a polyether polyol selected from the group consisting of an aromatic polyester polyol (a1-2) and an epoxyalkyl group added to bisphenol More than one polyol in the group of alcohols (a1-3);

[R ¹ in the above formula (1) independently represents a group having an aliphatic structure or an aromatic structure, and R ^{2 each} independently represents an alkylene group].

The urethane resin composition of the present invention can be used for a film having a high refractive index comparable to that of a polyethylene terephthalate substrate, and can be preferably used because of its good film formability and adhesion. For example, it is used in the manufacture of optical films and lenses used for image display devices such as liquid crystal displays and touch panels, and polarizing plates.

The urethane resin composition of the present invention is characterized by containing a polyol (a1-1) represented by the formula (1) and optionally comprising an aromatic polyester polyol (a1-2) An amino acid obtained by reacting an epoxyalkyl group with a polyol (a1) of one or more kinds of polyols in a group of polyether polyols (a1-3) of bisphenol and a polyisocyanate (a2) Ester resin (A).

[R ¹ in the above formula (1) independently represents a functional group having an aliphatic structure or an aromatic structure, and R ^{2 each} independently represents an alkylene group].

The urethane resin (A) is used as a polyol (a1-1) represented by the formula (1), and is selected from the group consisting of an aromatic polyester polyol (a1-2) and a ring. Oxyalkyl group added to bisphenol polyether polyol The polyol (a1) of one or more kinds of polyols in the group (a1-3) and the polyisocyanate (a2) are reacted.

The polyol (a1-1) used for the production of the urethane resin (A) may, for example, be a polyol represented by the following formula (1).

[R ¹ in the above formula (1) independently represents a group having an aliphatic structure or an aromatic structure, and R ^{2 each} independently represents an alkylene group].

The R ¹ in the above formula (1) can be, for example, an aliphatic structure having a cyclopentenyl group, a cyclohexyl group or the like, an aromatic structure such as a cyclopentenyl group or a cyclohexyl group, and an aromatic structure having an aryl group or the like. . Further, as R ² , an alkylene group having 1 to 5 carbon atoms can be exemplified, and specifically, an alkylene group such as an ethyl group, a propyl group or a butyl group can be given.

Specific examples of the polyhydric alcohol (a1-1) include bisphenoxyethanol oxime (wherein R ¹ in the formula (1) is an aryl group and R ² is an exoethyl group).

In order to obtain a film having a high refractive index which can be used for an optical use level, the polyol (a1-1) is preferably used in an amount of from 5 to 85% by mass based on the total amount of the polyol (a1). It is preferably in the range of 10% by mass to 65% by mass.

Moreover, as the aromatic polyester polyol (a1-2) used for the production of the urethane resin (A), a polyester polyol obtained by reacting a polycarboxylic acid and a polyhydric alcohol can be used.

As the polycarboxylic acid, an aromatic polycarboxylic acid such as terephthalic acid, isophthalic acid or an acid anhydride such as these can be used.

As the above polyol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 3-methyl-1,5-pentane can be used. Glycol and the like.

As the aromatic polyester polyol (a1-2), in order to impart good adhesion to the substrate, particularly to the polyethylene terephthalate substrate, the urethane resin composition of the present invention is provided. It is preferred to use an average molecular weight of 800 to 5,000, and it is preferred to use a number average molecular weight having a range of 1,000 to 3,000.

The aromatic polyester polyol (a1-2) is preferably used in an amount of from 5 to 80% by mass, more preferably from 10 to 65% by mass, based on the total amount of the polyol (a1). Range used.

Further, as the polyether polyol (a1-3) used for the production of the urethane resin (A), an epoxy group is added to a bisphenol.

The polyether polyol (a1-3) is a polyether polyol obtained by adding an alkylene oxide group to a hydroxyl group of a bisphenol, and can be added by a conventionally known method using the above bisphenol as a starting agent. Made from an alkylene oxide.

As the bisphenol, for example, bisphenol A, bisphenol F, bisphenol S, bisphenol AD, fluorinated bisphenol A, chlorinated bisphenol A, brominated bisphenol A, 4,4-bis(hydroxybenzene) can be used. Sulfide, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)amine, tricyclo[5,2,1,0 ^2.6 ]decane Phenol and the like. Among them, bisphenol A is particularly used because it imparts good adhesion to a substrate, particularly to a polyethylene terephthalate substrate, and a urethane resin capable of forming a coating film having a high refractive index. The composition is good.

As the alkylene oxide group to be added to the hydroxyl group of the bisphenol, for example, ethylene oxide, propylene oxide or the like can be used, and one or more selected from the group consisting of ethylene oxide and propylene oxide can be used. It is better.

The epoxyalkyl group is preferably added in an amount of 2 moles to 20 moles per mole of the bisphenol, and the addition of 2 moles to 10 moles can form a good film forming property and has a base material. In particular, it is preferable for a film having a good adhesion property of a polyethylene terephthalate substrate or the like.

The polyether polyol (a1-3) is preferably used in an amount of from 5% by mass to 80% by mass based on the total amount of the polyol (a1), and is preferably used in an amount of from 10% by mass to 65% by mass.

In the present invention, either or both of the aromatic polyester polyol (a1-2) and the polyether polyol (a1-3) described above can be used as the polyol (a1).

The urethane resin (A) is used in combination with the polyol (a1-1), the aromatic polyester polyol (a1-2), and the polyether polyol (a1-3). [Polyol (a1-1) / the total amount of the above aromatic polyester polyol (a1-2) and the above polyether polyol (a1-3)] (mass ratio) = 10/90 to 90/10 The urethane resin obtained is preferably a urethane resin composition having a film-forming property such as a film having a high refractive index which can be used for an optical use level, and is preferably used in the urethane resin composition. The urethane resin obtained is used in the range of 20/80 to 85/15, and more preferably the urethane resin obtained in the range of 40/60 to 70/30 is used.

In addition to the polyol (a1-1), the aromatic polyester polyol (a1-2), and the polyether polyol (a1-3), the polyol (a1) may be used in combination as needed. Polyol.

As the other polyol, for example, when an aqueous medium (B) is used as a solvent for the urethane resin (A), from the viewpoint of imparting a hydrophilic group to the urethane resin (A), A polyol having a hydrophilic group can be used.

