TWI804644B - Method for producing scratch-resistant hard coating film - Google Patents

Abstract

The subject of this invention is to provide the manufacturing method of the hard coating film which has excellent scratch resistance. The solution is a method for producing a scratch-resistant hard coating film, which at least includes the steps of applying a curable composition capable of forming a hard coating layer on a film substrate to form a coating film, and irradiating the coating film. A method for producing a scratch-resistant hard coat film in which the hard coating film is hardened by active energy rays, wherein the solvent contained in the curable composition is a solvent having a solvent swelling degree of 70% or less of the film base material at its normal boiling point .

Description

Method for producing scratch-resistant hard coating film

The present invention relates to a method for producing a scratch-resistant hard coating, and more specifically, to a method for producing a hard coating having excellent scratch resistance.

Many electronic devices, such as household electrical appliances such as televisions, communication equipment such as mobile phones, office equipment such as photocopiers, entertainment equipment such as game machines, medical equipment such as X-ray imaging equipment, and living equipment such as microwave ovens, are installed. A touch panel display using a liquid crystal display element or an OLED (organic EL) display element that can be operated by a human finger. In these touch panel displays, in order to prevent damage to the surface of the touch panel due to fingernails when people operate with their fingers, a transparent plastic film on the base material is provided on the uppermost surface of the touch panel to prevent Damaged hard coatings with scratch-resistant hard coatings.

On the other hand, in recent years, in order to improve the designability of the above-mentioned electronic equipment, there are cases where the above-mentioned touch panel display part is curved. When bending with the touch panel side as the outside, stress in the tensile direction is generated on the outermost hard coat layer. Therefore, the hard coating is required to have a certain degree of extensibility.

As a general method for forming a hard coat layer, a multifunctional acrylate containing a main agent, a photopolymerization initiator for initiating a hardening reaction by free radical polymerization of the multifunctional acrylate by active energy rays, and The hard coating solution for diluting the organic solvent that imparts coatability is coated on the base material, the organic solvent is removed by heating and drying, and then cured by irradiation with active energy rays to obtain a hard coating layer. However, materials based on multifunctional acrylates have low molecular mobility and resistance to external forces due to their high cross-linking density. Therefore, although scratch resistance is obtained, they usually do not have extensibility.

Therefore, in order to impart a certain degree of scratch resistance and extensibility to the hard coat layer, a polyfunctional acrylate oligomer with a molecular weight of, for example, 1,000 to 10,000 with an acrylate group density adjusted, or a polyfunctional aminomethyl Method of ester acrylate oligomer. These multifunctional acrylate oligomers have crosslinking sites and extension sites in their molecular structures, and through the molecular mobility of the extension sites, they can exhibit moderate scratch resistance and extensibility. A hard coat layer using a polyfunctional acrylate modified with polycaprolactone as such a polyfunctional acrylate oligomer is disclosed (Patent Document 1).

In addition, as a method of imparting antifouling properties and sliding properties to the surface of the hard coat layer, a method of adding a small amount of a fluorine-based surface modifier to a coating solution for forming the hard coat layer is used. The added fluorine-based surface modifier, due to its low surface energy, segregates on the surface of the hard coating to impart water and oil repellency. This fluorine-based surface modifying agent uses a perfluoropolyether having a poly(oxyperfluoroalkylene) chain, which has an active energy ray hardening site, and has a value of about 1,000 to 5,000 from the viewpoint of water repellency and oil repellency. number average molecular weight oligomers. However, these perfluoropolyethers have high fluorine concentration, so they have specific solubility in organic solvents, and only limited organic solvents can be used. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2013/191254

[Problem to be Solved by the Invention]

The object of this invention is to provide the manufacturing method of the hard coat film which has excellent scratch resistance. [Means to solve the problem]

The inventors of the present invention, as a result of repeated and intensive studies in order to solve the above-mentioned problems, have found that at least the step of forming a coating film is formed by applying a curable composition capable of forming a hard coat layer on a film substrate, and irradiating the coating film. In the method of producing a scratch-resistant hard coating film in the step of hardening with active energy rays, if the solvent swelling degree of the aforementioned film base material at its normal boiling point is 70% or less as the solvent contained in the aforementioned curable composition , can produce a hard coating with excellent scratch resistance, and complete the present invention. Furthermore, the inventors of the present invention also found that by using an appropriate film base material, it is possible to manufacture a hard coating film imparted with elongation in addition to excellent scratch resistance.

That is, the present invention, as a first point of view, relates to a method for producing a scratch-resistant hard coating film, which at least includes coating a curable composition capable of forming a hard coating layer on a film substrate to form a coating film. step, and the step of irradiating the coating film with active energy rays to harden the scratch-resistant hard coating film, wherein the solvent contained in the above-mentioned curable composition is a solvent of the above-mentioned film substrate at its normal boiling point Solvent with swelling degree below 70%. As a 2nd viewpoint, it is related with the manufacturing method like a 1st viewpoint, wherein the said film base material is a thermoplastic polyurethane film. As a third aspect, it relates to the production method according to the first aspect or the second aspect, wherein the curable composition contains (a) 100 parts by mass of an oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, (b) The two ends of the molecular chain containing poly(oxyperfluoroalkylene) groups are between 0.1 parts by mass and 10 parts by mass of perfluoropolyether modified with organic groups with or without the poly(oxyalkylene) groups parts by mass and (c) 1 to 20 parts by mass of a polymerization initiator that generates free radicals by active energy rays. As a fourth viewpoint, it relates to the production method as described in the third viewpoint, wherein the two ends of the molecular chain containing a poly(oxyperfluoroalkylene) group in the aforementioned (b) are interposed or not interposed between poly(oxyalkylene) groups. ) base, perfluoropolyether modified by organic group, is a perfluoropolyether selected from the following (b1) to (b6). (b1) Both ends of the molecular chain containing poly(oxyperfluoroalkylene) groups are modified with alcohol, sunflower group, carboxylic acid or Ester modified perfluoropolyether (b2) The alkoxysilyl group is bonded to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group through a poly(oxyalkylene) group and a divalent linking group. Perfluoropolyether (b3) Perfluoropolyether in which an alkoxysilyl group is bonded to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a link structure that does not have a poly(oxyalkylene) structure (b4) Having an active energy ray polymerizable group via a poly(oxyalkylene) group at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and having a poly(oxyalkylene) group at the other end of the molecular chain perfluoropolyether with hydroxyl groups (b5) At both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, a poly(oxyalkylene) group or a poly(oxyalkylene) group and a carbamate are separated in sequence bond, and perfluoropolyether with active energy ray polymerizable groups (b6) A perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond (but, in the aforementioned poly( Perfluoropolyethers having a poly(oxyalkylene) group between the oxyperfluoroalkylene) group and the aforementioned urethane linkage) As a fifth viewpoint, it relates to the production method as in the fourth viewpoint, wherein the two ends of the molecular chain containing a poly(oxyperfluoroalkylene) group in the aforementioned (b) are interposed or not interposed between poly(oxyalkylene) The base, the perfluoropolyether modified by the organic group, is the aforementioned (b6) at the two ends of the molecular chain containing the poly(oxyperfluoroalkylene) group, and has an active energy line through a urethane bond Perfluoropolyether with a polymerizable group (except for perfluoropolyether having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond). As a sixth viewpoint, it relates to the production method according to any one of the first viewpoint to the fifth viewpoint, wherein the solvent contained in the curable composition is selected from methanol, ethanol, n-propanol, and isopropanol , n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol, and ethylene glycol of one or more alcohols. As a seventh aspect, it relates to the production method according to the sixth aspect, wherein the solvent contained in the curable composition is methanol. [Effect of Invention]

According to the present invention, a method for producing a hard coat film having excellent scratch resistance can be provided. In addition, it is also possible to provide a method for producing a hard coat film imparted with elongation in addition to excellent scratch resistance by using an appropriate film base material.

