JP7012458B2 - A composition for forming a hard coat of a resin base material, a method for forming a hard coat, and an article using the same. - Google Patents

Description

The present invention relates to a composition for forming a hard coat for protecting the surface of a resin substrate. More specifically, a composition for forming a hard coat and a method for forming a hard coat for protecting the surface of a hard plastic base material such as a plastic lens made of polycarbonate or a flexible resin film made of polyimide used for an electronic material. And related to articles using it.

Conventionally, treatment with a hard coat agent has been widely performed in order to protect the surface of a plastic chemical product such as polycarbonate from scratches and stains. However, even if an attempt was made to apply the coating composition to a plastic base material to form a hard coat layer, the adhesion was insufficient and it was not practically usable. Therefore, in order to impart adhesion, a two-step process of applying a primer solution to a plastic base material and then applying a hard coat agent was required. In particular, in the case of a plastic base material made of polycarbonate, the adhesion to the hard coat layer was poor and primer treatment was indispensable.
Disclosed are coating compositions that adhere to a thermoplastic sheet by incorporating an adhesion promoting component into a polycarbonate substrate to obtain a hard coat layer that adheres without primer treatment (Patent Documents 1 to 3). ), Sufficient adhesion has not been obtained while maintaining performance such as hardness and appearance.

Further, in recent years, with the rapid progress of displays such as liquid crystals, organic ELs and electronic papers, and electronics such as solar cells and touch panels, there is a demand for thinner and lighter devices and more flexibility. Therefore, instead of the glass base material used in these devices, a resin film base material that can be made thinner, lighter, and more flexible is being studied. Polyimide is widely studied as a glass substitute base material due to its excellent heat resistance and mechanical properties, but a hard coat having sufficient adhesion, bending resistance, and surface hardness to these base materials has not been developed yet. do not have.

Japanese Unexamined Patent Publication No. 2006-251413 Japanese Patent Application Laid-Open No. 6-256718 Japanese Unexamined Patent Publication No. 2001-247769

The present invention has excellent adhesion and scratch resistance to thermoplastic resin and thermosetting resin base materials without primer treatment, and even when applied to flexible resin base materials, bending resistance It is an object of the present invention to provide a composition for forming a hard coat having properties (crack resistance) and surface hardness. Furthermore, a method for forming a hard coat using such a composition for forming a hard coat and an article using the same are also provided.

By blending the following components A to E, the present inventors have excellent adhesion and scratch resistance to various thermoplastic or thermosetting resin substrates such as polycarbonate resin substrates and polyimide resin substrates. It has been found that a composition for forming a hard coat having a property can be provided.
A component: Metal oxide fine particles B component: Organosilicon compound or its hydrolyzate C component: Adhesion promoting component having an alkoxysilyl group D component: Curing catalyst E component: Solvent

Since the composition for forming a hard coat of the present invention contains an adhesion promoting component having an alkoxysilyl group as a reactive functional group, it adheres to a polycarbonate substrate or a polyimide substrate without the primer treatment which was indispensable in the past. A hard coat can be formed.

When the composition for forming a hard coat of the present invention is used, it is not necessary to apply a primer solution to the resin base material in order to impart adhesion, it has excellent adhesion, and has high scratch resistance and bending resistance. A hard coat layer having both properties and surface hardness can be formed.

The schematic diagram explaining the procedure of forming a hard coat on a resin base material using the composition for forming a hard coat of this invention. The schematic diagram explaining the procedure of forming a hard coat on a resin base material using a conventional composition for forming a hard coat.

The composition for forming a hard coat of the present invention is at least
A component: Metal oxide fine particles B component: Organosilicon compound or its hydrolyzate C component: Adhesion promoting component having an alkoxysilyl group D component: Curing catalyst E component: Containing a solvent.

<Metal oxide fine particles>
The metal oxide fine particles are used for improving the scratch resistance of the formed hard coat and adjusting the refractive index. Examples of the metal oxide fine particles forming the hard coat layer include titanium oxide, silicon oxide, zirconium oxide, aluminum oxide, iron oxide, antimony oxide, tin oxide, tungsten oxide, or a composite thereof, and titanium oxide. , Silicon oxide, zirconium oxide, tin oxide are preferable. The metal oxide fine particles can be used, for example, as a colloidal sol dispersed in water, an organic solvent or a mixture thereof.