As the polyol having a hydrophilic group, for example, a polyhydric alcohol having an anionic group, a polyhydric alcohol having a cationic group, a polyhydric alcohol having a nonionic group, and preferably a polyhydric alcohol having an anionic group can be used. . Further, as the polyol having a hydrophilic group, a polyester polyol having a hydrophilic group obtained by reacting a polyol having a low molecular weight hydrophilic group as described above with various polycarboxylic acids such as adipic acid can also be used. Wait.

As the polyhydric alcohol having an anionic group, for example, a carboxyl group such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid or 2,2-dimethylolvaleric acid can be used. a polyhydric alcohol having a sulfonic acid group such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid or 5[4-sulfophenoxy]isophthalic acid .

The anionic group is partially or wholly neutralized by a basic compound or the like, and is excellent in exhibiting good water dispersibility. The neutralization system may be carried out on the hydrophilic group of the hydrophilic group-containing polyol, or may be a hydrophilic group obtained by using the hydrophilic group-containing polyol to produce the urethane resin (A). get on.

As the basic compound which can be used for neutralizing the anionic group, for example, ammonia, triethylamine, morpholine, an organic amine such as monoethanolamine or diethylethanolamine having a boiling point of 100 ° C or higher, and sodium hydroxide can be used. a metal hydroxide such as potassium hydroxide or lithium hydroxide. The basic compound is preferably used in the range of a basic compound/anionic group = 0.2 to 3.0 (mole ratio) from the viewpoint of improving the dispersion stability of the obtained urethane resin composition. Preferably, it is used in the range of 0.6 to 1.5 (mole ratio).

Further, as the polyhydric alcohol having a cationic group, for example, a polyhydric alcohol having a tertiary amino group can be used, and specifically, N-methyl-diethanolamine can be used, and a compound having two epoxy groups in one molecule can be used. A polyol obtained by a 2-stage amine reaction or the like.

The cationic group may be partially or wholly neutralized with an acidic compound such as formic acid, acetic acid, phosphoric acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid or the like, or may also be composed of dimethylsulfuric acid. The quaternization agent such as diethyl sulphate, chlorinated methane or chlorinated ethane is subjected to quaternization.

The polyol having a cationic or anionic hydrophilic group can be 0.1% by mass to 25 based on the total amount of the polyol (a1) which can be used in the raw material of the urethane resin (A). The range of mass % is used.

Further, as the polyol having a nonionic group, a polyalkylene glycol having a structural unit derived from ethylene oxide or the like can be used.

Further, the polyisocyanate (a2) which is reacted with the polyol (a1) may be used singly or in combination of two or more kinds, for example, a phenylene group. Aromatic diisocyanate such as isocyanate, methylphenyl diisocyanate, diphenylmethane diisocyanate or naphthalene diisocyanate, hexamethylene diisocyanate, octadecyl diisocyanate, cyclohexane diisocyanate, isophorone II A diisocyanate containing an aliphatic or aliphatic cyclic structure such as isocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate or tetramethylxylylene diisocyanate. In particular, methylphenylene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate are used, since a good adhesion to the substrate, in particular to the polyethylene terephthalate substrate, can be obtained. It is preferred that the urethane resin composition of the high refractive index coating film can be formed.

The urethane resin (A) can be reacted by, for example, reacting the polyol (a1) with the polyisocyanate (a2) and, if necessary, a chain extender, in the absence of a solvent or in the presence of an organic solvent. Manufacturing. When the aforementioned organic solvent is used, when the urethane resin (A) is dispersed in the aqueous medium (B), it is preferred to remove the organic solvent by distillation or the like as necessary.

As the organic solvent which can be used in the production of the urethane resin (A), two or more ketones such as acetone or methyl ethyl ketone can be used alone or in combination; tetrahydrofuran, An ether such as an alkane; an acetate such as ethyl acetate or butyl acetate; a nitrile such as acetonitrile; dimethylformamide or N-methylpyrrolidone;

The reaction between the polyol (a1) and the polyisocyanate (a2) is, for example, based on the hydroxyl group of the polyol (a1), and the equivalent ratio of the isocyanate group of the polyisocyanate (a2) is from 0.8 to 2.5. The range is preferably carried out, preferably in the range of 0.9 to 1.5.

The chain extender which can be used in the production of the urethane resin (A) can improve the durability of the laminate of the image display device obtained by increasing the molecular weight of the urethane resin (A) and the like. Used for the purpose.

As the chain extender which can be used in the production of the urethane resin (A), a polyamine, a ruthenium compound, another compound containing an active hydrogen atom, or the like can be used.

As the polyamine, for example, ethylenediamine, 1,2-propylenediamine, 1,6-hexanediamine, and piperazine can be used. 2,5-Dimethyl pipe , isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine Equivalent diamines, N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine, diamethylene Amine, diexamine, triethylenetetramine, and the like.

As the hydrazine compound, for example, hydrazine, N,N'-dimethylhydrazine, 1,6-hexamethylbiguanide or the like can be used.

As the other active hydrogen-containing compound, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol can be used. , diols such as hexanediol, neopentyl glycol, sucrose, methylene glycol, glycerol, sorbitol, etc.; bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-di A phenol such as hydroxydiphenyl ether, 4,4'-dihydroxybiphenyl hydrazine, hydrogenated bisphenol A or hydroquinone, or water.

The chain extender is, for example, an amine group and an active hydrogen atom-containing equivalent of the chain extender, and a urethane prepolymer obtained by reacting the polyol (a1) with the polyisocyanate (a2). Have The isocyanate group equivalent is preferably used in the range of 1.9 or less (equivalent ratio), and is preferably used in the range of 0.3 to 1 (equivalent ratio).

The chain extender can be used when the polyol (a1) and the polyisocyanate (a2) are reacted or after the reaction. Further, the above-described chain extender can also be used in the case where the obtained urethane resin (A) is dispersed in an aqueous medium (B) to be aqueous.