The present invention relates to a method for producing a scratch-resistant hard coating film, which at least includes the steps of applying a curable composition capable of forming a hard coating layer on a film substrate to form a coating film, and irradiating the coating film. A method for producing a scratch-resistant hard coat film in which the hard coating film is hardened by active energy rays, wherein the solvent contained in the curable composition is a solvent having a solvent swelling degree of 70% or less of the film base material at its normal boiling point . The method for producing the scratch-resistant hard coat film of the present invention will be described in detail below. ＜Hardening composition＞ The curable composition that can form a hard coat layer that can be used in the present invention is not particularly limited as long as it is a composition that can be cured to form a hard coat layer by irradiation of active energy rays, and conventionally known ones can be used. It is preferable to include (a) 100 parts by mass of an oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, (b) The two ends of the molecular chain containing poly(oxyperfluoroalkylene) groups are between 0.1 parts by mass and 10 parts by mass of perfluoropolyether modified with organic groups with or without the poly(oxyalkylene) groups parts by mass, and (c) 1 to 20 parts by mass of a polymerization initiator that generates free radicals by active energy rays sclerosing composition. Hereinafter, each component of said (a)-(c) is demonstrated.

[(a) Oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups] The oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups refers to the oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups. In the curable composition of the present invention, preferred (a) oxyalkylene modified polyfunctional monomers having at least 3 active energy ray polymerizable groups are selected from the group having at least 3 active energy ray polymerizable groups. A group of monomers consisting of an oxyalkylene-modified polyfunctional (meth)acrylate compound and an oxyalkylene-modified polyfunctional urethane (meth)acrylate compound. In addition, in this invention, a (meth)acrylate compound means both an acrylate compound and a methacrylate compound. For example, (meth)acrylic acid refers to acrylic acid and methacrylic acid.

(a) The oxyalkylene group in the oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, for example, oxyethylene group, oxygen (methylethylene group), and Preferable oxyethylene modified polyfunctional monomers include oxyethylene modified polyfunctional monomers.

The above-mentioned oxyalkylene-modified polyfunctional (meth)acrylate compounds include, for example, polyol (meth)acrylate compounds modified with oxyethylene or oxy(methylethylene). Examples of the polyhydric alcohol include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerol, hexaglycerin, decaglycerin, polyglycerol, trimethylolpropane, di-trimethylolpropane, pentaerythritol, and dipentaerythritol.

(a) The active energy ray polymerizable group in the oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, for example, (meth)acryloxy group, vinyl group, ring Oxygen.

With respect to one molecule of (a) an oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, an oxyalkylene group such as an oxyethylene group or an oxy(methylethylene group) The base addition number is 1 to 30, preferably 1 to 12.

In the present invention, the above-mentioned (a) oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups can be used alone or in combination of two or more.

Preferred (a) oxyalkylene-modified polyfunctional monomers having at least 3 active energy ray polymerizable groups are (a1) oxyethylene-modified polyfunctional monomers having at least 3 active energy ray polymerizable groups. As for the polyfunctional monomer, the average amount of modified oxyethylene group can be listed, relative to 1 mol of the polymerizable group, the oxyethylene modified polyfunctional monomer (also referred to as (a1) only) has less than 3 mol. Oxyethylene modified polyfunctional monomers with at least 3 active energy ray polymerizable groups). Preferred (a1) oxyethylene-modified polyfunctional monomers having at least 3 active energy ray polymerizable groups in the curable composition capable of forming a hard coat layer are selected from the group having at least 3 active energy ray polymerizable groups. Energy line polymerizable group, and the average oxyethylene modified amount is less than 3 mol of oxyethylene modified polyfunctional (meth)acrylate compound and oxyethylene group relative to 1 mol of the polymerizable group A group of monomers that modify polyfunctional urethane (meth)acrylate compounds.

(a1) The average amount of modified oxyethylene groups in an oxyethylene-modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, relative to 1 mol of active energy ray polymerizable groups possessed by the monomer Specifically, it is less than 3 mol, preferably less than 2 mol with respect to 1 mol of active energy ray polymerizable groups that the monomer has. Also, (a) the average amount of oxyethylene modified in an oxyethylene-modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, relative to the active energy ray polymerizable group of the monomer 1 mol of radicals is greater than 0 mol, preferably 0.1 mol or more, more preferably 0.5 mol or more, relative to 1 mol of active energy ray polymerizable groups of the monomer.

The above-mentioned oxyethylene-modified polyfunctional (meth)acrylate compounds include, for example, oxyethylene-modified polyol (meth)acrylate compounds.

With respect to one molecule of (a1) oxyethylene group-modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, the addition number of oxyethylene group is 1 to 30, preferably 1 to 30 12.

[(b) Both ends of the molecular chain containing poly(oxyperfluoroalkylene) groups are perfluoropolyethers modified with organic groups with or without poly(oxyalkylene) groups] The component (b) plays a role as a surface modifying agent in the hard coat layer to which the curable composition of the present invention is applied. Moreover, since (b) component and (a) component are excellent in compatibility, cloudiness of a hard-coat layer can be suppressed by this, and the hard-coat layer which shows a transparent appearance can be formed. (b) Preferred organic groups in the component include, for example, alcohol (hydroxyl), helianthyl, carboxylic acid (carboxyl), ester (alkoxycarbonyl, acyloxy), alkoxysilyl, active energy ray polymerization sex base. Preferred (b) both ends of the molecular chain containing poly(oxyperfluoroalkylene) groups that can be used in hardening compositions that can form hard coatings are separated or not separated by poly(oxyalkylene) groups , perfluoropolyethers modified with organic groups, for example, can be selected from the following (b1) to (b6) (hereinafter also described as perfluoropolyethers (b1) to (b6)). (b1) Both ends of the molecular chain containing poly(oxyperfluoroalkylene) groups are modified with alcohol, sunflower group, carboxylic acid or Ester modified perfluoropolyether (b2) The alkoxysilyl group is bonded to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group through a poly(oxyalkylene) group and a divalent linking group. Perfluoropolyether (b3) Perfluoropolyether in which an alkoxysilyl group is bonded to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a link structure that does not have a poly(oxyalkylene) structure (b4) Having an active energy ray polymerizable group via a poly(oxyalkylene) group at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group, and having a poly(oxyalkylene) group at the other end of the molecular chain perfluoropolyether with hydroxyl groups (b5) At both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, a poly(oxyalkylene) group or a poly(oxyalkylene) group and a carbamate are separated in sequence bond, and perfluoropolyether with active energy ray polymerizable groups (b6) A perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond (but, in the aforementioned poly( perfluoropolyether having a poly(oxyalkylene) group between the oxyperfluoroalkylene) group and the aforementioned urethane linkage).

The number of carbon atoms of the alkylene group that can be used in the poly(oxyperfluoroalkylene) group of the perfluoropolyethers (b1) to (b6) is not particularly limited, but preferably 1 to 4 carbon atoms. That is to say, the poly(oxyperfluoroalkylene) group refers to the base of the structure obtained by interlinking divalent carbon fluoride groups with 1 to 4 carbon atoms and oxygen atoms, and the oxyperfluoroalkylene group refers to A base having a structure in which a divalent fluorinated carbon group with 1 to 4 carbon atoms is linked to an oxygen atom. Specifically, -[OCF ₂ ]-(oxyperfluoromethylene), -[OCF ₂ CF ₂ ]-(oxyperfluoroethylenyl), -[OCF ₂ CF ₂ CF ₂ ]-(oxygen perfluoropropane-1,3-diyl), -[OCF ₂ C(CF ₃ )F]-(oxyperfluoropropane-1,2-diyl) and the like. The aforementioned oxyperfluoroalkylene groups may be used alone or in combination of two or more. In this case, the bonding of the plurality of oxyperfluoroalkylene groups may be either block bonding or random bonding.