<Organosilicon compounds and their hydrolysates>
Organic silicon compounds having hydrolyzable functional groups increase the cross-linking density of the hard coat by forming siloxane bonds by dehydration condensation of silanol groups generated by hydrolysis or by forming chemical bonds by reaction between organic functional groups. Used for. Specific examples of the hydrolyzable functional group include an alkoxy group such as a methoxy group and an ethoxy group, a halogen group such as a chloro group and a bromo group, and an acyloxy group. These hydrolyzable functional groups are easily hydrolyzed in aqueous solutions to give silanol groups.
The organic silicon compound is a silane cup having a hydrocarbon group having a functional group selected from the group consisting of an amino group, an isocyanate group, an epoxy group, an acrylic group, a vinyl group, a methacrylic group, a styryl group, a ureido group and a mercapto group. It is preferable to use at least one of the ring agents. for example,
General formula (1):

（式中、aは０～３の整数を示し、１または複数個のR¹は、それぞれ、同一または異なって、アミノ基、イソシアネート基、エポキシ基、アクリル基、ビニル基、メタクリル基、スチリル基、ウレイド基、メルカプト基および炭化水素基よりなる群から選択される官能基を有する炭素数１～２０の炭化水素基を示し、１または複数個のR²は、それぞれ、同一または異なって、炭素数１～３の炭化水素基を示す。）で表わされる有機ケイ素化合物、それらの加水分解物および部分加水分解オリゴマー；
一般式（２）：

(In the formula, a represents an integer of 0 to 3, and one or more R ^1s are the same or different, respectively, and have an amino group, an isocyanate group, an epoxy group, an acrylic group, a vinyl group, a methacrylic group and a styryl group. , A hydrocarbon group having 1 to 20 carbon atoms having a functional group selected from the group consisting of a ureido group, a mercapto group and a hydrocarbon group, wherein one or more R ^2s are the same or different, respectively. Organic silicon compounds represented by (1) to 3 hydrocarbon groups, their hydrolysates and partially hydrolyzed oligomers;
General formula (2):

（式中、bおよびcは、それぞれ、同一または異なって０～２の整数を示し、１または複数個のR³～R⁶は、それぞれ、同一または異なって炭素数１～３のアルキル基を示し、Xは炭素数１～２０のアルキレン基を示す。）で表わされる有機ケイ素化合物およびそれらの加水分解物；ならびに
一般式（３）：

(In the formula, b and c represent the same or different integers of 0 to 2, respectively, and one or more R ³ to R ⁶ each have the same or different alkyl groups having 1 to 3 carbon atoms. Indicated, X represents an alkylene group having 1 to 20 carbon atoms.) Organic silicon compounds represented by) and their hydrolyzates; and general formula (3) :.

（式中、dは１～２０の整数を示し、R⁷、R⁸および複数個のR⁹は、それぞれ、同一または異なって炭素数１～３のアルキル基を示し、複数個のYは、それぞれ、同一または異なってビニル基、エポキシ基、メタクリル基、メルカプト基を示し、波線で示される炭素数１～３のアルキレン基を介してＳｉ元素に結合する。）で表される有機ケイ素化合物およびそれらの加水分解物；
よりなる群から選択される少なくとも一種を用いることができる。

(In the formula, d represents an integer of 1 to 20, R ⁷ , R ⁸ and a plurality of R ^9s each represent the same or different alkyl groups having 1 to 3 carbon atoms, and the plurality of Ys are. The organic silicon compound represented by the same or different vinyl group, epoxy group, methacrylic group, mercapto group, and bonded to the Si element via the alkylene group having 1 to 3 carbon atoms shown by the wavy line, respectively, and the organic silicon compound. Those hydrolysates;
At least one selected from the group consisting of can be used.

<Adhesion promoting component having an alkoxysilyl group>
As the adhesion promoting component, various compounds such as polyurethane, polyester, polycarbonate, and polyester carbonate can be applied.
The introduction of the alkoxysilyl group into these adhesion promoting components can be carried out, for example, by chemically introducing an alkoxysilane compound having an isocyanate group into the above polymer having a hydroxyl group as a functional group by a urethanization reaction. It is not limited.
By introducing an alkoxysilyl group as a reactive functional group, a silanol group generated by its hydrolysis forms a covalent bond with a hydroxyl group on the surface of metal oxide fine particles or a silanol group generated by hydrolysis of an organic silicon compound by a dehydration condensation reaction. be able to. As a result, the adhesion promoting component can be incorporated into the coating film via a covalent bond and immobilized, whereby the heat resistance test of the hard coat film and the decrease in adhesion due to aging are suppressed, and stable adhesion is obtained. be able to. Further, by introducing an alkoxysilyl group into the adhesion promoting component, the compatibility of the adhesion promoting component in the hard coat resin is improved, whereby whitening of the hard coat film after curing can be suppressed.