As the urethane resin (A) obtained by the above method, in order to obtain a urethane resin composition having good adhesion to a substrate, particularly a polyethylene terephthalate substrate Preferably, those having a weight average molecular weight in the range of 10,000 to 200,000 are used, and those having a weight average molecular weight in the range of 20,000 to 100,000 are preferably used.

When the urethane resin (A) is produced, a reaction catalyst can be used in combination in order to shorten the reaction time of the polyol (a1) and the polyisocyanate (a2).

As the reaction catalyst, for example, a tertiary amine catalyst or an organic metal catalyst can be used. As the tertiary amine catalyst, for example, triethylenediamine, pentamethylenediethylenetriamine, triethylamine, N,N-dimethylethanolamine, ethylmorpholine or the like can be used. As the organic metal catalyst, for example, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, sodium hydrogencarbonate or the like can be used.

As the urethane resin (A) obtained by the above method, it is preferable to use a urethane resin having a hydrophilic group as described above, and it is also possible to use the above-mentioned amine group without using the aforementioned hydrophilic group. Formate resin (A). In this case, the surfactants described later are used in combination. It is preferred to contribute to the dispersion of the urethane resin (A). Further, even when a urethane resin having a hydrophilic group is used as the urethane resin (A), the same interface can be used as needed from the viewpoint of further enhancing water dispersion stability. Active agent.

As the aforementioned surfactant, for example, polyoxyethylene B can be used. Allyl nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene. Nonionic surfactant of polyoxypropylene copolymer; fatty acid salt of sodium oleate, alkyl sulfate, alkylbenzenesulfonate, alkylsulfosuccinate, naphthalenesulfonate, polyoxyethylene Anionic surfactants such as alkyl sulfates, sodium alkane sulfonates, sodium alkyl diphenyl ether sulfonates, etc.; alkylamine salts, alkyl trimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts Etc. cationic surfactants. Among them, in particular, from the viewpoint of improving the dispersion stability of the urethane resin composition of the present invention, it is preferred to use an anionic or nonionic surfactant.

When using the aforementioned surfactant, from the primer layer From the viewpoint of low water resistance, it is preferably used in the range of 0.5% by mass to 5% by mass based on the total amount of the urethane resin (A).

As the urethane resin to be obtained by the aforementioned method (A) The method of dispersing into the aqueous medium (B) can be exemplified by the following methods 1 and 2.

[Method 1] When a urethane having a hydrophilic group is used When the resin is used as the urethane resin (A), a part or all of the hydrophilic group of the urethane resin obtained by the above method is used by using the above-mentioned basic compound or the like as necessary. Neutralization or level 4 A method of mixing and stirring with an aqueous medium (B) to obtain an aqueous dispersion of the urethane resin (A).

[Method 2] When using an aminocarboxylic acid having no hydrophilic group When the ester resin is used as the urethane resin (A), the urethane resin obtained by the above method and a surfactant described later are mixed under stirring, and then the aqueous medium (B) is introduced. A method of obtaining an aqueous dispersion of the urethane resin (A) by emulsifying and dispersing or by emulsifying and dispersing using an emulsifier or the like.

The aforementioned urethane resin is carried out in the presence of an organic solvent In the production of (A), after the aqueous dispersion of the urethane resin (A) is produced by the above methods 1 and 2, it is preferred to remove the organic solvent by distillation or the like as necessary.

As can be used for the aforementioned urethane resin (A) The aqueous medium (B) of the solvent may, for example, be water, an organic solvent mixed with water, or a mixture thereof. Examples of the organic solvent to be mixed with water include alcohols such as methanol, ethanol, n-propanol, and isopropanol; ketones such as acetone and methyl ethyl ketone; and ethylene glycol, diethylene glycol, and propylene glycol. Polyalkylene glycol; alkyl ether of polyalkylene glycol; N-methyl-2-pyrrolidone. In the present invention, only water may be used, or a mixture of water and an organic solvent mixed with water may be used, or only an organic solvent mixed with water may be used. From the standpoint of safety and environmental burden, it is preferred to use only water, or a mixture of water and an organic solvent mixed with water, and particularly preferably only water.

In any of the above methods 1 and 2, the urethane is used. When the ester resin (A) is dispersed in the aqueous medium (B), a machine such as a homogenizer can be used as needed.

Composition of urethane resin obtained by the aforementioned method The urethane resin (A) is preferably contained in an amount of from 5% by mass to 60% by mass based on the total amount of the urethane resin composition, and preferably contains 10% by mass. 40% by mass range. Further, the aqueous medium (B) is preferably used in an amount of from 35 to 85% by mass based on the total amount of the urethane resin composition, and preferably from 50 to 85% by mass. The range of mass %.

The urethane resin composition of the present invention can be Need to use filming aids, crosslinkers, hardening accelerators, plasticizers, antistatic agents, waxes, light stabilizers, flow regulators, dyes, leveling agents, rheology control agents, UV absorbers, antioxidants Various additives such as photocatalyst compounds, inorganic pigments, organic pigments, and extender pigments.

The crosslinking agent is preferably used from the viewpoint of achieving the effect of improving the heat and humidity resistance of the coating film and the primer layer formed by using the urethane resin composition described above, and can be selected from, for example, a melamine-containing compound or a ring. Oxygen compounds, One or more of the group consisting of an oxazoline compound, a carbodiimide compound, and an isocyanate compound. Among them, a melamine compound or an epoxy compound is particularly preferable.

As the melamine compound, it is particularly preferred to use an alkylated methylol melamine resin.

The alkylated methylol melamine resin can be obtained, for example, by reacting a methylolated melamine resin with a lower alcohol (an alcohol having 1 to 6 carbon atoms) such as methyl alcohol or butyl alcohol. Specifically, an alkylated methylol melamine resin containing an imide group, an alkylated methylol melamine resin containing an amine group, or the like can be used.

As the aforementioned methylolated melamine resin, it can be used For example, an amine group-containing hydroxymethyl type melamine resin obtained by condensing melamine and formaldehyde, a hydroxymethyl type melamine resin containing an imine group, a trimethoxy hydroxymethyl type melamine resin, and a hexamethoxymethylol type melamine resin Etc., it is preferred to use a trimethoxymethylol type melamine resin or a hexamethoxymethylol type melamine resin.