Among these, from the viewpoint of obtaining a cured film with good scratch resistance, it is particularly preferable to use a poly(oxyperfluoroalkylene) group having -[OCF ₂ ]-(oxyperfluoromethylene) and -[OCF Both ₂ CF ₂ ]-(oxyperfluoroethylenyl) are used as the base of the repeating unit. Wherein the above-mentioned poly(oxyperfluoroalkane) groups, especially the repeating unit: -[OCF ₂ ]- and -[OCF ₂ CF ₂ ]-, are expressed as [repeating unit: -[OCF ₂ ]-] in molar ratio : [Repeat unit: -[OCF ₂ CF ₂ ]-] = The base is preferably contained in a ratio of 2:1 to 1:2, more preferably the base is contained in a ratio of about 1:1. The bonding of these repeating units may be any of block bonding and random bonding. The number of repeating units of the above-mentioned oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, in terms of the total number of repeating units. Also, the weight average molecular weight (Mw) of the poly(oxyperfluoroalkylene) group measured in terms of polystyrene by gel permeation chromatography (GPC) is 1,000 to 5,000, preferably 1,500 to 3,000, Or 1,500 to 2,000.

The number of carbon atoms of the alkylene group that can be used in the poly(oxyalkylene) group of perfluoropolyether (b1), (b2), (b4) and (b5) is not particularly limited, and the number of carbon atoms is preferably 1 to 4. That is to say, the above-mentioned poly(oxyalkylene) group refers to the base of the structure obtained by interlinking an alkylene group having 1 to 4 carbon atoms and an oxygen atom, and the oxyalkylene group refers to a group having a structure having 1 to 4 carbon atoms. The base of the structure obtained by linking a divalent alkylene group with an oxygen atom. Examples of the above-mentioned alkylene group include ethylene group, 1-methylethylene group, trimethylene group, and tetramethylene group. The above-mentioned oxyalkylene groups may be used alone or in combination of two or more. In this case, the bonding of the plurality of oxyalkylene groups may be either block bonding or random bonding. Among them, the above-mentioned poly(oxyalkylene) group is especially preferably a poly(oxyethylene) group. The number of repeating units of the oxyalkylene group in the poly(oxyalkylene) group is, for example, in the range of 1 to 15, for example, in the range of 5 to 12, for example, in the range of 7 to 12 is more preferable.

Active energy ray polymerizable groups that can be used in perfluoropolyethers (b4) to (b6) include, for example, (meth)acryl groups, urethane (meth)acryl groups, and vinyl groups. The active energy ray polymerizable group is not limited to one having one active energy ray polymerizable moiety such as a (meth)acryl moiety, and may have two or more active energy ray polymerizable moieties.

In the present invention, (b) the two ends of the molecular chain comprising poly(oxyperfluoroalkane) groups are perfluoropolyethers modified by organic groups with or without poly(oxygen alkane) groups, It is more desirable to use in the ratio of 0.1-10 mass parts with respect to 100 mass parts of said (a) components, Preferably it is 0.2-5 mass parts.

Hereinafter, each perfluoropolyether (b1) to (b6) will be described in more detail.

[(b1) The two ends of the molecular chain containing poly(oxyperfluoroalkylene) groups, with or without poly(oxyalkylene) groups, modified with alcohol, sunflower group, or carboxylic acid or ester modified perfluoropolyether] Alcohol-modified, sunflower-modified, carboxylic acid-modified or ester-modified perfluoropolyether in perfluoropolyether (b1) means two-terminal alcohol-modified perfluoropolyether, two-terminal sunflower-modified perfluoropolyether Quality perfluoropolyether, two-terminal carboxylic acid modified perfluoropolyether, two-terminal ester modified perfluoropolyether.

Specific examples of the perfluoropolyether (b1) include, for example, the following. ･Alcohol modification at both ends: FOMBLIN (registered trademark) ZDOL 2000, same ZDOL 2500, same ZDOL 4000, same TX, same ZTETRAOL 2000GT, FLUOROLINK (registered trademark) D10H, same E10H [all manufactured by Solvay Specialty Polymers]; ･Sunflower base modified at both ends: FOMBLIN (registered trademark) AM2001, same as AM3001 [both manufactured by Solvay Specialty Polymers]; ･Carboxylic acid modification at both ends: FLUOROLINK (registered trademark) C10 [manufactured by Solvay Specialty Polymers]; ･Ester modified at both ends: FLUOROLINK (registered trademark) L10H [manufactured by Solvay Specialty Polymers];

上述式[1]中，R¹ 表示碳原子數1至5之烷基，R² 表示碳原子數1至5之烷基或苯基，a表示1至3之整數。[(b2) The alkoxysilyl group is bonded to both ends of the molecular chain containing the poly(oxyperfluoroalkylene) group through the poly(oxyalkylene) group and further through the divalent linking group Perfluoropolyether] The alkoxysilyl group in the perfluoropolyether (b2) is preferably a group represented by the following formula [1].

In the above formula [1], R ¹ represents an alkyl group having 1 to 5 carbon atoms, R ² represents an alkyl group or a phenyl group having 1 to 5 carbon atoms, and a represents an integer of 1 to 3.

The above-mentioned divalent linking group includes, for example, divalent groups such as alkylene groups having 1 to 5 carbon atoms, oxygen atoms, ester bonds, amide bonds, urethane bonds, and urea bonds, and combinations thereof. base.

上述式[2]中，R¹ 及R³ 係分別獨立地表示碳原子數1至5之烷基，R² 及R⁴ 係分別獨立地表示碳原子數1至5之烷基或苯基，a及b係分別獨立地表示1至3之整數，L¹ 至L⁴ 係分別獨立地表示碳原子數1至5之伸烷基，X¹ 及X² 係分別獨立地表示-OC(=O)-、-OC(=O)NH-、-NHC(=O)-、-NHC(=O) NH-或-O-，m及n係分別表示使m+n成為2至40之正整數，PFPE1表示以聚(氧全氟伸烷基)構造為核心，且其兩側具有與氧伸烷基連結的末端構造之基。The perfluoropolyether (b2) is preferably a compound represented by the following formula [2].

In the above-mentioned formula [2], R ¹ and R ³ represent independently an alkyl group with 1 to 5 carbon atoms, R ² and R ⁴ represent independently an alkyl group with 1 to 5 carbon atoms or a phenyl group, a and b each independently represent an integer of 1 to 3, ^L1 to ^L4 each independently represent an alkylene group with 1 to 5 carbon atoms, ^X1 and ^X2 each independently represent -OC(=O )-, -OC(=O)NH-, -NHC(=O)-, -NHC(=O) NH- or -O-, m and n respectively represent that m+n is a positive integer from 2 to 40 , PFPE1 represents a poly(oxyperfluoroalkylene) structure as the core, and has a terminal structure linked to an oxyalkylene group on both sides.

Specific examples of the alkyl group having 1 to 5 carbon atoms in ^R1 and ^R3 above include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- Butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, sec-pentyl, 3-pentyl, cyclopentyl. Among these specific examples, R ¹ and R ³ are particularly preferably methyl or ethyl.

Specific examples of the alkyl group having 1 to 5 carbon atoms in the above-mentioned R ² and R ⁴ include the groups exemplified for the above-mentioned R ¹ and R ³ . R ² and R ⁴ are preferably methyl or phenyl.

The above-mentioned a and b are preferably 3.

In addition, specific examples of alkylene groups having 1 to 5 carbon atoms in L ^{to L} include methylene, ethylene, trimethylene, methylethylene, tetramethylene, 1 -Methyltrimethylene, 2-methyltrimethylene, 1,1-dimethylethylenyl, pentamethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1 , 1-dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-ethyltrimethylene. Among these specific examples, L ¹ and L ² are especially preferably ethylidene or trimethylene, more preferably trimethylene. Also, L ³ and L ⁴ are preferably ethylidene or methylethylidene, more preferably ethylidene. That is, the oxyalkylene group represented by (L ₃ O) or (OL ₄ ) is preferably an oxyethylene group.