As the adhesion promoting component, for example, the general formula (4):

（式中、eおよびfは０～２の整数を示し、R¹⁰はポリウレタン、ポリエステル、ポリカーボネート、ポリエステルカーボネートよりなる群から選択される密着促進性のポリマー主鎖を示し、２個のR¹¹は、それぞれ、同一または異なって、炭素数１～２０のアルキレン基を示し、当該アルキレン基は、不飽和炭化水素基、芳香族炭化水素基、脂環式炭化水素基又はヘテロ原子を有していてもよく、１または複数個のR¹²およびR¹³は、それぞれ、同一または異なって、炭素数１～４のアルキル基を示し、２つのZは、それぞれ、同一または異なって、アミド結合、イミド結合、ウレタン結合、ウレア結合、エーテル結合、エステル結合、カーボネート結合、スルフィド結合、チオウレタン結合、チオウレア結合、チオエステル結合よりなる群から選択される化学結合を示す。）で表される、両末端にアルコキシシリル基を有する化合物を用いることができる。

(In the formula, e and f represent integers from 0 to 2, R ¹⁰ represents a adhesion-promoting polymer main chain selected from the group consisting of polyurethane, polyester, polycarbonate, and polyester carbonate, and two R ^11s represent an adhesion-promoting polymer main chain. Each of the same or different alkylene groups has 1 to 20 carbon atoms, and the alkylene group has an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a hetero atom. Often, one or more R ^12s and R ^13s represent the same or different alkyl groups with 1 to 4 carbon atoms, respectively, and the two Zs are the same or different, respectively, amide or imide bonds. , Urethane bond, urea bond, ether bond, ester bond, carbonate bond, sulfide bond, thiourethane bond, thiourea bond, thioester bond. Compounds having a silyl group can be used.

In the case of a polyurethane polymer backbone, R ¹⁰ is the general formula (5) :.

（式中、gはポリマー主鎖の分子量が５００～５００００に対応する整数を示し、複数個のR¹⁴およびR¹⁵は、それぞれ、同一または異なって、炭素数１～２０のアルキレン基を示し、当該アルキレン基は、不飽和炭化水素基、芳香族炭化水素基、脂環式炭化水素基又はヘテロ原子を有していてもよい。）で表される。

(In the formula, g represents an integer corresponding to the molecular weight of the polymer main chain of 500 to 50,000, and the plurality of R ¹⁴ and R ¹⁵ each represent the same or different alkylene groups having 1 to 20 carbon atoms. The alkylene group may have an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heteroatom).

Alternatively, for example, polyurethane obtained by reacting a polyol such as a polyether polyol, a polyester polyol, or a polyether ester polyol with an isocyanate group-containing compound having at least two isocyanate groups per molecule, which will be described later, can be mentioned. Examples of the isocyanate group-containing compound having at least two isocyanate groups per molecule include the following aliphatic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates. Alternatively, it may be a mixture thereof.

Examples of the aliphatic polyisocyanis include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylenedisisethylene, 1,3-butyrenisisisocyanis, and dodecamethylene diisocyanate. , 2,4,4-trimethylhexamethylene diisocyanis, lysine isocyanate, hydrogenated xylenize isocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-bis (diisocyanismethyl) cyclohexane, 4,4'-dicyclohexamethylene diisocyanate and the like.

Examples of the aromatic polyisocyanate include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, and 1,3. , 5-Triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4''-triphenylmethane triisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, Examples thereof include 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and polymethylenepolyphenylene polyisocyanate (MDI).

Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1 , 4-Tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate and the like.

In the case of polyester polymer main chain, R ¹⁰ is the general formula (6) :.

（式中、hはポリマー主鎖の分子量が５００～５００００に対応する整数を示し、複数個のR¹⁶およびR¹⁷は、それぞれ、同一または異なって、炭素数１～２０のアルキレン基を示し、当該アルキレン基は、不飽和炭化水素基、芳香族炭化水素基、脂環式炭化水素基又はヘテロ原子を有していてもよい。）で表される。

(In the formula, h represents an integer corresponding to the molecular weight of the polymer main chain of 500 to 50,000, and the plurality of R ¹⁶ and R ¹⁷ each represent the same or different alkylene groups having 1 to 20 carbon atoms. The alkylene group may have an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heteroatom).

In the case of the polycarbonate-based polymer main chain, R ¹⁰ is expressed by the general formula (7) :.

（式中、kはポリマー主鎖の分子量が５００～５００００に対応する整数を示し、複数個のR¹⁸は、それぞれ、同一または異なって、炭素数１～２０のアルキレン基を示し、当該アルキレン基は、不飽和炭化水素基、芳香族炭化水素基、脂環式炭化水素基又はヘテロ原子を有していてもよい。）で表される。

(In the formula, k represents an integer corresponding to the molecular weight of the polymer main chain of 500 to 50,000, and the plurality of R ^18s each represent the same or different alkylene group having 1 to 20 carbon atoms, and the alkylene group thereof. May have an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heteroatom).

In the case of the polyester carbonate polymer main chain, R ¹⁰ is the general formula (8) :.