The aforementioned alkylated methylol melamine resin is relative to The mass of the urethane resin (A) is preferably from 3% by mass to 50% by mass, and more preferably from 3% by mass to 30% by mass.

Further, as an epoxidation which can be used for the aforementioned crosslinking agent For example, an epoxy resin such as bisphenol A epichlorohydrin type, vinyl epoxy propyl ether, polyethylene glycol epoxy propyl ether, glycerol diepoxypropyl ether, glycerol tricyclic ring can be used. Oxypropyl propyl ether, 1,6-hexanediol epoxy propyl ether, trimethylolpropane triepoxypropyl ether, diepoxypropyl aniline, diamine glycidylamine, N, N, N ', N'-tetraepoxypropyl-m-xylylenediamine, 1,3-bis(N,N'-diamine-glycidylaminomethyl)cyclohexane, and the like.

Especially as the aforementioned epoxy compound, if epoxy The amount of 100 to 300 is preferred because durability is imparted. Specifically, it is preferred to use one or more kinds of trimethylolpropane polyepoxypropyl ether or glycerol triepoxypropyl ether. Preferably, trimethylolpropane triepoxypropyl ether or glycerol triepoxypropyl ether is used.

Further, as the epoxy compound, an epoxy compound having a hydrolyzable silyl group can also be used.

As the above-mentioned epoxy compound having a hydrolyzable decyl group, For example, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiepoxydecane, 3-epoxypropane Oxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, etc. .

The aforementioned urethane resin composition can be appropriately made Used in coatings, adhesives, etc. Among them, it is particularly preferably used for coating, and it is preferably used as a primer.

The primer of the present invention obtained by the above method can be used for the production of various laminates typified by image display devices.

As a laminate of the present invention, a substrate surface can be mentioned There is a primer layer formed using the primer described above, and the surface of the primer layer has a laminate of a photohardenable layer formed using a photocurable resin composition.

First, a substrate constituting the laminate of the present invention will be described.

The laminate of the present invention is composed of at least a substrate, a primer layer, and a photohardenable layer.

As the base material layer, for example, a polyester substrate, an acrylic substrate, a polycarbonate substrate, a polyolefin substrate, an acrylonitrile-butadiene-styrene substrate, a polystyrene substrate, or the like can be used. One or more plastic substrates in a group of a polyurethane substrate, an epoxy resin substrate, a polyvinyl chloride material, and a polyamide substrate are used in the manufacture of the image display device described above. It is preferred to use one or more selected from the group consisting of a polyester substrate, an acrylic substrate, a polycarbonate substrate, and a polyolefin substrate. It is preferred to use a polyester substrate, and it is more preferable to use a substrate comprising polyethylene terephthalate or polyethylene naphthalate having good light transmittance.

The substrate may also be in the form of a plate, a sphere, a film, or a sheet. Any shape. The thickness of the substrate is preferably 10 μm to 200 μm.

Further, as the substrate, a uniaxial or biaxial axis has been used in advance. The stretcher is better for improving the strength and durability of the substrate.

Moreover, the primer layer constituting the laminate can be coated by The cloth comprising a primer of the aforementioned urethane resin composition is formed on a part or all of the surface of the substrate, followed by drying.

As a method of applying the aforementioned primer to the surface of the aforementioned substrate, Examples of the spray method, the curtain flow coating method, the shower coating method, the roll coating method, the gravure printing method, the brush coating method, and the dipping method can be exemplified.

The primer is coated before the substrate is stretched as good. The base material to which the primer is applied is then stretched as needed, and the adhesion of the primer layer and the substrate is further improved.

As a method of drying the aforementioned primer to form the aforementioned primer layer The method may be, for example, a method of curing at a normal temperature for about 1 to 10 days, but from the viewpoint of rapid curing, it is preferred to heat at a temperature of 50 ° C to 250 ° C for about 1 second to 600 seconds. Further, when a plastic substrate which is easily deformed and discolored at a relatively high temperature is used, it is preferred to carry out aging at a relatively low temperature of about 30 ° C to 100 ° C.

As the primer layer, in order to prevent the light of the substrate The optical characteristics such as penetrability are preferably as low as 20 nm to 10,000 nm.

The element of the primer layer on the surface area of the substrate may be wound in a state such as a roll or the like for storage and fixation.

Further, the layer of the photohardenable layer constituting the laminate is partially or entirely formed on the surface of the primer layer by a layer formed by curing the photocurable resin composition.

As the photocurable resin composition, for example, a vinyl ester resin and a vinyl monomer can be used.

As the vinyl ester resin, for example, a polyester (meth) acrylate, an epoxy (meth) acrylate, a urethane (meth) acrylate, or the like can be used.

The polyester (meth) acrylate can be produced by reacting a polyhydric alcohol and a polycarboxylic acid with a compound having a polymerizable unsaturated double bond.

As the above polyol, for example, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexanediol, dimethylolcyclohexane, 2,4,4-trimethyl-1,3-pentene can be used. Glycol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, and the like.

Further, as the polycarboxylic acid, for example, phthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic acid, tetrabromophthalic acid, malonic acid, succinic acid, or the like can be used. Diacid, sebacic acid, 1,1,2-dodecanoic acid, methylene succinic acid, caric acid, HET acid, and the like.

Further, as the compound having a polymerizable unsaturated double bond, for example, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate can be used.

Further, as the epoxy (meth) acrylate which can be used as the vinyl ester resin, those obtained by reacting various epoxy compounds and unsaturated monobasic acids can be used.

As the epoxy compound, for example, a glycidyl ether such as a low molecular weight diol, an epoxy compound of a bisphenol type, and an epoxy compound of a phenol type can be used.

As the bisphenol type epoxy compound, for example, a compound obtained by reacting epichlorohydrin with bisphenol, a compound obtained by reacting methyl epichlorohydrin with bisphenol, and an alkylene oxide by bisphenol can be used. A compound obtained by a reaction of an adduct with epichlorohydrin or the like.

As the unsaturated monobasic acid capable of reacting with the above epoxy compound, for example, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, monomethyl maleate, monopropyl maleate, and cis-butyl can be used. Monobutylene olefinate, sorbic acid or maleic acid mono(2-ethylhexyl) or the like.