The aforementioned X ¹ and X ² are preferably -OC(=O)- or -OC(=O)NH-, more preferably -OC(=O)NH-, and more preferably *-OC(=O) NH-(In the formula, * represents the bonding terminal with (L ³ O) _m or (OL ⁴ ) _n ).

Also, m and n are preferably positive integers such that m+n becomes 12-20, respectively.

PFPE1 represents a poly(oxyperfluoroalkylene) structure as a core, and a group having a terminal structure linked to an oxyalkylene group on both sides. As the structure of the poly(oxyperfluoroalkylene) group, those specifically exemplified in the aforementioned poly(oxyperfluoroalkylene) group can be mentioned as a suitable structure. In addition, the terminal structure connected to the oxyalkylene group present on both sides, for example, when bonding to the -O- terminal of the poly(oxyperfluoroalkylene) group, **-(via 1 to 3 fluorine atoms) a substituted C2 or C3 alkylene group)- or **-CF ₂ C (=O)-, and the fluoroalkylene terminal of the poly(oxyperfluoroalkylene) group (for example -CF ₂ - , -C(CF ₃ )F-) bonding can include **-O-(an alkylene group with 2 or 3 carbon atoms substituted by 1 to 3 fluorine atoms)- or **-O-CF ₂ C(=O)-(** all represent the bonded terminal with the poly(oxyperfluoroalkylene) group). The aforementioned alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms includes, for example, -CHFCH ₂ -, -CF ₂ CH ₂ -, -CF ₂ CHF-, -CHFCH ₂ CH ₂ -, -CF ₂ CH ₂ CH ₂ -, -CF ₂ CHFCH ₂ -, preferably -CF ₂ CH ₂ -.

In the curable composition capable of forming a hard coat layer, perfluoropolyether (b2) may be used alone or in combination of two or more.

The above-mentioned perfluoropolyether (b2) is, for example, a compound having a hydroxyl group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group. The hydroxyl group can be obtained, for example, by reacting an alkoxysilane having an isocyanato group such as (3-isocyanatopropyl)trimethoxysilane.

[(b3) Perfluoropolyether in which an alkoxysilyl group is bonded to both terminals of a molecular chain containing a poly(oxyperfluoroalkylene) group via a link structure not having a poly(oxyalkylene) group] The above-mentioned poly(oxyperfluoroalkylene) group and alkoxysilyl group are exemplified by those listed in the above-mentioned perfluoropolyether (b2). Moreover, the linking structure which does not have a poly(oxyalkylene) structure can be mentioned as an example of the group mentioned in the "divalent linking group" in the said perfluoropolyether (b2).

上述式[3]中，R⁵ 及R⁷ 係分別獨立地表示碳原子數1至5之烷基，R⁶ 及R⁸ 係分別獨立地表示碳原子數1至5之烷基或苯基，r及s係分別獨立地表示1至3之整數，L⁵ 及L⁶ 係分別獨立地表示碳原子數1至5之伸烷基，X³ 及X⁴ 係分別獨立地表示-OC(=O)-、-OC(=O)NH-、-NHC(=O)-、-NHC(=O) NH-或-O-，PFPE2表示以聚(氧全氟伸烷基)構造為核心，其兩側具有與X³ 或X⁴ 連結的末端構造之基。The perfluoropolyether (b3) is preferably a compound represented by the following formula [3].

In the above formula [3], ^R5 and ^R7 are each independently representing an alkyl group with 1 to 5 carbon atoms, ^R6 and ^R8 are each independently representing an alkyl group or a phenyl group with 1 to 5 carbon atoms, r and s represent independently an integer of 1 to 3, L5 and ^L6 represent independently an alkylene group ^with 1 to 5 carbon atoms, ^X3 and ^X4 represent independently -OC(=O )-, -OC(=O)NH-, -NHC(=O)-, -NHC(=O) NH- or -O-, PFPE2 means poly(oxygen perfluoroalkylene) structure as the core, its Both sides have the base of the terminal structure linked to ^X3 or ^X4 .

In the above-mentioned formula [3], the alkyl group having 1 to 5 carbon atoms in R ⁵ and R ⁷ and R ⁶ and R ⁸ includes the alkyl groups exemplified in the above-mentioned R ¹ and R ³ . R ⁵ and R ⁷ are preferably methyl or ethyl. R ⁶ and R ⁸ are preferably methyl or phenyl. Also, the above-mentioned r and s are preferably 3.

In addition, specific examples of the alkylene group having 1 to 5 carbon atoms in ^L5 and ^L6 include the alkylene groups exemplified in the aforementioned ^L1 to ^L4 . Among the specific examples of the above-mentioned alkylene groups, L ⁵ and L ⁶ are especially preferably ethylene or trimethylene, more preferably trimethylene.

The aforementioned X ³ and X ⁴ are preferably -OC(=O)- or -OC(=O)NH-, more preferably -OC(=O)NH-, and more preferably *-OC(=O) NH-(wherein, * represents the bonding end with PFPE2).

PFPE2 represents a poly(oxyperfluoroalkylene) structure as the core, with bases of terminal structures linked to ^X3 or ^X4 on both sides. Examples of the poly(oxyperfluoroalkylene) structure and the terminal structures linked to ^X3 and ^X4 existing on both sides thereof include those exemplified in the aforementioned PFPE1.

The above-mentioned perfluoropolyether (b3), for example, is obtained by using, for example, (3-isocyanic acid It is obtained by reacting alkoxysilanes with isocyanato groups such as propyl)trimethoxysilane and the like.

In the curable composition of the present invention, perfluoropolyether (b3) may be used alone or in combination of two or more.

[(b4) Having an active energy ray polymerizable group at one end of a molecular chain containing a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group, and having a poly(oxyalkylene) group at the other end of the molecular chain perfluoropolyether with hydroxyl groups] The above-mentioned active energy ray polymerizable group is not limited to those having one active energy ray polymerizable moiety such as a (meth)acryl moiety, but may have two or more active energy ray polymerizable moieties, for example, Examples include structures of formula [A1] to formula [A5] shown below, and structures in which the acryl group in these structures is substituted with a methacryl group.

Specific examples of such perfluoropolyethers (b4) include the compounds shown below and compounds in which the acryl group in these compounds is substituted with a methacryl group. Moreover, in the structural formula, A represents the structure represented by the aforementioned formula [A1] to formula [A5], and PFPE represents a poly(oxyperfluoroalkylene) structure as the core with The base of the terminal structure, n represents the number of repeating units of the oxyethylidene group, and preferably represents a number from 1 to 10. As the structure of the poly(oxyperfluoroalkylene) group, those specifically exemplified in the aforementioned poly(oxyperfluoroalkylene) group can be mentioned as a suitable structure. In addition, the terminal structure connected to the oxyalkylene group that exists on both sides, for example, when it is bonded to the -O- terminal of the poly(oxyperfluoroalkylene) group, **-(via 1 fluorine atom to 3 substituted alkylene groups with 2 or 3 carbon atoms)- or **-CF ₂ C (=O)-, and the fluoroalkylene terminal of the poly(oxyperfluoroalkylene) group (such as -CF ₂ When -, -C(CF ₃ )F-) are bonded, **-O-(an alkylene group with 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms)- or **-O- CF ₂ C(=O)-(** all represent the bonding terminal with the poly(oxyperfluoroalkylene) group). The aforementioned alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms includes, for example, -CHFCH ₂ -, -CF ₂ CH ₂ -, -CF ₂ CHF-, -CHFCH ₂ CH ₂ -, -CF ₂ CH ₂ CH ₂ -, -CF ₂ CHFCH ₂ -, etc., preferably -CF ₂ CH ₂ -.

