JP2019167530A - Aqueous coating agent for in-line coat, cured film, and laminate - Google Patents

Abstract

To provide an aqueous coating agent for an in-line coat that gives a laminate having excellent resistance (moist heat resistance) even when exposed to higher temperature and higher humidity than in the conventional art.SOLUTION: This invention relates to an aqueous coating agent for in-line coat containing a urethane poly (meth) acrylate (A) that contains a reactant between a hydroxy group-containing poly (meth) acrylate (a1) and an isocyanate (a2) containing a structure in which an aromatic ring is directly bonded to an isocyanate group, and an emulsifier (B) having a (meth) acryloyl group and an anionic group.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous in-line coating coating agent, a cured film, and a laminate.

  Inline coating, which is one of the surface modification methods for films used for substrates, is a technique for surface modification during stretching in the machine and transverse directions of the film, and has fewer manufacturing steps than offline coating. Moreover, thin film application | coating is possible and there exists an advantage that a drying process can be skipped, and it can apply to the surface protection film of a flat panel display, the protection film of a solar cell, etc. In such applications, scratch resistance and heat-and-moisture resistance are required.

  As a coating agent used for in-line coating, water-based ones have been studied. For example, specific mono- or polypentaerythritol (meth) acrylate, urethane poly (meth) acrylate having a radical polymerizable unsaturated double bond, An emulsion coating composition containing a radical polymerization reactive surfactant is known (Patent Document 1). However, the heat and humidity resistance is not excellent, and there is a problem that the transparency of the laminate is lowered by exposure to such an environment.

Japanese Patent Laid-Open No. 9-137081

  The present invention provides a coating agent for an aqueous in-line coating that gives a laminate having a small decrease in transparency even when exposed to high temperature and high humidity as compared with the prior art, that is, having excellent moisture and heat resistance; cured film; laminate It is in.

  As a result of intensive studies, the present inventors have found that a coating agent for an aqueous in-line coating containing an emulsion of urethane poly (meth) acrylate produced from a specific isocyanate as a raw material solves the above problems, and has completed the present invention. It came to do. That is, the present invention relates to the following aqueous in-line coating coating agent, cured film, and laminate.

1. Urethane poly (meth) acrylate (A) containing a reaction product of a hydroxyl group-containing poly (meth) acrylate (a1) and an isocyanate (a2) containing a structure in which an aromatic ring and an isocyanate group are directly bonded, and a (meth) acryloyl group and A coating agent for aqueous in-line coating, comprising an emulsion with an emulsifier (B) having an anionic group.

2. The coating agent for aqueous in-line coating according to item 1, wherein the component (a1) contains dipentaerythritol (meth) acrylates and / or tripentaerythritol (meth) acrylates.

3. (A2) The coating agent for water-system in-line coating of the preceding clause 1 or 2 whose component is diisocyanate.

4). The coating agent for aqueous in-line coating according to any one of items 1 to 3, wherein the content of the component (B) is 1 to 10 parts by weight with respect to 100 parts by weight of the component (A) in terms of solid content.

5. Furthermore, the coating agent for water-system in-line coating in any one of Claims 1-4 containing poly (meth) acrylate (C).

6). Furthermore, the coating agent for water-system in-line coats in any one of Claims 1-5 containing an inorganic particle (D).

7). 7. A cured film of the coating agent for aqueous in-line coating according to any one of 1 to 6 above.

8). A laminate having the cured film as described in 7 above on at least one side of the substrate.

  According to the coating agent for aqueous in-line coating of the present invention, the laminate having the cured film has excellent moisture and heat resistance. Furthermore, it is excellent also in abrasion resistance.

  The coating agent for aqueous in-line coating of the present invention comprises a specific urethane poly (meth) acrylate (A) (hereinafter referred to as component (A)), an emulsifier (B) having a (meth) acryloyl group and an anionic group (hereinafter referred to as “component”). And (B) component).

  Component (A) is a hydroxyl group-containing poly (meth) acrylate (a1) (hereinafter referred to as (a1) component) and an isocyanate (a2) (hereinafter referred to as (a2) component) containing a structure in which an aromatic ring and an isocyanate group are directly bonded. Of the reaction product).