Further, a urethane (meth) acrylate which is the above vinyl ester resin can be used, and those obtained by reacting a polyisocyanate with a vinyl monomer having a hydroxyl group can be used.

As the polyisocyanate, 1,6-hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, methylphenyl diisocyanate, and xylene support can be exemplified. Diisocyanate, naphthalene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate And such adducts and the like. Further, as the polyisocyanate, a urethane prepolymer having an isocyanate group obtained by reacting the polyisocyanate with various polyols can be used.

As a hydroxyl group capable of reacting with the aforementioned polyisocyanate As the (meth) acrylate, for example, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate or the like can be used.

As the vinyl ester resin, in order to maintain the ease of coating It is preferred to use a weight average molecular weight of 500 to 20,000.

Also as B which can be used in combination with the aforementioned vinyl ester resin The ethylenic monomer can be used, for example, of styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinyltoluene, vinyl acetate, and phthalic acid. Diarylate, triaryl cyanate, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid Tertiary butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate , tridecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (methyl) Acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene Alcohol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether ( Methacrylate Ester, diethylene glycol mono 2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, dipropylene glycol monoethyl ether (meth) acrylate, dipropylene glycol monobutyl Ether (meth) acrylate, dipropylene glycol monohexyl ether (meth) acrylate, dipropylene glycol mono 2-ethylhexyl ether (methyl) Acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and the like.

a photocurable resin composition system forming the photohardenable layer It is preferable to contain the above-mentioned vinyl ester resin in the range of 10% by mass to 70% by mass based on the entire photocurable resin composition. In addition, it is preferable that the photocurable resin composition contains the vinyl monomer in the range of 20% by mass to 80% by mass based on the entire photocurable resin composition.

The photocurable resin composition is included to contain light A polymerization initiator which initiates polymerization is preferred.

As the polymerization initiator, for example, diethoxygen can be used. Acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxyl -2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl 2-dimethylamino-1-(4-morpholinylphenyl)butanone, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] Acetone}, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)benzyl]phenyl}-2-methylpropan-1-one, benzoin, benzoin methyl Ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenyl ketone, methyl phthalic acid benzoate, 4-phenyl diphenyl ketone, 4-benzylidene group - 4'-Methyl-diphenyl sulfide, 3,3',4,4'-tetrakis(tertiary butylperoxycarbonyl)diphenyl ketone, 2,4,6-trimethyldiphenyl ketone 4-Benzylmercapto-N,N-dimethyl-N-[2-(1-oxy-2-propenyloxy)ethyl]benzylammonium bromide, (4-benzylidenebenzyl) Trimethylammonium chloride, 2-isopropylthioxanthone, 4-isopropyl Thiopinone, 2,4-diethylthiazinone, 2,4-dichlorothiazepinone, 1-chloro-4-propoxythiazinone, 2-(3-dimethyl Amino-2-hydroxy)-3,4-dimethyl-9H-thiaxanthone-9-one m-chloride, oxy-phenyl-acetic acid 2-[2-oxy-2-phenyl- Ethyloxy-ethoxy]ethyl ester, oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]ethyl ester, bis(2,4,6-trimethylbenzylidene)- Phenylphosphine oxide, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, and the like.

The aforementioned polymerization initiator is relative to the aforementioned photohardenable tree The total amount of the lipid composition is preferably from 0.1% by mass to 10% by mass.

As a method of forming the photohardenable layer, it is possible to The photocurable resin composition is applied to a part or all of the surface of the primer layer and hardened.

Applying the photocurable resin composition to the foregoing The method of the surface of the primer layer can be exemplified by a spray method, a curtain flow coating method, a shower coating method, a roll coating method, a brush coating method, a dipping method, and the like.

As a method of curing the photocurable resin composition, a method of irradiating light such as ultraviolet rays can be exemplified. The light irradiation is preferably carried out in an energy range of about 0.2 J/cm ² to ² J/cm ² .

The aforementioned photohardenable layer is thicker by about 0.01 μm to 0.5 mm. Degree is better.

The laminated system of the present invention obtained by the foregoing method is not Since interference fringes are generated, it can be applied to, for example, the manufacture of optical films and lenses, and the manufacture of image display devices such as touch panels.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples.

[Synthesis Example 1]

In a 4-necked flask, 287 parts by mass of ethylene glycol, 481 parts by mass of neopentyl glycol, 635 parts by mass of terephthalic acid, 635 parts by mass of isophthalic acid, and 0.05 parts by mass of tetrabutyl titanate were placed. The reaction was carried out at 220 ° C for 24 hours under a nitrogen stream to obtain a polyester polyol (PES-1) [acid value 0.3, hydroxyl group 74.5].

[Synthesis Example 2]

In a 4-necked flask, 305 parts by mass of ethylene glycol, 512 parts by mass of neopentyl glycol, 335 parts by mass of adipic acid, 888 parts by mass of isophthalic acid, and 0.05 parts by mass of tetrabutyl titanate were placed. The reaction was carried out at 220 ° C for 24 hours under a nitrogen stream to obtain a polyester polyol (PES-2) [acid value 0.2, hydroxyl group 111.9].

<Preparation of urethane resin> [Synthesis Example 3]

149 parts by mass of 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene, and 150 parts by mass of the aforementioned polyester polyol (PES-1) were mixed, and dehydrated at 100 ° C under reduced pressure. After cooling to 80 ° C, 357 parts by mass of methyl ethyl ketone was added and thoroughly stirred, and 26 parts by mass of 2,2-dimethylolpropionic acid was added, and then 111 parts by mass of methylphenyl diisocyanate and 0.2 parts by mass of octanoic acid were added. The tin was reacted at 75 ° C for 8 hours.

After confirming that the isocyanate content after the above reaction [mass ratio of the isocyanate group to the total amount of the reactants] is 0.1% by mass or less, the reaction product is cooled to 50° C., and 20 parts by mass of triethylamine is added for neutralization, and added. 2000 parts by mass of water.

Next, after removing methyl ethyl ketone at 40 to 60 ° C under reduced pressure, the concentration was adjusted by adding water to obtain a urethane resin composition (PUD-1) having a nonvolatile content of 25% by mass.