｛式中、mはポリマー主鎖の分子量が５００～５００００に対応する整数を示し、複数個のR¹⁹は、それぞれ、同一または異なって、一般式（９）：

{In the formula, m represents an integer corresponding to the molecular weight of the polymer main chain of 500 to 50,000, and the plurality of R ^19s are the same or different, respectively, and the general formula (9):

（式中、nはR¹⁹の分子量が１５０～２５０００に対応する整数を示し、複数個のR²⁰およびR²¹は、それぞれ、同一または異なって、炭素数１～２０のアルキレン基を示し、当該アルキレン基は、不飽和炭化水素基、芳香族炭化水素基、脂環式炭化水素基又はヘテロ原子を有していてもよい。）で表される。｝で表される。

(In the formula, n represents an integer corresponding to the molecular weight of R ¹⁹ of 150 to 25,000, and the plurality of R ²⁰ and R ²¹ each represent the same or different alkylene groups having 1 to 20 carbon atoms. The alkylene group may have an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a heteroatom). }.

In the present specification, for example, the notation "one or more R ³ to R ⁶ indicate the same or different alkyl groups having 1 to 3 carbon atoms" means one or more R ³ ,. Each group of one or more R ⁴ , one or more R ⁵ and one or more R ⁶ is independently an alkyl group having 1 to 3 carbon atoms, and the groups are each other. It means that they may be the same alkyl group or different alkyl groups. The same applies to other similar notations.

<Curing catalyst>
Examples of curing catalysts that can be mixed into the coating compositions of the present invention are (i) metal acetylacetonates; (ii) diamides; (iii) imidazoles; (iv) amines and ammonium salts; (v) organic sulfonic acids and Their amine salts; (vi) carboxylic acids and their alkali metal salts; (vii) alkali metal hydroxides; (viii) fluoride salts; (ix) organic tin compounds; and (x) perchlorates. ..
Examples of such catalysts include acetylacetonates of aluminum, zinc, iron and cobalt as group (i); dicyandiamide as group (ii); 2-methylimidazole, 2-ethyl as group (iii). -4-Methylimidazole and 1-cyanoethyl-2-propylimidazole, etc .; as a group (iv), such as benzyldimethylamine and 1,2-diaminocyclohexane; as a group (v), such as trifluoromethanesulfonic acid; group (vi). As a group (vii), such as sodium hydroxide and potassium hydroxide; as a group (viii), tetra n-butylammonium fluoride; as a group (ix), such as dibutyltin dilaurate; and as a group ( As x), magnesium perchlorate, aluminum perchlorate and the like are included.

<Solvent>
As volatile solvents, alcohols such as water, methanol, ethanol and isopropanol, glycol ethers such as propylene glycol monomethyl ether, glycol esters such as ethylene glycol monoethyl ether acetate, ketones such as methyl ethyl ketone and acetyl acetone, ethyl acetate, etc. Examples thereof include esters such as butyl acetate. These volatile solvents may be used alone or in combination of two or more.
These volatile solvents can also be added separately to the composition, but also include other components such as water, organic solvents or solvents derived from colloidal sol dispersed in mixtures thereof.

<Others>
The composition for forming a hard coat of the present invention includes, if desired, an anti-blocking agent, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, etc., as long as the effect of the present invention is not adversely affected. May be added.

<Method of forming a hard coat on a resin substrate>
A method of forming a hard coat on a resin substrate using the composition for forming a hard coat of the present invention will be described (FIG. 1).
On a resin base material 1 such as a thermoplastic resin or a thermosetting resin (FIG. 1a), a composition for forming a hard coat is generally applied to a dip coat, a roll coat, a spin coat, a flow coat, a spray coat, a gravure coat, or the like. It is applied by the method to form the resin layer 2 (FIG. 1b). The obtained resin layer 2 is heated and cured to form a hard coat 3 which is a cured product, and a laminate of a resin base material and a hard coat layer directly formed on the resin base material is produced. (Fig. 1c).

On the other hand, when a conventional hard coat forming composition is used, the primer 4 is first applied to the surface of the resin base material 1 to perform surface treatment (FIG. 2b). A composition for forming a hard coat is applied onto the surface treated with a primer to form a resin layer 2 (FIG. 2c). The obtained resin layer 2 is heat-cured to form a hard coat 3 to obtain a laminate of a resin base material and a hard coat layer surface-treated with a primer (FIG. 2d).

That is, since the composition for forming a hard coat of the present invention has high adhesion to a resin substrate, if the composition of the present invention is used, it does not require primer treatment and is directly applied onto the resin substrate and cured. By doing so, it is possible to obtain a laminate composed of two layers, a resin base material and a hard coat layer.
For example, when applied to a lens made of polycarbonate, primer treatment is not required, so productivity can be improved and product yield can be expected to be improved by omitting the primer treatment step. Further, even when it is used as a hard coat composition for a flexible substrate for electronics, which has not been developed so far, it exhibits sufficient adhesion, bending resistance, and surface hardness.