  The component (a1) is not particularly limited as long as it is a compound having at least one hydroxyl group and at least one (meth) acryloyl group in the molecule. For example, erythritol di (meth) acrylate, erythritol tri (meta) ) Erythritol (meth) acrylates such as acrylate; Pentaerythritol (meth) acrylates such as pentaerythritol di (meth) acrylate and pentaerythritol tri (meth) acrylate; Dipentaerythritol di (meth) acrylate and dipentaerythritol tri ( Dipentaerythritol (meth) acrylates such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate; tripentaerythritol (meta) Tripentaerythritol (meth) acrylate such as acrylate. These may be used alone or in combination of two or more. Among them, dipentaerythritol (meth) acrylates and tripentaerythritol (meth) acrylates are preferable because the hardness of the cured film is increased and the scratch resistance is easily excellent, and dipentaerythritol penta (meth) acrylate and tripentaerythritol are preferable. (Meth) acrylate is more preferred. In addition, (meth) acryloyl group means a methacryloyl group or acryloyl group, and (meth) acrylate means methacrylate or acrylate. The same applies to the following (meta).

  The component (a1) may contain a hydroxyl-free poly (meth) acrylate. The hydroxyl-free poly (meth) acrylate is not particularly limited, and examples thereof include erythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. As content of a hydroxyl-free poly (meth) acrylate, it is about 1-90 weight part with respect to 100 weight part of (a1) component.

  As a commercial item of the component (a1), “Aronix M305”, “Aronix M306”, “Aronix M400”, “Aronix M402”, “Aronix M403”, “Aronix M404”, “Aronix M405”, “Aronix M406” ( Manufactured by Toagosei Co., Ltd.), “KAYARAD DPHA” (manufactured by Nippon Kayaku Co., Ltd.), “A-9550”, “A-DPH” (manufactured by Shin-Nakamura Chemical Co., Ltd.), “Biscoat # 300”, “Biscoat # 802” (manufactured by Osaka Organic Chemical Co., Ltd.), “Miramer M600” (manufactured by MIWON Specialty Chemical Co, Ltd.) and the like can be obtained.

  The component (a2) is an isocyanate including a structure in which an aromatic ring and an isocyanate group are directly bonded, and examples thereof include monoisocyanates such as phenyl isocyanate, 2-methylphenyl isocyanate, 3-methylphenyl isocyanate, 4-methylphenyl isocyanate; 1,4-phenylene diisocyanate, toluene diisocyanate (toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or mixtures thereof), 2,2′-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4 ′ -Diisocyanates such as diphenylmethane diisocyanate, diphenyl ether-4,4'-diisocyanate; triisocyanates such as triphenylmethane triisocyanate; Dimers of these isocyanates, multimers such as trimer and the like. These may be used alone or in combination of two or more. Among these, diisocyanate is preferable from the viewpoint of heat and heat resistance, and toluene diisocyanate and 4,4'-diphenylmethane diisocyanate are more preferable.

  The component (A) is not particularly limited, and can be obtained by various known production methods. As the production method, for example, the (a1) component and the (a2) component are reacted in the presence of a catalyst, or the (a2) component is dropped and reacted in a solution in which the (a1) component and the catalyst are mixed. Etc. Also, the production conditions are not particularly limited. For example, the temperature is usually about 50 to 100 ° C., preferably about 60 to 80 ° C., and the time is usually about 1 to 24 hours, preferably about 1 to 12 hours.

Although it does not specifically limit as the usage-amount of (a1) component and (a2) component, By the ratio (NCO _(a2) / OH _(a1) ) of the number of hydroxyl groups of (a1) component and the number of isocyanate groups of (a2) component. 0.1 to 1 is preferable, about 0.2 to 1 is more preferable, and about 0.5 to 1 is more preferable.

  The catalyst is not particularly limited, and for example, triethylenediamine, 1,8-diazabicyclo- [5,4,0] -7-undecene, stannous octylate, lead dioctylate, bismuth dioctylate, bismuth trioctylate. Bismuth trineodecanoate, dibutyltin dilaurate, dioctyltin laurate and the like. Further, the content of the catalyst is not particularly limited, and is usually less than 1 part by weight, preferably less than 0.1 part by weight with respect to 100 parts by weight of all reaction components.