The above-mentioned perfluoropolyether (b4) is, for example, a compound having a hydroxyl group via a poly(oxyalkylene) group at both ends of a poly(oxyperfluoroalkylene) group, the hydroxyl group at one of the two ends, Method for subjecting 2-(meth)acryloxyethyl isocyanate to urethane reaction, method for subjecting (meth)acrylic acid chloride or chloromethylstyrene to dehydrochlorination reaction, subjecting (methyl ) acrylic acid dehydration reaction method, the method of subjecting itaconic anhydride to esterification reaction, etc. to obtain. Among these methods, especially in a compound having a hydroxyl group at both ends of a poly(oxyperfluoroalkylene) group via a poly(oxyalkylene) group, 2-(methyl The method of carrying out the urethanization reaction of acryloxyethyl isocyanate, or the method of carrying out the dehydrochlorination reaction of (meth)acrylic acid chloride or chloromethylstyrene on the hydroxyl group, from the viewpoint of ease of reaction Very good.

[(b5) At both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, a poly(oxyalkylene) group or a poly(oxyalkylene) group and a carbamic acid are separated in sequence ester bond, and perfluoropolyether with active energy ray polymerizable groups] The above-mentioned active energy ray polymerizable group is not limited to those having one active energy ray polymerizable moiety such as a (meth)acryl moiety, but may have two or more active energy ray polymerizable moieties, for example, Examples include structures of the aforementioned formula [A1] to formula [A5], and structures in which the acryl group in these structures is substituted with a methacryl group.

聚(氧全氟伸烷基)構造，可列舉與前述聚(氧全氟伸烷)基中所具體列舉之基，作為適合的構造。 又，其兩側所存在的與氧伸烷基連結之末端構造，例如，與聚(氧全氟伸烷)基之-O-末端鍵結時可列舉**-(經氟原子1個至3個取代之碳原子數2或3之伸烷基)-或**-CF₂ C (=O)-，與聚(氧全氟伸烷)基之氟伸烷基末端(例如-CF₂ -、 -C(CF₃ )F-)鍵結時，可列舉**-O-(經氟原子1個至3個取代之碳原子數2或3之伸烷基)-或**-O-CF₂ C(=O)-(**均表示與聚(氧全氟伸烷)基之鍵結端)。 上述經氟原子1個至3個取代之碳原子數2或3之伸烷基，例如可列舉-CHFCH₂ -、-CF₂ CH₂ -、-CF₂ CHF-、     -CHFCH₂ CH₂ -、-CF₂ CH₂ CH₂ -、-CF₂ CHFCH₂ -，較佳為   -CF₂ CH₂ -。Such a perfluoropolyether (b5), from the viewpoint of ease of industrial production, compounds represented by the structural formula shown below and compounds in which the acryl group is substituted with a methacryl group as preferred examples . Furthermore, in this structural formula, A represents one of the structures represented by the aforementioned formula [A1] to formula [A5], and PFPE represents a poly(oxyperfluoroalkylene) structure as the core, with oxygen stretches on both sides. In the base of the terminal structure of the alkyl link, n each independently represents the number of repeating units of the oxyethylene group, preferably represents the number of 1 to 15, more preferably represents the number of 5 to 12, and more preferably represents the number of 7 to 12 number.

As the structure of the poly(oxyperfluoroalkylene) group, those specifically mentioned for the above-mentioned poly(oxyperfluoroalkylene) group can be mentioned as a suitable structure. In addition, the terminal structure connected to the oxyalkylene group existing on both sides thereof, for example, when it is bonded to the -O- terminal of the poly(oxyperfluoroalkylene) group, **-(via 1 fluorine atom to 3 substituted alkylene groups with 2 or 3 carbon atoms)- or **-CF ₂ C (=O)-, and the fluoroalkylene terminal of the poly(oxyperfluoroalkylene) group (such as -CF ₂ When -, -C(CF ₃ )F-) are bonded, **-O-(an alkylene group with 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms)- or **-O -CF ₂ C(=O)-(** all represent the bonding terminal with the poly(oxyperfluoroalkylene) group). The aforementioned alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms includes, for example, -CHFCH ₂ -, -CF ₂ CH ₂ -, -CF ₂ CHF-, -CHFCH ₂ CH ₂ -, -CF ₂ CH ₂ CH ₂ -, -CF ₂ CHFCH ₂ -, preferably -CF ₂ CH ₂ -.

The perfluoropolyether (b5) used in the present invention preferably has a poly(oxyalkylene) group and an amine group interposed therebetween at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group. A formate linkage group, that is, a poly(oxyalkylene) group is respectively bonded to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, and each poly(oxyalkylene) group at the two ends is respectively A perfluoropolyether in which one urethane bond is bonded and an active energy ray polymerizable group is bonded to each of the urethane bonds at both ends. Furthermore, it is preferable that among the aforementioned perfluoropolyethers, the active energy ray polymerizable group is a perfluoropolyether having at least two or more active energy ray polymerizable moieties.

The above-mentioned perfluoropolyether (b5), for example, is obtained by applying 2- (Meth)acryloxyethyl isocyanate or 1,1-bis((meth)acryloxymethyl)ethyl isocyanate and other polymerizable isocyanate compounds subjected to urethanization reaction It can be obtained by the method of subjecting (meth)acrylic acid chloride or chloromethylstyrene to dehydrochlorination reaction, the method of subjecting (meth)acrylic acid to dehydration reaction, and the method of subjecting itaconic anhydride to esterification reaction. Among these methods, especially in compounds having hydroxyl groups interposed between poly(oxyalkylene) groups at both ends of the poly(oxyperfluoroalkylene) group, 2-(methyl) A method for urethanizing isocyanate compounds having polymerizable groups such as acryloxyethyl isocyanate or 1,1-bis((meth)acryloxymethyl)ethyl isocyanate, or A method in which the hydroxyl group dehydrochlorides (meth)acrylic acid chloride or chloromethylstyrene is particularly preferred from the viewpoint of ease of reaction.

[(b6) A perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond (but, in the aforementioned poly Perfluoropolyether having a poly(oxyalkylene) group between the (oxyperfluoroalkylene) group and the aforementioned urethane linkage)] The above-mentioned perfluoropolyether (b6) is not limited to one having an active energy ray polymerizable group such as a (meth)acryl group at both ends, and may have two or more active energy ray polymerizable groups at both ends. For example, the terminal structure including the active energy ray polymerizable group includes structures of the aforementioned formula [A1] to formula [A5], and structures in which the acryl group is substituted with a methacryl group in these structures.

(式[4]中，A表示前述式[A1]至式[A5]表示之構造及此等構造中之丙烯醯基取代為甲基丙烯醯基之構造中的1者，PFPE表示以聚(氧全氟伸烷基)構造為核心，其兩側具有與氧伸烷基連結的末端構造之基，n係分別獨立地表示1至5之整數，L⁷ 表示由n+1元之醇去除OH的n+1價殘基)。The perfluoropolyether (b6) is preferably, for example, a perfluoropolyether having at least 2 active energy ray polymerizable groups at both ends, a perfluoropolyether having at least 3 active energy ray polymerizable groups at both ends, etc. ether. As such a perfluoropolyether (b6), the compound represented by following formula [4] is mentioned, for example.

(In formula [4], A represents one of the structures represented by the aforementioned formula [A1] to formula [A5] and the structure in which the acryl group in these structures is substituted with a methacryl group, and PFPE represents poly( Oxygen perfluoroalkylene) is structured as the core, and its two sides have the base of the terminal structure linked to the oxyalkylene group. The n systems represent independently an integer from 1 to 5, and L ⁷ represents the removal of alcohol from n+1 yuan. n+1 valent residue of OH).

As the structure of the poly(oxyperfluoroalkylene) group, those specifically exemplified in the aforementioned poly(oxyperfluoroalkylene) group can be mentioned as a suitable structure. In addition, the terminal structure connected to the oxyalkylene group existing on both sides, for example, when it is bonded to the -O- terminal of the poly(oxyperfluoroalkylene) group, **-(via 1 fluorine atom) to 3 substituted C2 or C3 alkylene groups)- or ** -CF ₂ C(=O)-, and the fluoroalkylene terminal of the poly(oxyperfluoroalkylene) group (for example -CF ₂ -, -C(CF ₃ )F-) bonding, examples include **-O-(alkylene group with 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms)- or **- O-CF ₂ C(=O)-(** all represent the bonding terminal with the poly(oxyperfluoroalkylene) group). The aforementioned alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms includes, for example, -CHFCH ₂ -, -CF ₂ CH ₂ -, -CF ₂ CHF-, -CHFCH ₂ CH ₂ -, -CF ₂ CH ₂ CH ₂ -, -CF ₂ CHFCH ₂ -, preferably -CF ₂ CH ₂ -.