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

[Synthesis of adhesion promoting ingredients]
Example 1
Introduction of terminal alkoxysilyl group into polyester polyol Polyester polyol (trade name: New Ace V14-90, manufactured by ADEKA Co., Ltd.) in a 200 ml reaction vessel equipped with a thermometer, agitator, reflux condenser, and nitrogen introduction tube. A solid content concentration of 100%, a hydroxyl value of 56.2 mgKOH / g), 40.0 parts by mass, 40.0 parts by mass of dried acetonitrile, and 0.03 parts by mass of dibutyltin dilaurate were charged under a nitrogen stream. To this, 9.92 parts by mass of 3-isocyanatepropyltriethoxysilane was added dropwise over 10 minutes at room temperature. Then, the reaction vessel was heated to 70 ° C. under a nitrogen stream and reacted at that temperature overnight to obtain a product having a non-volatile solid content of 50.5%.
When the infrared absorption spectrum of the obtained product was measured, it was confirmed that the absorption of the isocyanate group had disappeared.
The product synthesized in this example is referred to as adhesive polymer A.

Example 2
Introduction of terminal alkoxysilyl group into polyurethane polyol Polyurethane polyol (trade name: Takelac E-550, manufactured by Mitsui Chemicals, Inc., solid) in a 200 ml reaction vessel equipped with a thermometer, agitator, reflux condenser, and nitrogen introduction tube. A fraction concentration of 50%, a hydroxyl value of 20 mgKOH / g), 80.0 parts by mass, and 0.03 parts by mass of dibutyltin dilaurate were charged under a nitrogen stream. To this, 7.06 parts by mass of 3-isocyanatepropyltriethoxysilane was added dropwise over 10 minutes at room temperature. Then, the reaction vessel was heated to 70 ° C. under a nitrogen stream and reacted at that temperature overnight to obtain a product having a non-volatile solid content of 50.4%.
When the infrared absorption spectrum of the obtained product was measured, it was confirmed that the absorption of the isocyanate group had disappeared.
The product synthesized in this example is referred to as an adhesive polymer B.

Example 3
Introduction of terminal alkoxysilyl group into polycarbonate polyol A polycarbonate polyol (trade name: Praxel CD220PL, manufactured by Daicel Co., Ltd., solid content concentration 100) is placed in a 200 ml reaction vessel equipped with a thermometer, agitator, a reflux condenser, and a nitrogen introduction tube. %, Hydroxyl value 59.6 mgKOH / g) 40.0 parts by mass, dried acetonitrile 40.0 parts by mass, and dibutyl tin dilaurate 0.03 parts by mass were charged under a nitrogen stream. To this, 10.5 parts by mass of 3-isocyanatepropyltriethoxysilane was added dropwise over 10 minutes at room temperature. Then, the reaction vessel was heated to 70 ° C. under a nitrogen stream and reacted at that temperature overnight to obtain a product having a non-volatile solid content of 50.6%.
When the infrared absorption spectrum of the obtained product was measured, it was confirmed that the absorption of the isocyanate group had disappeared.
The product synthesized in this example is referred to as adhesive polymer C.

Example 4
Introduction of terminal alkoxysilyl groups into polyester / carbonate polyols Polyester / carbonate polyols (trade name: Desmophen C1200, Sumika Bayer Urethane Co., Ltd.) in a 200 ml reaction vessel equipped with a thermometer, stirrer, reflux condenser, and nitrogen introduction tube. Made by the company, solid content concentration 100%, hydroxyl group content 1.77%) 40.0 parts by mass, dry acetonitrile 49.8 parts by mass, and dibutyltin dibutylate 0.03 parts by mass were charged under a nitrogen stream. 10.2 parts by mass of 3-isocyanatepropyltriethoxysilane was added dropwise thereto over 10 minutes at room temperature. Then, the reaction vessel was heated to 70 ° C. under a nitrogen stream and reacted at that temperature overnight to obtain a product having a non-volatile solid content of 45.6%.
When the infrared absorption spectrum of the obtained product was measured, it was confirmed that the absorption of the isocyanate group had disappeared.
The product synthesized in this example is referred to as an adhesive polymer D.