[Synthesis Example 4]

180 parts by mass of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene and 120 parts by mass of the aforementioned polyester polyol (PES-2) were mixed, and dehydrated and cooled at 100 ° C under reduced pressure. After adding to 80 ° C, 11 parts by mass of 1,4-butanediol and 395 parts by mass of methyl ethyl ketone were added and stirred well, and 26 parts by mass of 2,2-dimethylolpropionic acid was added, followed by addition of 147 parts by mass. Phenyl diisocyanate and 0.2 parts by mass of tin octylate were reacted and reacted at 75 ° C for 8 hours.

After confirming that the isocyanate content after the above reaction [mass ratio of isocyanate groups to the total amount of the reactants] is 0.1% by mass or less, the reactant is cooled to 50° C., and 20 parts by mass of triethylamine is added for neutralization. 2000 parts by mass of water was added.

Next, after removing methyl ethyl ketone at 40 to 60 ° C under reduced pressure, the concentration was adjusted by adding water to obtain a urethane resin composition (PUD-2) having a nonvolatile content of 25% by mass.

[Synthesis Example 5]

Mixing 178 parts by mass of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, and 119 parts by mass of a diol of 8 mil propylene oxide in bisphenol A (hydroxyl number = 168), Dehydration was carried out at 100 ° C under reduced pressure, and after cooling to 80 ° C, 7.8 parts by mass of neopentyl glycol and 393 parts by mass of methyl ethyl ketone were added and thoroughly stirred, and 30 parts by mass of 2,2-dimethylolpropionic acid was added. Further, 153 parts by mass of methylphenyl diisocyanate and 0.2 parts by mass of tin octylate were added and reacted at 75 ° C for 8 hours.

After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50° C., and 23 parts by mass of triethylamine was added thereto for neutralization, and 2000 parts by mass of water was added thereto.

Next, after removing methyl ethyl ketone at 40 to 60 ° C under reduced pressure, the concentration was adjusted by adding water to obtain a urethane resin composition (PUD-3) having a nonvolatile content of 25% by mass.

[Synthesis Example 6]

Mixing 210 parts by mass of 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene, and 90 parts by mass of a diol of bisphenol A in addition of 3 moles of propylene oxide (hydroxyl number = 231), Dehydration was carried out at 100 ° C under reduced pressure, and after cooling to 80 ° C, 386 parts by mass of methyl ethyl ketone was added and thoroughly stirred, and 24 parts by mass of 2,2-dimethylolpropionic acid was added, followed by addition of 148 parts by mass of Liu Ya. Methyl diisocyanate and 0.2 parts by mass of tin octylate were reacted at 75 ° C for 8 hours.

After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50° C., and 18 parts by mass of triethylamine was added thereto for neutralization, and 2000 parts by mass of water was added thereto.

Next, after removing methyl ethyl ketone at 40 to 60 ° C under reduced pressure, the concentration was adjusted by adding water to obtain a urethane resin composition (PUD-4) having a nonvolatile content of 25% by mass.

[Synthesis Example 7]

Mixing 195 parts by mass of 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene and 105 parts by mass of 6 gram propylene oxide in bisphenol A diol (hydroxyl number = 229), Dehydration was carried out at 100 ° C under reduced pressure, and after cooling to 80 ° C, 389 parts by mass of methyl ethyl ketone was added and stirred well, and 27 parts by mass of 2,2-dimethylolpropionic acid was added, followed by the addition of 150 parts by mass of methylbenzene. The bis-isocyanate and 0.2 parts by mass of tin octoate were reacted at 75 ° C for 8 hours.

After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50° C., and 20 parts by mass of triethylamine was added thereto for neutralization, and 2000 parts by mass of water was added thereto.

Next, after removing methyl ethyl ketone at 40 to 60 ° C under reduced pressure, the concentration was adjusted by adding water to obtain a urethane resin composition (PUD-5) having a nonvolatile content of 25% by mass.

[Synthesis Example 8]

150 parts by mass of 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene and 150 parts by mass of the aforementioned polyester polyol (PES-2) and 150 parts by mass of 6-mole propylene oxide are mixed The diol of bisphenol A (hydroxyl price = 229), dehydrated at 100 ° C under reduced pressure, and after cooling to 80 ° C, 559 parts by mass of methyl ethyl ketone was added and stirred well, and 41 parts by mass of 2, 2 - 2 was added. Hydroxymethylpropionic acid, followed by 193 parts by mass of methylphenyl diisocyanate and 0.2 parts by mass of tin octoate and reacted at 75 ° C for 8 hours.

After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reaction product was cooled to 50° C., and 31 parts by mass of triethylamine was added thereto for neutralization, and 2000 parts by mass of water was added thereto.

Next, after removing methyl ethyl ketone at 40 to 60 ° C under reduced pressure, the concentration was adjusted by adding water to obtain a urethane resin composition (PUD-6) having a nonvolatile content of 25% by mass.

[Comparative Synthesis Example 1]

77 parts by mass of a diol of 2 gram of propylene oxide in bisphenol A (hydroxyl number = 325) and 221 parts by mass of the above polyester polyol (PES-2) were mixed, and dehydrated at 100 ° C under reduced pressure, and cooled to After 80 ° C, 357 parts by mass of methyl ethyl ketone was added and stirred well, and 26 parts by mass of 2,2-dimethylolpropionic acid was added, followed by 111 parts by mass of methylphenyl diisocyanate and 0.2 parts by mass of tin octoate. The reaction was carried out at 75 ° C for 8 hours.

After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reactant was cooled to 50° C., and 20 parts by mass of triethylamine was added thereto for neutralization, and 1600 parts by mass of water was added.

Then, after removing methyl ethyl ketone at 40 to 60 ° C under reduced pressure, the concentration was adjusted by adding water to obtain a urethane resin composition (PUD'-1) having a nonvolatile content of 25% by mass.

[Comparative Synthesis Example 2]

300 parts by mass of 6 molar propylene oxide was added to the diol of bisphenol A under reduced pressure at 100 ° C, and after cooling to 80 ° C, 6.3 parts by mass of neopentyl glycol and 398 parts by mass of methyl ethyl ketone were added. After thoroughly stirring, 28 parts by mass of 2,2-dimethylolpropionic acid was added, followed by 153 parts by mass of methylphenyl diisocyanate and 0.2 parts by mass of tin octoate and reacted at 75 ° C for 8 hours.