  In addition, an antioxidant such as 3,5-di-t-butyl-4-hydroxytoluene, tetrakis [methylene-3- (3 ′, 5′-t-butyl-4-hydroxyphenyl) propionate] methane is added. May be.

  Moreover, although the said manufacturing method is preferable without a solvent, you may use an organic solvent suitably. The organic solvent is preferably one that dissolves in water, for example, alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as methyl cellosolve and ethyl cellosolve; propylene And ethers such as glycol monomethyl ether.

  The physical properties of the component (A) are not particularly limited. For example, the viscosity (solid) at a temperature of 25 ° C. is usually about 1,000 to 200,000 mPa · s, preferably 5,000 to 100,000 mPa · s. Degree.

  The component (B) is an emulsifier having a (meth) acryloyl group and an anionic group. The (meth) acryloyl group means an acryloyl group or a methacryloyl group, and the number of (meth) acryloyl groups in the component (B) is not particularly limited, but one or two is preferable, and one is more preferable.

Examples of the anionic group include sulfate ester base (—OSO ₃ X), sulfonate group (—SO ₃ X), phosphate ester base (—OPO (OX) ₂ ), and phosphonate base (—PO (OX)). ₂ ), carboxylate group (—COOX), boronate group (—B (OX) ₂ ) (X is a cationic group) and the like.

Examples of the cationic group represented by X include an ammonium group (NH ₄ ); an alkali metal atom such as lithium, sodium, and potassium; NRa ₃ Rb (Ra is independently a hydrogen atom or a carbon number of 1 to 10). And Rb is a monovalent organic group having 1 to 20 carbon atoms.) And the like.

  Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by Ra include an alkyl group having 1 to 10 carbon atoms. As a C1-C10 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group etc. are mentioned, for example.

  Examples of the monovalent organic group having 1 to 20 carbon atoms represented by Rb include a monovalent group containing a hydrocarbon group having 1 to 20 carbon atoms and a (meth) acryloyl group.

  The component (B) preferably has a polyoxyalkylene group from the viewpoint of emulsification with the component (A).

  The component (B) preferably has an aromatic ring, and more preferably has a plurality of aromatic rings. When the component (B) has an aromatic ring, the scratch resistance and wet heat resistance of the cured film can be improved. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. This aromatic ring may be unsubstituted or substituted with an alkyl group, an aryl group, a combination thereof or the like.

  (B) As a component, the compound which has a (meth) acryloyl group, an anionic group, an aromatic ring, and a polyoxyalkylene group is preferable.

  (B) As a commercial item of a component, RE1000, Antox MS60 (above, Nippon Emulsifier Co., Ltd. product) etc. are mentioned, for example.

  As the component (B), a compound having a sulfate ester base is more preferable. For example, a polyoxyethylene polycyclic phenyl ether sulfate salt having a methacryloyl group, bis (polyoxyethylene polycyclic phenyl ether methacrylate sulfate salt), Examples include polyoxyethylene polycyclic phenyl ether sulfate having an acrylic group.

  Although it does not specifically limit as content of (B) component, About 1-10 weight part is preferable with respect to 100 weight part of (A) component by solid content weight, and about 1.5-6 weight part is more. Preferably, about 2 to 5 parts by weight is particularly preferable. By making content of (B) component into the said range, it can emulsify efficiently and also can make the abrasion resistance and wet heat resistance of a cured film compatible.

  The coating agent for aqueous in-line coating of the present invention may contain an emulsifier (B2) having no (meth) acryloyl group (hereinafter referred to as component (B2)). Examples of the component (B2) include nonionic emulsifiers and anionic emulsifiers.

  The nonionic emulsifier is not particularly limited, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene polycyclic phenyl ether, and polyoxyethylene sorbitan fatty acid ester. These may be used alone or in combination of two or more.