[Formation of composition for forming a hard coat and formation of a hard coat layer]
Example 5 (prescription using polyester raw material)
<Preparation of composition>
In a 2 L volume beaker, under stirring, water-dispersed colloidal silica sol (trade name: ^Snowtex RO, manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 20%), 75.0 parts by mass, propylene glycol monomethyl ether dispersed colloidal silica sol (trade name: Snowtex RO, solid content concentration 20%) Product name: PGM-ST, manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 30%) 303.0 parts by mass and propylene glycol monomethyl ether (PGME) 388.0 parts by mass were mixed and stirred at room temperature. A mixture of 225.0 parts by mass of 3-glycidoxypropyltrimethoxysilane (GPTMS) and 10.9 parts by mass of the adhesive polymer A synthesized in Example 1 was added dropwise thereto at room temperature over 1 hour. Then, the solution temperature was raised to 30 ° C., and the mixture was stirred at that temperature for 2 hours. After cooling, add 9.0 parts by mass of aluminum trisacetylacetonate and 0.4 parts by mass of silicone-based surfactant (trade name: DOW CORNING TORAY L-7001, manufactured by Toray Dow Corning Co., Ltd.) at room temperature. Stirring for 2 hours prepared a composition for forming a hard coat.

<Creating a hard coat lens>
The above composition for forming a hard coat is dip-coated on a polycarbonate resin plastic lens base material, pre-dried at 80 ° C. for 10 minutes, and then heat-cured at 120 ° C. for 1 hour to obtain a polycarbonate lens having a hard coat layer on the surface. Obtained.

Example 6 (prescription using polyurethane raw material)
A polycarbonate lens having a hard coat layer on the surface was obtained by the same operation as in Example 5 except that the adhesive polymer was changed to 10.9 parts by mass of the adhesive polymer B synthesized in Example 2.

Example 7 (prescription using polycarbonate raw material)
A polycarbonate lens having a hard coat layer on the surface was obtained by the same operation as in Example 5 except that the adhesive polymer was changed to 10.9 parts by mass of the adhesive polymer C synthesized in Example 3.

Example 8 (prescription using polyester carbonate raw material)
A polycarbonate lens having a hard coat layer on the surface was obtained by the same operation as in Example 5 except that the adhesive polymer was changed to 12.1 parts by mass of the adhesive polymer D synthesized in Example 4.

Comparative Example 1 (Adhesive polymer without introducing an alkoxysilyl group)
A hard coat layer on the surface by the same operation as in Example 5 except that the adhesive polymer was changed to 5.5 parts by mass of a polyester polyol (trade name: New Ace V14-90) having no alkoxysilyl group introduced at the end. A polycarbonate lens having the above was obtained.

Comparative Example 2 (without adhesive polymer, with primer treatment)
<Preparation of composition>
In a 2 L volume beaker, under stirring, water-dispersed colloidal silica sol (trade name: Snowtex O, manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 20%) 75.0 parts by mass, propylene glycol monomethyl ether dispersed colloidal silica sol (commodity) Name: PGM-ST, manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 30%) 303.0 parts by mass and propylene glycol monomethyl ether (PGME) 388.0 parts by mass were mixed and stirred at room temperature. To this, 225.0 parts by mass of 3-glycidoxypropyltrimethoxysilane (GPTMS) was added dropwise at room temperature over 1 hour. Then, the solution temperature was raised to 30 ° C., and the mixture was stirred at that temperature for 2 hours. After cooling, add 9.0 parts by mass of aluminum trisacetylacetonate and 0.4 parts by mass of silicone-based surfactant (trade name: DOW CORNING TORAY L-7001, manufactured by Toray Dow Corning Co., Ltd.) at room temperature. The mixture was stirred for 2 hours.

<Creating a hard coat lens>
The above mixed solution is dip-coated on a polycarbonate resin plastic lens substrate coated with a polyurethane primer layer in advance, pre-dried at 80 ° C. for 10 minutes, and then heat-cured at 120 ° C. for 1 hour to form a hard coat layer on the surface. Obtained a polycarbonate lens having.

Example 9 (prescription using polyester raw material)
<Paint preparation>
Under stirring in a 2 L volume beaker, water-dispersed colloidal silica sol (trade name: ^Snowtex RO, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 20%) 178.0 parts by mass, propylene glycol monomethyl ether dispersed colloidal silica sol ( Product name: PGM-ST, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30%) 574.0 parts by mass were mixed and heated to 40 ° C. with stirring. Here, 225.0 parts by mass of 3-glycidoxypropyltrimethoxysilane (GPTMS), 101.0 parts by mass of 1,2-bis (triethoxysilyl) ethane, and the adhesive polymer A 13. 6 parts by weight of the mixture was added dropwise over 1 hour. Then, the mixture was stirred for 2 hours while maintaining the solution temperature at 40 ° C. After cooling, add 12.8 parts by mass of aluminum trisacetylacetonate and 0.4 parts by mass of a silicone-based surfactant (trade name: DOW CORNING TORAY L-7001, manufactured by Toray Dow Corning Co., Ltd.) at room temperature. The mixture was stirred for 2 hours.

<Making a hard coat film>
The above mixture was applied to one surface of a polyimide film (manufactured by Sumitomo Chemical Co., Ltd., thickness 50 μm) with a bar coater and cured by heating at 130 ° C. for 2 minutes. The thickness of the obtained coating film was 10 μm.