After confirming that the isocyanate content after the reaction was 0.1% by mass or less, the reactant was cooled to 50° C., and 21 parts by mass of triethylamine was added thereto for neutralization, and 1700 parts by mass of water was added.

Then, after removing methyl ethyl ketone at 40 to 60 ° C under reduced pressure, the concentration was adjusted by adding water to obtain a urethane resin composition (PUD'-2) having a nonvolatile content of 25% by mass.

<Preparation of Light Curable Resin Composition> [Modulation Example 1]

50 parts by mass of UNIDIC V-4260 (manufactured by DIC Corporation, urethane acrylate resin), 50 parts by mass of tripropylene glycol diacrylate, and 3 parts by mass of IRGACURE 184 (BASF) A photopolymerization initiator (manufactured by Seiko) was used to obtain a photocurable resin composition (UV-1).

[Modulation Example 2]

50 parts by mass of UNIDIC V-5500 (epoxy acrylate resin, manufactured by DIC Corporation), 50 parts by mass of tripropylene glycol diacrylate, and 3 parts by mass of IRGACURE 184 (photopolymerization initiator manufactured by BASF Corporation) were mixed. A photocurable resin composition (UV-2) was obtained.

[Example 1]

The bottom portion was prepared by mixing 100 parts by mass of the aforementioned urethane resin composition (PUD-1), 5 parts by mass of BECKAMINE M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water. Paint (P-1).

On the surface of the base material comprising polyethylene terephthalate having a film thickness of 125 μm, the primer (P-1) was applied to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes to form the base. The surface of the material forms a primer layer.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Embodiment 2]

On the surface of the base material comprising polyethylene terephthalate having a film thickness of 125 μm, the primer (P-1) was applied to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes to form the base. The surface of the material forms a primer layer.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Example 3]

By mixing 100 parts by mass of the aforementioned urethane resin composition (PUD-1), 2 parts by mass of CR-5L (manufactured by DIC Corporation, an epoxy crosslinking agent), and 168 parts by mass of ion-exchanged water. Modulate the primer (P-2).

The surface of the base material containing the polyethylene terephthalate having a film thickness of 125 μm was applied to the base (P-2) to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Example 4]

The surface of the base material containing the polyethylene terephthalate having a film thickness of 125 μm was applied to the base (P-2) to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Example 5]

By mixing 100 parts by mass of the aforementioned urethane resin composition (PUD-1), 4 parts by mass of CARBODILITE V-02-L2 (manufactured by Nisshin Chemical Co., Ltd., carbodiimide cross-linking agent), and 162 The mass of ion-exchanged water is used to prepare the primer (P-3).

The surface of the base material (P-3) which was coated with polyethylene terephthalate having a film thickness of 125 μm was applied to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Embodiment 6]

The surface of the base material (P-3) which was coated with polyethylene terephthalate having a film thickness of 125 μm was applied to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Embodiment 7]

The mixture was prepared by mixing 100 parts by mass of the aforementioned urethane resin composition (PUD-2), 5 parts by mass of BECKAMINE M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water. Primer (P-4).

The primer (P-4) was applied to the surface of a substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Embodiment 8]

The primer (P-4) was applied to the surface of a substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Embodiment 9]

The mixture was prepared by mixing 100 parts by mass of the aforementioned urethane resin composition (PUD-3), 5 parts by mass of BECKAMINE M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water. Primer (P-5).

The primer (P-5) was applied to the surface of the substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Embodiment 10]

The primer (P-5) was applied to the surface of the substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Example 11]

The mixture was prepared by mixing 100 parts by mass of the aforementioned urethane resin composition (PUD-4), 5 parts by mass of BECKAMINE M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water. Primer (P-6).

The primer (P-6) was applied to the surface of a substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Embodiment 12]

The primer (P-6) was applied to the surface of a substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Example 13]

The mixture was prepared by mixing 100 parts by mass of the aforementioned urethane resin composition (PUD-5), 5 parts by mass of BECKAMINE M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water. Primer (P-7).

The primer (P-7) was applied to the surface of a substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Embodiment 14]

The primer (P-7) was applied to the surface of a substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Example 15]

The mixture was prepared by mixing 100 parts by mass of the aforementioned urethane resin composition (PUD-6), 5 parts by mass of BECKAMINE M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water. Primer (P-8).

The primer (P-8) was applied to the surface of the substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Example 16]

The primer (P-8) was applied to the surface of the substrate containing polyethylene terephthalate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. The surface of the material forms a primer layer.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Comparative Example 1]

100 parts by mass of the aforementioned urethane resin composition (PUD'-1), 5 parts by mass of BECKAMINE M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water were mixed. Modulate the primer (P'-1).

The surface of the substrate containing the polyethylene terephthalate having a film thickness of 125 μm was applied with the primer (P'-1) to a thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. A primer layer is formed on the surface of the substrate.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Comparative Example 2]

The surface of the substrate containing the polyethylene terephthalate having a film thickness of 125 μm was applied with the primer (P'-1) to a thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. A primer layer is formed on the surface of the substrate.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Comparative Example 3]

100 parts by mass of the aforementioned urethane resin composition (PUD'-2), 5 parts by mass of BECKAMINE M-3 (manufactured by DIC Corporation, melamine crosslinking agent), and 185 parts by mass of ion-exchanged water were mixed. Modulate the primer (P'-2).

The surface of the base material containing the polyethylene terephthalate having a film thickness of 125 μm was applied with the primer (P'-2) to a thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. A primer layer is formed on the surface of the substrate.

The photocurable resin composition (UV-1) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Comparative Example 4]

The surface of the base material containing the polyethylene terephthalate having a film thickness of 125 μm was applied with the primer (P'-2) to a thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes. A primer layer is formed on the surface of the substrate.