  The anionic emulsifier is not particularly limited, and examples thereof include dialkyl sulfosuccinic acid ester salts, alkane sulfonic acid salts, α-olefin sulfonic acid salts, polyoxyethylene alkyl ether sulfosuccinic acid ester salts, and polyoxyethylene styryl phenyl ether sulfosuccinic acid esters. Salt, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl ether sulfate, polyoxyethylene dialkyl ether sulfate, polyoxyethylene trialkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, etc. . These may be used alone or in combination of two or more.

  Although it does not specifically limit as content of (B2) component, About 0.1-10 weight part is preferable with respect to 100 weight part of (A) component by solid content weight, About 0.2-6 weight part Is more preferable. In addition, the content ratio (solid content weight) with the component (B) is preferably about (B) / (B2) = 1/100 to 1/10, more preferably about 1/30 to 1/3.

  The aqueous in-line coating agent of the present invention preferably contains a dispersion medium. As the dispersion medium, water is preferable from the viewpoint of environmental load, but a mixed dispersion medium containing water and an organic solvent may be used.

  The organic solvent is not particularly limited as long as it is soluble in water. For example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol N-hexyl alcohol, n-octyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, diacetone alcohol and other alcohols; ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and other ethers, etc. Can be mentioned. These may be used alone or in combination of two or more. In addition, when containing an organic solvent, as an upper limit of content of an organic solvent, less than 10 weight% is preferable, for example.

  The coating agent for aqueous in-line coating of the present invention can be obtained by emulsification after adding (A) component, (B) component and water and, if necessary, a dispersion medium other than water and mixing. The emulsification method is not particularly limited, and various known methods such as an inversion emulsification method and a mechanical emulsification method can be applied. The emulsification conditions are not particularly limited, and for example, the temperature is usually about 5 to 70 ° C, preferably about 10 to 50 ° C. The time is usually about 1 to 24 hours, preferably about 1 to 12 hours. In addition, you may pre-emulsify the mixture of (A) component and (B) component before emulsification.

  The apparatus used for the emulsification is not particularly limited, and examples thereof include a propeller mixer, a turbine mixer, a homomixer, a disper mixer, an ultramixer, a colloid mill, a high-pressure homogenizer, and an ultrasonic wave. An apparatus can be used in combination as appropriate.

  Although it does not specifically limit as a physical property of the coating agent for water-system in-line coats obtained by the said manufacturing method, For example, the average primary particle diameter by a light-scattering method is about 0.05-2 micrometers, and about 0.1-1 micrometers is preferable. More preferred.

  The viscosity at a solid concentration of 50% by weight and a temperature of 25 ° C. is preferably about 1 to 50 mPa · s, more preferably about 2 to 20 mPa · s.

  The coating agent for aqueous in-line coating of the present invention may further contain poly (meth) acrylate (C) (hereinafter referred to as “component (C)”). The component (C) is not particularly limited. For example, erythritol (meth) acrylates such as erythritol di (meth) acrylate, erythritol tri (meth) acrylate, erythritol tetra (meth) acrylate; pentaerythritol di (meth) acrylate , Pentaerythritol (meth) acrylates such as pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate; dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meta) ) Dipentaerythritol (meth) acrylates such as acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Relate like; tripentaerythritol (meth) acrylate. These may be used alone or in combination of two or more. Of these, dipentaerythritol (meth) acrylates and tripentaerythritol (meth) acrylate are preferred from the viewpoint of curability.

  The content of the component (C) is not particularly limited, and is 500 parts by weight or less, preferably 300 parts by weight or less, based on 100 parts by weight of the component (A) in terms of solid content.

  The coating agent for aqueous in-line coating of the present invention may further contain inorganic particles (D) (hereinafter referred to as “component (D)”). The component (D) is not particularly limited, and examples thereof include metal oxides such as aluminum oxide, silicon oxide, zirconium oxide, zinc oxide, and titanium oxide. In addition, (D) component may be surface-treated by the compound which has an alkoxy group, a carboxy group, a (meth) acryloyl group, an epoxy group, a thiol group, etc. As the compound, a (meth) acryloyl group-containing silane compound is preferable, and among these, a silicon oxide surface-treated with (meth) acryloxypropyltrimethoxysilane is particularly preferable.