Example 10 (prescription using polyurethane raw material)
A hard coat film having a hard coat layer on the surface was obtained by the same operation as in Example 9 except that the adhesive polymer was changed to 13.7 parts by mass of the adhesive polymer B synthesized in Example 2.

Example 11 (prescription using polycarbonate raw material)
A hard coat film having a hard coat layer on the surface was obtained by the same operation as in Example 9 except that the adhesive polymer was changed to 13.6 parts by mass of the adhesive polymer C synthesized in Example 3.

Example 12 (prescription using polyester carbonate raw material)
A hard coat film having a hard coat layer on the surface was obtained by the same operation as in Example 9 except that the adhesive polymer was changed to 15.1 parts by mass of the adhesive polymer D synthesized in Example 4.

Example 13 (prescription using polyester carbonate raw material)
<Preparation of composition>
In a 2 L volume beaker, under stirring, water-dispersed colloidal silica sol (trade name: ^Snowtex RO-40, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 40%) 173.3 parts by mass, propylene glycol monomethyl ether dispersed colloidal. Silica sol (trade name: PGM-ST, manufactured by Nissan Chemical Industry Co., Ltd., solid content concentration 30%) 303.0 parts by mass, aqueous dispersion colloidal silica sol (trade name: Optreak 3342, manufactured by JGC Catalysts and Chemicals Co., Ltd., solid content concentration) 30%) 69.3 parts by mass were mixed and heated to 40 ° C. with stirring. Here, 92.1 parts by mass of a reactive silane oligomer (trade name: KR-516, manufactured by Shin-Etsu Chemical Industry Co., Ltd., solid content concentration 71.7%), 3-glycidoxypropyltrimethoxysilane (GPTMS) 93. 2 parts by mass, 1,2-bis (triethoxysilyl) ethane 88.5 parts by mass, adhesion polymer D 8.8 parts by mass synthesized in Example 4, methyl silicate oligomer (trade name: MKC ^(R) silicate MS51) , Mitsubishi Chemical Co., Ltd., solid content concentration: 51.1%) A mixture of 5.4 parts by mass and 10 parts by mass of tetraethoxysilane was added dropwise over 1 hour. Then, the solution temperature was raised to 50 ° C., and the mixture was stirred at that temperature for 30 minutes. After lowering the temperature to 40 ° C., stirring was performed for 1 hour and 30 minutes. After cooling the liquid temperature to 25 ° C or lower, 14.9 parts by mass of aluminum trisacetylacetonate, silicone-based surfactant (trade name: DOW CORNING TORAY L-7001, manufactured by Toray Dow Corning Co., Ltd.) 4.8 A mass portion was added and the mixture was stirred for 30 minutes or more to prepare a composition for forming a hard coat.

<Making a hard coat film>
The above mixture was applied to one surface of a polyimide film (manufactured by Sumitomo Chemical Co., Ltd., thickness 50 μm) with a bar coater, and cured by heating at 130 ° C. for 2 minutes. The thickness of the obtained coating film was 10 μm.

Comparative Example 3 (without adhesive polymer)
<Paint preparation>
Under stirring in a 2 L volume beaker, water-dispersed colloidal silica sol (trade name: ^Snowtex RO, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 20%) 178.0 parts by mass, propylene glycol monomethyl ether dispersed colloidal silica sol ( Product name: PGM-ST, manufactured by Nissan Chemical Industries, Ltd., solid content concentration 30%) 574.0 parts by mass were mixed and heated to 40 ° C. with stirring. A mixture of 225.0 parts by mass of 3-glycidoxypropyltrimethoxysilane (GPTMS) and 101.0 parts by mass of 1,2-bis (triethoxysilyl) ethane was added dropwise thereto over 1 hour. Then, the mixture was stirred for 2 hours while maintaining the solution temperature at 40 ° C. After cooling, 12.8 parts by mass of aluminum trisacetylacetonate and 0.4 parts by mass of a silicone-based surfactant (trade name: BYK-347, manufactured by BYK-Chemie) were further added, and the mixture was stirred at room temperature for 2 hours.

<Making a hard coat film>
The above mixture was applied to one surface of a polyimide film (manufactured by Sumitomo Chemical Co., Ltd., thickness 50 μm) with a bar coater and cured by heating at 130 ° C. for 2 minutes. The thickness of the obtained coating film was 10 μm.

Comparative Example 4 (without adhesive polymer, film corona treatment)
A hard-coated film having a hard-coat layer on the surface was obtained by the same operation as in Comparative Example 3 except that the surface of the polyimide film was subjected to corona discharge treatment in advance.