(式[B1]至式[B12]中，A表示前述式[A1]至式[A5]表示之構造及此等構造中之丙烯醯基取代為甲基丙烯醯基之構造中的1者)。 上述式[B1]至式[B12]表示之構造中，式[B1]及式[B2]相當於n=1的情況，式[B3]至式[B6]相當於n=2的情況，式[B7]至式[B9]相當於n=3的情況，式[B10]至式[B12]相當於n=5的情況。 此等之中，尤以式[B3]表示之構造為佳、特佳為式[B3]與式[A3]之組合。Examples of the partial structure (A-NHC(=O)O) _n L ⁷ - in the compound represented by the above formula [4] include the structures represented by the following formula [B1] to formula [B12].

(In formula [B1] to formula [B12], A represents one of the structures represented by the aforementioned formula [A1] to formula [A5] and the structure in which the acryl group in these structures is substituted with a methacryl group) . In the structure represented by the above formula [B1] to formula [B12], formula [B1] and formula [B2] correspond to the case of n=1, formula [B3] to formula [B6] correspond to the case of n=2, formula [B7] to formula [B9] correspond to the case of n=3, and formula [B10] to formula [B12] correspond to the case of n=5. Among them, the structure represented by the formula [B3] is particularly preferable, and the combination of the formula [B3] and the formula [A3] is particularly preferable.

式[5]表示之部分構造，相當於由前述式[4]表示之化合物中去除A-NHC(=O)的部分。 式[5]中之n，表示重複單位-[OCF₂ CF₂ ]-之數與重複單位-[OCF₂ ]-之數的總數，較佳為5至30之範圍、更佳為7至21之範圍。又，重複單位-[OCF₂ CF₂ ]-之數與重複單位   -[OCF₂ ]-之數的比率，較佳為2：1至1：2之範圍、更佳為約1：1之範圍。此等重複單位之鍵結，可為嵌段鍵結及隨機鍵結的任意者。Preferable perfluoropolyether (b6) includes compounds having a partial structure represented by the following formula [5].

The partial structure represented by the formula [5] corresponds to a portion in which A-NHC (=O) is removed from the compound represented by the aforementioned formula [4]. n in formula [5] represents the total number of repeating units -[OCF ₂ CF ₂ ]- and repeating units -[OCF ₂ ]-, preferably in the range of 5 to 30, more preferably 7 to 21 range. Also, the ratio of the number of repeating units -[OCF ₂ CF ₂ ]- to the number of repeating units -[OCF ₂ ]- is preferably in the range of 2:1 to 1:2, more preferably in the range of about 1:1 . The linkage of these repeating units may be either a block linkage or a random linkage.

(式中，PFPE、L⁷ 及n，表示與前述式[4]相同意義)表示之化合物的兩末端所存在之羥基，使具有聚合性基之異氰酸酯化合物，亦即於前述式[A1]至式[A5]表示之構造及此等構造中之丙烯醯基取代為甲基丙烯醯基之構造中的鍵結部位上鍵結有異氰酸基的化合物(例如2-(甲基)丙烯醯氧基乙基異氰酸酯、1,1-雙((甲基)丙烯醯氧基甲基)乙基異氰酸酯)進行反應，形成胺基甲酸酯鍵而得到。The above-mentioned perfluoropolyether (b6), for example, can be obtained by the following formula [6]

(In the formula, PFPE, L ⁷ and n represent the same meaning as the aforementioned formula [4]) The hydroxyl groups present at the two ends of the compound represented make the isocyanate compound with a polymerizable group, that is, in the aforementioned formula [A1] to The structure represented by the formula [A5] and the compound in which the acryl group in these structures is substituted with a methacryl group has an isocyanate group bonded to the bonding site (such as 2-(meth)acryl Oxyethyl isocyanate and 1,1-bis((meth)acryloxymethyl)ethyl isocyanate) are reacted to form a urethane bond.

Preferred perfluoropolyethers (b6) include, for example, at least 3 active energy ray polymerisation groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond. Perfluoropolyether compounds with neutral groups (except for perfluoropolyether having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond). The aforementioned perfluoropolyether compound having polymerizable groups at both terminals is preferably a compound having a partial structure represented by the aforementioned formula [5].

Preferred (b) component (perfluoropolyether) can be exemplified by perfluoropolyether (b6), that is, (b6) is at both ends of the molecular chain containing poly(oxyperfluoroalkylene) group, separated by amine urethane bond, and perfluoropolyether having an active energy ray polymerizable group (but, there is a poly(oxyalkylene) between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond based perfluoropolyethers).

[(c) Polymerization initiator that generates free radicals by active energy rays] Among curable compositions capable of forming a hard coat layer, preferable polymerization initiators that generate radicals by active energy rays (hereinafter, also simply referred to as "(c) polymerization initiators") are, for example, Active energy rays such as electron beams, ultraviolet rays, and X-rays, especially polymerization initiators that generate free radicals by ultraviolet irradiation. The aforementioned (c) polymerization initiators include, for example, benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acyl Phosphine oxides, oxime esters, organic peroxides, benzophenones, dicoumarins, bisimidazoles, titanocenes, mercaptans, halogenated hydrocarbons, trichloromethyltriazines, Onium salts such as iodonium salts and cerium salts. These can be used individually by 1 type or in mixture of 2 or more types. Among the specific examples of the above (c) polymerization initiator, it is particularly preferable to use alkyl phenones in the present invention from the viewpoint of transparency, surface hardening properties, and film hardening properties. By using alkyl phenones, a cured film having improved scratch resistance can be obtained.

The above-mentioned alkyl phenones include, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-1-(4-(2- Hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl )-2-methylpropane-1-one and other α-hydroxyalkylphenones; 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane-1- α-aminoalkylphenones such as ketones, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one; 2,2-di Methoxy-1,2-diphenylethan-1-one; Methyl phenylglyoxylate.

In the present invention (c) the polymerization initiator, with respect to 100 parts by mass of the aforementioned (a) oxyalkylene modified polyfunctional monomer having at least 3 active energy ray polymerizable groups, it is more desirable to use 1 mass 20 parts by mass, preferably 2 parts by mass to 10 parts by mass.