  Although it does not specifically limit as a volume average particle diameter of (D) component, About 10-200 nm is preferable from the point which ensures the transparency of a cured film, and about 20-100 nm is more preferable. In addition, it does not specifically limit as a measuring method of a volume average particle diameter, For example, the light-scattering method etc. are mentioned.

  The content of the component (D) is not particularly limited, and is about 1 to 50 parts by weight, preferably 1 with respect to the total of 100 parts by weight of the component (A) and the component (B) in terms of solid content. About 30 parts by weight.

  The coating agent for aqueous in-line coating of the present invention further comprises an antifoaming agent, leveling agent, preservative, antioxidant, antistatic agent, thickener, foaming agent, thickener, plasticizer, ultraviolet absorber, and colorant. Further, additives such as a polymerization initiator and a polymerization inhibitor may be contained.

  Polymerization initiators are roughly classified into those that generate active species by light irradiation or heating. The polymerization initiator can be either water-soluble or oil-soluble.

  The polymerization initiator that generates active species by light irradiation is not particularly limited. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one 3-methylacetophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2- Droxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2- Methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. These may be used alone or in combination of two or more.

  The polymerization initiator that generates active species by heating is not particularly limited. For example, hydroperoxide, peroxyester, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, peroxyketal, ketone Organic peroxides such as peroxides; persulfates such as ammonium persulfate, sodium persulfate, potassium persulfate; 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (N-butyl) -2-methylpropionamide), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′- Azobis [N- (2-propenyl) -2-methylpropioamide], 1-[(1-sia 1-azo compounds such as methyl ethyl) azo] formamide. These may be used alone or in combination of two or more.

  It does not specifically limit as content of a polymerization initiator, It is about 0.1-20 weight part normally with respect to 100 weight part of (A) component by solid content weight, Preferably it is about 1-10 weight part. is there.

  It does not specifically limit as a polymerization inhibitor, For example, p-methoxyphenol, a phenothiazine etc. are mentioned as a commercial item, for example. Moreover, as a commercial item, IRGANOX1010, IRGANOX1035 (above, BASF Japan Co., Ltd. product), SumilizerGA-80 (Sumitomo Chemical Co., Ltd.), Kinopower QS-30, Kinopower QS-W10 (above, Kawasaki Chemical Industries (above) Etc.). These may be used alone or in combination of two or more.

  The content of the polymerization inhibitor is not particularly limited, and is usually less than 1 part by weight and preferably less than 0.1 part by weight with respect to 100 parts by weight of component (A) in terms of solid content.

  Although it does not specifically limit as solid content concentration of the coating agent for water-system in-line coating of this invention, Preferably it is about 10-60 weight%, More preferably, it is about 15-50 weight%.

<Curing film>
The cured film of the present invention is obtained by curing the aqueous in-line coating agent. The curing method is not particularly limited, and heating or active energy rays such as a hydrolamp or a xenon lamp can be appropriately used, and heating and active energy rays may be combined.

  It does not specifically limit as thickness of a cured film, Usually, it is about 0.2-10 micrometers, Preferably it is about 0.5-5 micrometers.

<Laminate>
The laminate of the present invention has the cured film on at least one side of a substrate. Specifically, the coating agent for aqueous in-line coating is applied to at least one side of the substrate, and then heated and cured. Is obtained.

  The shape of the substrate is usually a film, and the type of the substrate is not particularly limited, and various known materials can be used. For example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polypropylene, and ethylene-vinyl acetate are used. Examples of the polymer include polycarbonate, polyamide, polyimide, polyamideimide, polyphenylene ether, polyphenylene sulfide, polyarylate, polysulfone, and cycloolefin polymer.

  As the resin film that is a material of the base material, for example, an unstretched resin film obtained by molding a resin into a sheet shape, or a stretched resin film obtained by stretching this unstretched resin film can be used.