[Characteristic evaluation of hard coat layer]
Each characteristic of the hard-coated layer of the hard-coated lens or the hard-coated film obtained in the above-mentioned Examples and Comparative Examples was measured under the following conditions.
The measurement results of Examples 5 to 8 are shown in Table 1, and the measurement results of Comparative Examples 1 and 2 are shown in Table 2.
The measurement results of Examples 9 to 12 are shown in Table 3, and the measurement results of Comparative Examples 3 and 4 are shown in Table 4.

<Pencil hardness of paint film>
In order to evaluate the hardness of the coating film, a pencil hardness test was conducted in accordance with JIS standard (JIS K 5600-5-4).
Specifically, the surface is scratched with a lead having a different pencil density, and the hardest pencil density that does not cause scratches is defined as the pencil hardness. The pencil density is 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H from the soft side to the hard side.

<Scratch resistance test of coating film (steel wool scratch test)>
In order to evaluate the scratch resistance of the coating film, a steel wool scratch test was conducted under the following conditions.
# 0000 steel wool was fixed to a steel wool holder of a surface measuring machine (model number: TYPE14DR, manufactured by Shinto Kagaku Co., Ltd.), a load of 1000 g was applied, and the surface was rubbed back and forth 100 times. The evaluation criteria are as follows.
A ... No scratches can be confirmed B ... Some scratches can be confirmed (1 to 10)
C ... Many scratches can be confirmed (11 or more)

<Appearance of coating film>
In order to evaluate the appearance of the coating film, the haze value was measured in accordance with the ASTM standard (ASTM D1003).
The haze value of the lens was measured using a haze meter (BYK Gardner Haze-Guard Plus, manufactured by BYK Gardener; ASTM standard). The evaluation criteria are as follows.
A ... Haze value less than 0.2% B ... Haze value 0.2% or more and less than 1% C ... Haze value 1% or more

<Adhesion of coating film>
In order to evaluate the adhesion, a crosshatch test was conducted in accordance with the 100-square grid test method of the old JIS standard (JIS K5400-8.5; JIS D0202: 1988).
Specifically, using a single-blade cutting tool (cutter knife), make 11 cuts that reach the base material at 2 mm intervals in the coating film formed on the base material, and change the direction by 90 ° in the same manner. Make 11 cuts and make cuts in a grid pattern. Adhesive tape is attached on the grid-shaped cuts. Keep this tape at right angles to the paint film surface and peel it off momentarily.
The numbers in the table indicate the number of grids in which peeling was not confirmed among the 100 grids.

<Mandrel bending test>
In order to evaluate the bending resistance, a mandrel bending test was conducted in accordance with JIS standard (JIS K 5600-5-1).
Specifically, the hardcourt coated surface was turned to the outside, bent 180 ° along a mandrel having a diameter of 2 mm, and the presence or absence of cracks was evaluated.
The evaluation criteria are as follows.
○ ・ ・ ・ No cracks occur in the hard coat layer × ・ ・ ・ Cracks occur in the hard coat layer

By using the composition for forming a hard coat of the present invention, a coat film can be formed on the surface of a useful resin film base material with good adhesion without a primer. Not only that, it also has high bending resistance and surface hardness, so it is very useful as a hard coat for flexible resin film substrates such as polyimide, which has been attracting attention in recent years.

1 Resin base material 2 Composition layer for forming a hard coat 3 Hardened layer (hard coat)
4 Primer

Claims (4)

At least:
A component: Metal oxide fine particles B component: Organic silicon compound or its hydrolyzate C component: Alkoxysilyl group which is a reactive functional group is at both ends of a compound selected from the group consisting of polyurethane and polyester carbonate. Adhesion promoting component having an alkoxysilyl group characterized by being bonded D component: curing catalyst E component: containing a solvent,
The adhesion promoting component having an alkoxysilyl group is the general formula (4):

(In the formula, e and f represent integers from 0 to 2, R ¹⁰ represents an adhesion-promoting polymer main chain selected from the group consisting of polyurethanes and polyester carbonates, and the two R ^11s are the same, respectively. Alternatively, it may indicate an alkylene group having 1 to 20 carbon atoms, and the alkylene group may have an unsaturated hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group or a hetero atom. Alternatively, multiple R ^12s and R ^13s represent the same or different alkyl groups with 1 to 4 carbon atoms, respectively, and the two Zs are the same or different, respectively, amide bond, imide bond, urethane bond, It shows a chemical bond selected from the group consisting of urea bond, ether bond, ester bond, carbonate bond, sulfide bond, thiourethane bond, thiourea bond, and thioester bond.) It has an alkoxysilyl group at both ends. A composition for forming a hard coat, which is a compound . A laminate of a resin base material and a hard coat layer directly formed on the resin base material, wherein the hard coat layer is a cured body of the hard coat forming composition according to claim 1 . Laminate. The laminate according to claim 2 , wherein the resin base material is a polycarbonate lens base material. The laminate according to claim 2 , wherein the resin base material is a flexible base material made of polyimide.

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