The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer. The photocurable resin composition (UV-2) was applied to the surface of the primer layer at a coating thickness of 15 μm, and the base was obtained by irradiating ultraviolet rays with an irradiation intensity of 0.5 J/cm ² on the coated surface using a high-pressure mercury lamp as a light source. The surface of the material has a primer layer, and the surface of the primer layer is provided with a laminate of a photohardenable layer.

[Production of test board]

Coating the aforementioned primers (P-1) to (P-8) and (P'-1) and (P'-2) on the surface of a substrate comprising polyethylene terephthalate having a film thickness of 125 μm. Either the film thickness at the time of drying was about 1 μm, and the test piece containing the element of the base material surface layer primer layer was produced by heating at 150 ° C for 5 minutes.

[Adhesiveness of base material and primer layer (initial) <transparent adhesive tape peeling test>]

A 24 mm wide adhesive tape made of Nichiban Co., Ltd. was attached to the surface of the primer layer constituting the test plate prepared by the above method.

Next, the above-mentioned adhesive tape was stretched in a direction perpendicular to the aforementioned primer layer, and the state of the surface of the aforementioned primer layer when the above-mentioned adhesive tape was peeled off from the surface of the primer layer was visually evaluated in accordance with the following evaluation criteria.

◎: The primer layer was not peeled off from the surface of the substrate constituting the test plate at all.

○: A very small portion of the primer layer was peeled off from the surface of the substrate constituting the test plate, but the peeling range was less than 10% with respect to the entire area of the film constituting the test plate.

△: The primer layer in the range of 10% or more and less than 50% of the area of the primer layer constituting the test plate was peeled off from the surface of the substrate constituting the test plate.

X: The primer layer in the range of 50% or more of the entire area of the primer layer constituting the test plate was peeled off from the surface of the substrate constituting the test plate.

[Adhesiveness of primer layer and photohardenable layer (initial) <transparent adhesive tape peeling test>]

On the surface of the photohardenable layer constituting the laminate obtained in the examples and the comparative examples, a 24 mm wide adhesive tape manufactured by Nichiban Co., Ltd. was attached.

Next, the adhesive tape was stretched in a direction perpendicular to the photohardenable layer, and the state of the surface of the photohardenable layer when the adhesive tape was peeled off from the surface of the photohardenable layer was visually evaluated in accordance with the following evaluation criteria.

◎: The photohardenable layer is not peeled off from the surface of the substrate constituting the laminated body at all.

○: A very small portion of the photohardenable layer is peeled off from the surface of the substrate constituting the laminated body, but the peeling range thereof is less than 10% with respect to the entire area of the photohardenable layer constituting the laminated body.

△: The photohardenable layer having a range of 10% or more and less than 50% of the area of the photohardenable layer constituting the laminated body is peeled off from the surface of the substrate constituting the laminated body.

X: The photohardenable layer in the range of 50% or more of the entire area of the photohardenable layer constituting the laminated body is peeled off from the surface of the substrate constituting the laminated body.

[Adhesion of primer layer and photohardenable layer (after endurance test)]

The laminate obtained above was placed in a high-temperature humidifier having a temperature of 60 ° C and a relative humidity of 90% for 50 hours. Then, the laminated body was taken out, and the adhesion of the primer layer and the photohardenable layer was evaluated in the same manner as in the above [Adhesiveness of the primer layer and the photohardenable layer (initial) <transparent adhesive tape peeling test>].

[Evaluation method of refractive index]

The primers obtained in the examples and the comparative examples were applied to the surface of a polypropylene substrate to have a film thickness of 100 μm after drying, and then dried at room temperature for 24 hours, and then formed into a coating film by heat treatment at 150 ° C for 5 minutes. .

By dissolving the obtained coating film in N,N-dimethylformamide (DMF), the urethane which constitutes the urethane resin of the coating film is 10% by mass. A DMF solution of a resin, a DMF solution of a 20% by mass urethane resin, and a DMF solution of a 30% by mass urethane resin.

The refractive index of the DMF solution of the above three kinds of urethane resins was measured using a digital refractometer RX-5000 (manufactured by ATAGO Co., Ltd.), and the urethane was calculated by linearizing the obtained measured values. The refractive index of the resin when the solid content is 100% by mass.

The range of the refractive index of 1.55 to 1.65 can prevent the occurrence of interference fringes when laminated with a polyethylene terephthalate substrate (PET), and in particular, greater than 1.57 is evaluated as being particularly excellent for preventing the occurrence of the aforementioned interference fringes. . Further, when the aforementioned refractive index is less than 1.55, it is evaluated as having a high refractive index which is capable of being used in the range of optical use.

[Method for evaluating film formation]

The primer was applied to the surface of a polyethylene terephthalate substrate having a film thickness of 125 μm to have a film thickness of about 1 μm when dried, and heated at 150 ° C for 5 minutes to form a primer layer on the surface of the substrate.

○: The surface of the primer layer was visually observed to be transparent.

△: The surface of the primer layer was visually observed to be transparent, but cracks were confirmed.

X: The surface of the primer layer was visually observed to show cracks in the degree of whitening, and a part of the primer layer was easily peeled off from the polyethylene terephthalate substrate.

Claims (2)

An image display device comprising an image display device comprising a laminate having a primer layer formed on a surface of a substrate using a primer comprising a urethane resin composition, and on a surface of the primer layer An overcoat layer formed using a photocurable resin composition characterized in that the urethane resin composition contains a urethane resin (A) and an aqueous medium (B). a urethane resin composition obtained by reacting a polyol (a1) and a polyisocyanate (a2), wherein the polyol (a1) contains a formula (1) a polyol (a1-1) represented by a group selected from the group consisting of polyether polyols (a1-3) comprising an aromatic polyester polyol (a1-2) and an epoxyalkyl group added to bisphenol More than one type of polyol, wherein the aqueous medium (B) is only water, or is water and an alkyl ether selected from the group consisting of alcohols, ketones, polyalkylene glycols, and polyalkylene glycols. a mixture of organic solvents in the group; [R ¹ in the above formula (1) independently represents a group having an aliphatic structure or an aromatic structure, and R ^{2 each} independently represents an alkylene group]. The image display device according to claim 1, wherein the photocurable resin composition contains a resin having a polymerizable unsaturated double bond and a monomer having a polymerizable unsaturated double bond.