  The unstretched resin film can be obtained, for example, by molding a resin material into a sheet shape by a melt extrusion method, a melt flow method, a calendar method, or the like. Moreover, as a forming method, a melt extrusion method is preferable. Examples of the molding apparatus used in the melt extrusion method include a single screw extruder and a twin screw extruder. It does not specifically limit as melting | fusing conditions, For example, temperature is about 200 to 300 degreeC normally.

  The stretched resin film is obtained by stretching the unstretched resin film in the longitudinal direction (flow direction) or the short direction. As the stretched resin film, an unstretched resin film is preferably stretched in the longitudinal direction (flow direction).

  It does not specifically limit as a method of extending | stretching an unstretched resin film to a longitudinal direction, For example, the method of extending | stretching 2-5 times with the roll heated previously etc. are mentioned. Moreover, it is not specifically limited as said roll temperature, Usually, it is about 80-120 degreeC, Preferably it is about 80-100 degreeC.

  The method for stretching the unstretched resin film in the lateral direction is not particularly limited, and for example, a method of gripping the end by a method such as clipping and guiding the hot air zone to stretch 2.5 to 5 times, etc. Can be given. It does not specifically limit as temperature of a hot air zone, Usually, it is about 70-140 degreeC, Preferably it is about 80-120 degreeC.

  In the present invention, it is preferable to stretch the substrate before application of the aqueous in-line coating agent and before heating. The stretching direction may be the longitudinal direction (flow direction), the short direction, or both the longitudinal direction and the short direction, but may be stretched in the longitudinal direction before coating and stretched in the short direction before heating. preferable.

  The method for applying the coating agent for water-based in-line coating to the substrate is not particularly limited. For example, gravure coating method, die coating method, spray coating method, wire bar coating method, reverse roll coating method, curtain coating method, dip coating. Law.

  The heating means after applying the coating agent for aqueous in-line coating is not particularly limited, and examples thereof include a circulating dryer. Moreover, conditions are not specifically limited, For example, temperature is about 160-240 degreeC normally, and time is about 1 to 60 second.

When the coating agent for aqueous in-line coating of the present invention contains a polymerization initiator that generates active species by light irradiation, the coating film may be irradiated with light before heating. The light irradiation means is not particularly limited, and examples thereof include irradiation using a high pressure mercury lamp, a hydro lamp, a xenon lamp, and the like. Also as the amount of irradiation is not particularly limited, usually about 1,000~5,000J / ^{m 2.}

  The average thickness of the laminate obtained by the above preparation method is, for example, generally about 30 to 200 μm for the entire laminate, and about 0.2 to 10 μm for the cured film alone.

  The laminate of the present invention can be suitably used as a surface protective film such as a flat panel display, a solar battery, a touch panel, an antireflection film, or the like. Moreover, it can be used in a wide range of applications as various materials such as building materials and vehicles.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In addition, the part and% in an Example and a comparative example are a basis of weight unless there is particular notice.

Production Example 1 (Production of component (A-1))
In a reaction vessel equipped with a thermometer, a stirrer, and a cooling tube, Aronics M402 (a mixture of dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate = 65/35 (solid content weight), manufactured by Toagosei Co., Ltd.) 1000 parts, 4,4′-diphenylmethane diisocyanate (Millionate MT, manufactured by Tosoh Corporation), 59.3 parts, 3,5-di-tert-butyl-4-hydroxytoluene (BHT, Honshu Chemical Industry) 0.25 part made by Co., Ltd. and 0.06 part dioctyltin laurate were charged, and the temperature was raised to 80 ° C. with stirring and reacted. The reaction was conducted in accordance with JIS K7301 (reacting excess dibutylamine and back titrating the excess with hydrochloric acid. Using bromophenol blue as an indicator) until the reaction rate reached 95% or more. And urethane poly (meth) acrylate (A-1) was obtained.

Production Examples 2-3, Comparative Production Examples 1-2
With the composition shown in Table 1, urethane poly (meth) acrylates (A-2) to (A-3) and (E-1) to (E-2) were obtained in the same manner as in Production Example 1.

Production Example 4
Mixture of 50 parts (solid content: 50 parts) of component (A-1) obtained in Production Example 1 and KAYARAD DPHA (dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate = 60/40 (solids weight)) 50 parts (solid content: 50 parts) (manufactured by Yakuhin Co., Ltd.) (hereinafter also referred to as KAYARAD) were mixed at room temperature to obtain urethane poly (meth) acrylate (A-4).