(m₀ ：對溶劑浸漬後乾燥之試驗片質量、m₁ ：對溶劑浸漬後之試驗片質量) 上述溶劑，係考慮會溶解前述(a)至(c)成分，且形成後述硬化膜(硬質塗層)相關之塗覆時的作業性或硬化前後的乾燥性等來適當選擇。 上述溶劑例如可列舉苯、甲苯、二甲苯、乙基苯、四氫萘等之芳香族烴類；n-己烷、n-庚烷、礦油精、環己烷等之脂肪族或脂環式烴類；氯甲烷、溴甲烷、碘甲烷、二氯甲烷、氯仿、四氯化碳、三氯乙烯、全氯乙烯、o-二氯苯等之鹵化物類；乙酸乙酯、乙酸丁酯、乙酸甲氧基丁酯、甲基賽珞蘇乙酸酯、乙基賽珞蘇乙酸酯、丙二醇單甲基醚乙酸酯等之酯類或酯醚類；二乙基醚、四氫呋喃、1,4-二噁烷、甲基賽珞蘇、乙基賽珞蘇、丁基賽珞蘇、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單-n-丙基醚、丙二醇單異丙基醚、丙二醇單-n-丁基醚等之醚類；丙酮、甲基乙基酮、甲基異丁基酮、二-n-丁基酮、環己酮等之酮類；甲醇、乙醇、n-丙醇、異丙醇、n-丁醇、異丁醇、tert-丁醇、2-乙基己醇、苯甲醇、乙二醇等之醇類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等之醯胺類；二甲基亞碸等之亞碸類，以及混合此等溶劑中2種以上之溶劑。 使用熱可塑性聚胺基甲酸酯(TPU)薄膜作為薄膜基材時之溶劑，例如可列舉甲醇、乙醇、n-丙醇、異丙醇、n-丁醇、異丁醇、tert-丁醇、2-乙基己醇、苯甲醇、乙二醇等之醇類，以及混合此等溶劑中2種以上之溶劑，較佳為甲醇。 (d)溶劑之使用量並無特殊限定，例如以可形成硬質塗層之硬化性組成物中的固體成分濃度為1質量%至70質量%、較佳為5質量%至50質量%之濃度使用。此處固體成分濃度(亦稱為不揮發成分濃度)，係表示該硬化性組成物之相對於前述(a)至(d)成分(及依期望之其他添加劑)之總質量(合計質量)而言，固體成分(自全部成分去除溶劑成分者)之含量。[(d) Solvent] The curable composition capable of forming a hard coat layer further contains the (d) solvent, that is, it is in the form of a paint (film-forming material). The solvent contained in the curable composition is a solvent having a solvent swelling degree of 70% or less of the film base material at its normal boiling point. Also, it is preferably a solvent having a solvent swelling degree of 50% or less, more preferably a solvent of 30% or less. Here, the solvent swelling degree refers to the value calculated according to the following formula by measuring the mass immediately after immersion and drying of a solvent near the boiling point with an analytical balance.

(m ₀ : mass of the test piece dried after immersion in the solvent, m ₁ : mass of the test piece after immersion in the solvent) The above-mentioned solvents are considered to dissolve the above-mentioned components (a) to (c) and form the cured film (hard Coating) related to workability during coating and drying properties before and after hardening, etc., are appropriately selected. The aforementioned solvents include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; Hydrocarbons; halides such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene, etc.; ethyl acetate, butyl acetate, Esters or ester ethers of methoxybutyl acetate, methylcellosuloacetate, ethylcellosuloacetate, propylene glycol monomethyl ether acetate, etc.; diethyl ether, tetrahydrofuran, 1 , 4-Dioxane, Methyl Cellosulfate, Ethyl Cellosulfate, Butyl Cellosulfate, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Mono-n-Propyl Ether, Propylene Glycol Monoisopropyl Ether Ethers such as base ether and propylene glycol mono-n-butyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, etc.; methanol, ethanol , n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol, ethylene glycol and other alcohols; Amides such as amide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; amides such as dimethylsulfide, and a mixture of two or more of these solvents solvent. Solvents when using a thermoplastic polyurethane (TPU) film as a film substrate, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol , 2-ethylhexanol, benzyl alcohol, ethylene glycol and other alcohols, and a mixture of two or more of these solvents, preferably methanol. (d) The amount of the solvent used is not particularly limited, for example, the solid content concentration in the curable composition capable of forming a hard coat layer is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass use. Here, the solid content concentration (also referred to as the non-volatile content concentration) refers to the total mass (total mass) of the curable composition relative to the aforementioned (a) to (d) components (and other additives as desired) In other words, the content of solid content (those who remove solvent components from all components).

[other additions] Also, in the curable composition that can form a hard coat layer, as long as the effect of the present invention is not impaired, generally added additives such as polymerization inhibitors, photosensitizers, leveling agents, interface Activator, adhesion imparting agent, plasticizer, ultraviolet absorber, antioxidant, storage stabilizer, antistatic agent, inorganic filler, pigment, dye.

The method for producing a scratch-resistant hard coating film of the present invention includes at least the steps of applying the aforementioned curable composition capable of forming a hard coating layer on a film substrate to form a coating film, and irradiating the coating film with active energy rays. The hardening step is carried out.

The aforementioned film substrates, for example, can be enumerated from thermoplastic polyurethane (TPU), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate Resin films selected from polyester, polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose such as diester (PEN), for From the viewpoint of scratch resistance and elongation of the obtained hard coating film, a thermoplastic polyurethane (TPU) film is preferably mentioned. Thermoplastic polyurethane (TPU) film, if the solvent swelling degree of the thermoplastic polyurethane (TPU) film at its standard boiling point is 70% or less, it can be used as the solvent in the curable composition Containing a solvent, it is possible to produce a hard coating film that imparts elongation in addition to excellent scratch resistance.

For the coating method on the above-mentioned film substrate, for example, cast coating method, spin coating method, knife coating method, dip coating method, roll coating method, spray coating method, and bar coating method can be appropriately selected. , die coating method, inkjet method, printing method (such as letterpress printing method, gravure printing method, lithography method, screen printing method), among these methods, it can be used especially for roll-to-roll (roll-to-roll) Furthermore, from the viewpoint of film coatability, it is more desirable to use a letterpress printing method, especially a gravure coating method. Furthermore, it is preferable to filter the curable composition in advance using a filter with a pore size of about 0.2 μm before coating.

After coating the curable composition on the film substrate to form a coating film, the coating film is pre-dried by heating means such as a heating plate and an oven to remove the solvent if necessary (solvent removal step). The heating and drying conditions at this time are preferably, for example, about 40° C. to 120° C. for 30 seconds to 10 minutes.

After drying, irradiate active energy rays such as ultraviolet rays to harden the coating film. Examples of active energy rays include ultraviolet rays, electron beams, and X-rays, particularly preferably ultraviolet rays. As a light source for ultraviolet irradiation, for example, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs can be used. Further, the polymerization can be completed by post-baking thereafter, specifically by heating using heating means such as a hot plate and an oven. The film thickness of the hard coat layer obtained in this way is preferably 1 μm to 20 μm, more preferably 1 μm to 10 μm.

According to the manufacturing method of the scratch-resistant hard coat film of this invention, the hard coat film which has a hard coat layer on at least one side (surface) of a film base material can be manufactured. This hard coat film is suitably used for protecting the surface of various display elements, such as a flexible display, for example. [Example]

Examples are given below to describe the present invention more specifically, but the present invention is not limited by the following examples. In addition, in the examples, the apparatus and conditions used for preparation of samples and analysis of physical properties are as follows.

(1) Heating plate stirring bar Device: IKA Plate manufactured by IKA Japan Co., Ltd. (2) Coating by bar coating Device: PM-9050MC made by SMT Rod: A-Bar OSP-22 manufactured by OSG System Products Co., Ltd., with a maximum wet film thickness of 22 μm (equivalent to wire rod #9) Coating speed: 4m/min (3) Oven Device: Dust-free dryer DRC433FA manufactured by Advantec Toyo Co., Ltd. (4) UV hardening Device: CV-110QC-G manufactured by Heraeus Co., Ltd. Lamp: Heraeus Co., Ltd. high-pressure mercury lamp H-bulb (5) Determination of storage modulus Device: A&D Co., Ltd. Dynamic Viscoelasticity Automatic Tester RHEOVIBRON (registered trademark) DDV-01GP Sample size: length 4mm x width 1mm Measurement Mode: Tensile Measuring temperature: 25°C Measurement amplitude: 4μm Measurement frequency: 10Hz (6) Analytical Libra Device: XSE205 manufactured by Mettler Toledo Co., Ltd. (7) Gel Permeation Chromatography (GPC) Device: HLC-8220GPC manufactured by Tosoh Co., Ltd. String: Shodex (registered trademark) GPC K-804L, GPC K-805L manufactured by Showa Denko Co., Ltd. Column temperature: 40°C Eluent: Tetrahydrofuran Detector: RI (8) Scratch test Device: Shinto Science Co., Ltd. reciprocating abrasion tester TRIBOGEAR TYPE: 30S Scanning speed: 3,000mm/min Scanning distance: 50mm