Abbreviations for each component in Table 1 represent the following compounds.
<Hydroxyl-containing poly (meth) acrylate>
M402: trade name “Aronix M402” (mixture of dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate = 65/35 (solid content weight), manufactured by Toagosei Co., Ltd.)
V # 802: Trade name “Biscoat # 802” (tripentaerythritol acrylate (see also the chemical formula in the next paragraph), manufactured by Osaka Organic Chemical Industry Co., Ltd.)
KAYARAD: trade name “KAYARAD DPHA” (a mixture of dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate = 60/40 (solid content weight), manufactured by Nippon Kayaku Co., Ltd.)
<Isocyanate>
MDI: 4,4′-diphenylmethane diisocyanate (Millionate MT, manufactured by Tosoh Corporation)
TDI: Toluene diisocyanate (toluene-2,4-diisocyanate / toluene-2,6-diisocyanate = 4/1 (solid content weight) mixture, manufactured by Wako Pure Chemical Industries, Ltd.)
IPDI: Isophorone diisocyanate XDI: 3-xylylene diisocyanate

  V # 802 (trade name “Biscoat # 802”) used in Production Example 3 is represented by the following chemical formula.

Production Example 5 (Production of emulsifier (B-1))
To 171.2 parts by mass of N, N-diethylaminoethyl acrylate, water is added from a 30% aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate ammonium salt (trade name “New Coal 707-SF”, manufactured by Nippon Emulsifier Co., Ltd.). After adding 920.1 parts of polyoxyethylene polycyclic phenyl ether sulfate ammonium salt obtained by distilling off under reduced pressure, it was made to react for 1 hour, and 1074.5 parts of emulsifiers (B-1) were obtained.

Examples 1-8, Comparative Examples 1-3
After mixing water so that the solid content concentration is 50% with respect to the types and amounts of urethane poly (meth) acrylates and emulsifiers listed in Table 2, a high-pressure homogenizer (device name “C-ES008C”, Yoshida Machine) Kogyo Co., Ltd.) was used for emulsification under the conditions of a pressurized pressure of 200 MPa, a time of 60 minutes, and a temperature of 25 ° C., thereby preparing an aqueous in-line coating agent. The composition is shown in Table 2 (the same applies hereinafter).

Production Example 6
First, 100 parts of colloidal silica dispersion (trade name “PL-3”, manufactured by Fuso Chemical Industry Co., Ltd., concentration 20%) and 5 parts of 3-methacryloxypropyltrimethoxysilane were added and stirred at a temperature of 60 ° C. for 3 hours. Then, silica (D-1) having a volume average particle diameter of 35 nm modified with methacryloxypropyltrimethoxysilane (20% concentration aqueous dispersion, acrylic equivalent: 5,000 g / eq) was prepared.

Example 9
15 parts (solid content: 3 parts) of the component (D-1) were mixed with 194 parts (solid content: 97 parts) of the aqueous in-line coating agent of Example 1.

Comparative Example 4
Water-based in-line coating using 100 parts of KAYARAD DPHA (mixture of dipentaerythritol hexaacrylate / dipentaerythritol pentaacrylate = 60/40 (solid content weight), manufactured by Nippon Kayaku Co., Ltd.) instead of component (A) A coating agent was prepared.

[Base material]
After sufficiently drying pellets (homopolymer) of polyethylene terephthalate (hereinafter referred to as PET), the pellets are supplied to a single screw extruder, melted at 250 ° C., extruded into a sheet form from a T-die, and then cast by electrostatic application. A PET unstretched film was obtained by winding it around a 45 ° C. cooling roll and allowing it to cool and solidify. This unstretched film was heated to 90 ° C. and stretched 3.0 times in the longitudinal direction to obtain a uniaxially stretched PET film. This PET uniaxially stretched film was used as a substrate.

  The aqueous in-line coating agent obtained in each Example and Comparative Example was diluted with water to a concentration of 30%, and as a leveling agent, Footent 215M (nonionic polyoxyethylene ether, manufactured by Neos Co., Ltd.) was used. 0.3 part was added with respect to 100 parts of solid content of a coating agent.

[Laminate]
Each aqueous in-line coating coating agent was applied to one surface of the substrate by a reverse roll coating method. After guiding to the preheating zone and drying by heating at 130 ° C. for 1 minute, the film was stretched 3.0 times in the short direction at 90 ° C. The base material is stretched 3.0 times in the longitudinal direction and 3.0 times in the transverse direction, so the total stretch ratio is 9.0 times. Thereafter, the substrate is guided to the thermosetting zone, and is heated at 230 ° C. for 30 seconds to thermally cure the coating film, thereby being laminated on the substrate having an average thickness of 50 μm and one surface of the substrate. A laminate having an average thickness of 1 μm was obtained.

[Abrasion resistance]
Steel laminates (trade name “Bonstar No. 0000”, manufactured by Nippon Steel Wool Co., Ltd.) are applied to Gakushoku-type wear fastness tester (device name “AB-301”, manufactured by Test Sangyo Co., Ltd.). The surface of the cured film was attached and repeatedly rubbed 10 times under a load of 200 g / cm ² , and the presence or absence of scratches on the surface of the cured film was visually confirmed. The evaluation criteria are shown below. The results are shown in Table 2 (the same applies hereinafter).
(Evaluation criteria)
○: scars are scarce (less than 5)
Δ: Slightly scratched (5 or more and less than 10)
×: Many scratches (10 or more)

[Moisture and heat resistance]
The initial haze of each laminate was measured according to JIS K 7136: 2000. Next, the laminate was allowed to stand at a temperature of 85 ° C. and a humidity of 85% for 250 hours, and then the components bleeded out on the non-coated surface of the laminate were wiped off with gauze soaked with isopropanol. Thereafter, the haze of the laminate was measured again, and the difference between before and after the treatment (ΔHaze = haze after standing for 250 hours−initial haze) was determined. Here, the base material of the laminate includes a polyester oligomer as an impurity, and when the polyester oligomer is exposed to high temperature and high humidity, it penetrates the cured film and bleeds to the cured film side surface of the laminate. When it is out, the value of ΔHaze increases. ΔHaze is 1 or less.

* 1: Content based on 100 parts by weight (solid content) of urethane poly (meth) acrylate.
* 2: Mixed so that the total of urethane poly (meth) acrylate, emulsifier and component (D) is 100 parts by weight (solid content).

<Emulsifier>
-B-1: Use the emulsifier of Production Example 4-B-2: Emulsifier having a (meth) acryloyl group (trade name "RE-1000", manufactured by Nippon Emulsifier Co., Ltd.)
Nonionic: Nonionic emulsifier (trade name “New Coal N707”, manufactured by Nippon Emulsifier Co., Ltd.)

Claims (8)

  Urethane poly (meth) acrylate (A) containing a reaction product of a hydroxyl group-containing poly (meth) acrylate (a1) and an isocyanate (a2) containing a structure in which an aromatic ring and an isocyanate group are directly bonded, and a (meth) acryloyl group and A coating agent for aqueous in-line coating, comprising an emulsion with an emulsifier (B) having an anionic group.   The coating agent for aqueous in-line coating according to claim 1, wherein the component (a1) contains dipentaerythritol (meth) acrylates and / or tripentaerythritol (meth) acrylates.   The coating agent for aqueous in-line coating according to claim 1 or 2, wherein the component (a2) is diisocyanate.   Content of (B) component is 1-10 weight part with respect to 100 weight part of (A) component by solid content weight, The coating agent for water-system in-line coating in any one of Claims 1-3.   Furthermore, the coating agent for water-system in-line coating in any one of Claims 1-4 containing poly (meth) acrylate (C).   Furthermore, the coating agent for water-system in-line coats in any one of Claims 1-5 containing an inorganic particle (D).   The cured film of the coating agent for water-system in-line coating in any one of Claims 1-6.   The laminated body which has the cured film of Claim 7 in the at least single side | surface of a base material.