Also, the abbreviations have the following meanings. EOMA: Ethylene oxide-modified polyfunctional acrylate [Aronix (registered trademark) MT-3553 manufactured by Toagosei Co., Ltd., 4 or more functional bases] PFPE: Perfluoropolyether having two hydroxyl groups without interposing a poly(oxyalkylene) base at both ends [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers Co., Ltd.] BEI: 1,1-bis(acryloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.] DOTDD: Dioctyltin dineodecanoate [Neostann (registered trademark) U-830 manufactured by Nitto Kasei Co., Ltd.] I2959: 2-Hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [IRGACURE (registered trademark) 2959 manufactured by BASF Japan Co., Ltd.] TPU1: Polyurethane elastomer film [Sheedom Co., Ltd. Higress DUS270-CER, thickness 100 μm, storage modulus 92 MPa (measured value)] TPU2: Polyurethane elastomer film [Sheedom Co., Ltd. Higress DUS605-CER, thickness 100 μm, storage modulus 159 MPa (measured value)] PMMA: Poly(methyl methacrylate) film [Technolloy S000 manufactured by Sumika Acryl Sales Co., Ltd., thickness 125 μm] MeOH: Methanol EtOH: ethanol IPA: 2-propanol PGME: Propylene Glycol Monomethyl Ether MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone AcOEt: ethyl acetate AcOBu: butyl acetate

[Reference example] Solvent swelling degree of film base material Put 50mL of the solvent listed in Table 1 into a 100mL beaker, heat with a hot plate stirrer so that the liquid temperature becomes near the boiling point of the solvent. A test piece cut out to a size of 25 mm x 25 mm was dipped for 3 minutes. After immersion, gently wipe off the excess solvent attached to the surface of the test piece with a non-woven cloth [BEMCOT (registered trademark) M-1 manufactured by Ozu Sangyo Co., Ltd.], and immediately measure the mass of the test piece with an analytical balance m ₁ . Next, the test piece was dried at room temperature (about 23° C.) for 24 hours, and the mass m ₀ of the dried test piece was measured. The solvent swelling degree was calculated by the following formula. The results are shown in Table 1 together.

[Production Example 1] Production of perfluoropolyether (SM) having 4 acryl groups at both ends via urethane bonds 1.19 g (0.5 mmol) of PFPE, 0.52 g (2.0 mmol) of BEI, 0.017 g of DOTDD (0.01 times the total mass of PFPE and BEI), and 1.67 g of MEK were introduced into the spiral tube. This mixture was stirred at room temperature (about 23° C.) for 24 hours using a stirrer chip to obtain a 50% by mass MEK solution of SM of the target compound. The weight average molecular weight of the obtained SM measured in terms of polystyrene by GPC: Mw was 3,000, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Example 1 to Example 4, Comparative Example 1 to Comparative Example 6] The following components (1) to (4) were mixed to prepare a curable composition having a solid content concentration of 40% by mass. In addition, the solid content here means the component other than a solvent. (1) Multifunctional monomer: 100 parts by mass of EOMA (2) Surface modifying agent: 0.2 parts by mass of SM produced in Production Example 1 (calculated as solid content) (3) Polymerization initiator: 3 parts by mass of I2959 (4) Solvent: 154.6 parts by mass of the solvent described in Table 2 This curable composition was coated on the film substrate (B5 size) described in Table 2 by bar coating to obtain a coating film. The coating film was dried in an oven at the temperature described in Table 2 for 3 minutes to remove the solvent. The obtained film was exposed to UV light at an exposure dose of 300 mJ/cm ² in a nitrogen atmosphere to prepare a hard coat film having a hard coat layer (cured film) having a film thickness of about 5 μm.

The surface of the obtained hard coating was rubbed 10 back and forth with a load of 500g/ ^cm2 applied to the steel wool [Bonstar Sales (Co., Ltd.) Manufacture Bonstar (registered trademark) #0000 (ultra-fine)] installed in a back-and-forth abrasion tester, and visually inspected Confirm the degree of damage and evaluate according to the following criteria. The results are shown in Table 2 together. Furthermore, assuming that it is actually used as a hard coating, at least B is required, and A is more desirable. A: no damage B: damage less than 5mm long C: damage longer than 5mm

As shown in Table 2, it is obvious that the hard coating films (Example 1 to Example 3) produced by using the solvent swelling degree of the film base material used are low, that is, less than 70% of the hard coating film (Example 1 to Example 3) and the hard coating film produced by using AcOEt The hard coat film (Example 4) exhibited excellent scratch resistance. On the other hand, it is obvious that the hardness of PGME (Comparative Examples 1 to 3) and MEK (Comparative Examples 4 to 6) using a solvent with a high solvent swelling degree, that is, more than 70%, or a solvent in which the film substrate is completely dissolved coating film, the scratch resistance is greatly reduced.

Claims (5)

A method for producing a scratch-resistant hard coating film, comprising at least the steps of applying a curable composition capable of forming a hard coating layer on a film substrate to form a coating film, and irradiating the coating film with active energy rays The method for producing a scratch-resistant hard coating film in the step of hardening, wherein the solvent contained in the above-mentioned curable composition is a solvent having a solvent swelling degree of the above-mentioned film substrate at its normal boiling point of 70% or less, and the solvent is Aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, halides, esters, ester ethers, ethers, ketones, alcohols, amides, sulfides, or mixed in these solvents Two or more solvents, the aforementioned film substrate is selected from thermoplastic polyurethane, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate A resin film of the group consisting of ester, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, and triacetyl cellulose, wherein the curable composition contains (a) having at least 100 parts by mass of oxyalkylene modified polyfunctional monomers with 3 active energy ray polymerizable groups, (b) the two ends of the molecular chain containing poly(oxyperfluoroalkylene) groups are separated or not Poly(oxyalkylene) base, 0.1 to 10 parts by mass of organically modified perfluoropolyether, and (c) 1 mass of polymerization initiator that generates free radicals by active energy rays Parts to 20 parts by mass, the two ends of the molecular chains of the aforementioned (b) containing poly(oxyperfluoroalkylene) groups are organically modified perfluorinated Polyether is a perfluoropolyether selected from the following (b1) to (b4) and (b6); (b1) the two ends of the molecular chain containing poly(oxyperfluoroalkylene) groups are separated by or Alcohol-modified, sunflower-based modified, carboxylic acid-modified or ester-modified perfluoropolyether, (b2) alkoxysilane system separated by poly(oxygen) without intervening poly(oxyalkylene) base alkylene) group, and further through the divalent linking group, the perfluoropolyether bonded to the two ends of the molecular chain containing the poly(oxyperfluoroalkylene) group, the (b3) alkoxysilyl group A perfluoropolyether having a linking structure not having a poly(oxyperfluoroalkylene) structure bonded to both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group, (b4) in a structure containing a poly(oxyperfluoroalkylene) )-based perfluoropolyether having an active energy ray polymerizable group at one end of the molecular chain via a poly(oxyalkylene) group and a hydroxyl group at the other end of the molecular chain via a poly(oxyalkylene) group , (b6) Perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond (but, in the aforementioned poly Perfluoropolyether having a poly(oxyalkylene) group between the (oxyperfluoroalkylene) group and the aforementioned urethane linkage is excluded). The manufacturing method according to claim 1, wherein the aforementioned film substrate is a thermoplastic polyurethane film or a poly(methyl methacrylate) film. The production method as claimed in claim 1, wherein the two ends of the molecular chain containing poly(oxyperfluoroalkylene) groups in the aforementioned (b) are modified by organic groups with or without the poly(oxyalkylene) groups The perfluoropolyether of the above-mentioned (b6) is a perfluoropolyether having an active energy ray polymerizable group at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond. Ether (except for perfluoropolyether having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane linkage). The production method according to any one of claim 1 to claim 3, wherein the solvent contained in the aforementioned curable composition is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isopropanol, One or more alcohols of the group consisting of butanol, tert-butanol, 2-ethylhexanol, benzyl alcohol and ethylene glycol. The production method according to claim 4, wherein the solvent contained in the curable composition is methanol.