JPS6235340A - Surface treated laminate - Google Patents

Abstract

PURPOSE:To obtain the title laminate having excellent characteristics of an light transmittance, a surface smoothness, an adhesion, an anti-flaw property and a surface hardness by providing a layer composed of a specific resin composition as the most lower layer, and a layer composed of a specific UV curable resin as the most upper layer on the surface of an image forming layer. CONSTITUTION:The title laminate comprises the most lower layer composed of an epoxy acrylate resin having >=2 acryloyl groups and/or methacryloyl groups in a molecule, a copolymerized polyester resin and an aminosilane compd. and prepared by a multiple coating process having >=2 coatings, and the most upper layer composed of a photopolymerizable compd. having >=3 the acryloyl groups and/or the methacryloyl groups in the molecule and prepared by an UV curable process. Thus, the defects of the surface treatment which are brought by using a lith film are solved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a surface-treated laminate with excellent scratch resistance, adhesion, and surface hardness, particularly on at least one side of a flexible organic polymer film. Image forming layer? The present invention relates to the provided laminate.

[Conventional technology]

To produce a printing plate, first, a contact screen is used to enlarge or reduce the original and simultaneously separate halftone dots using camera work. This halftone dot separation film t and the return lithium film are used to convert the image into a closely inverted image, and this operation is repeated several times to obtain the desired image. The obtained image is exposed to light on a printing plate such as a tPS plate or a photosensitive resin plate and developed to produce a printing plate. Conventionally, such reversing lithographic films have been made using silver salt-based photosensitive emulsions or dye-V' pigments, and the photosensitive emulsion layer Vi of the lithographic film is exposed, and the photosensitive emulsion layer is very soft and easily coated. As the number of times the lith film is used increases, the accuracy of image formation decreases due to scratches on the photosensitive emulsion layer that occur during the mask alignment process. In addition, the photosensitive emulsion layer is coated with organic solvents or acids.
Because it is easily dissolved in alkaline aqueous solution, it also causes problems when cleaning lithium film with dust or resist film attached.
In order to improve these drawbacks, various surface treatment methods have been proposed to increase the surface hardness of the lithographic film on which images are formed and to impart scratch resistance. However, the surface treatment using thermosetting resins such as epoxy resins, urethane resins, and silicone resins deforms the lisphyminosylum due to the high temperatures and long hours required for relay processing. In addition, the surface of the ultraviolet curable resin is 8 in a circle.
As mentioned above, it is not possible to impart sufficient adhesion to both the film surface and the light-sensitive emulsion layer surface through processing, and there is no material that satisfies all aspects of adhesion, scratch resistance, unevenness, and surface hardness. Under these circumstances, the object of the present invention is to provide a low-temperature curing surface treatment that provides excellent adhesion, scratch resistance, and surface hardness. be.

Means for solving illumination points) The above laminates, for example, the refill surface treatment
As a result of our efforts to solve the drawbacks of up to It contains a hyalanic compound and a photopolymerizable compound having 7N on the acryloyl group or /ν meryl group at the bottom and more than one molecule. However, the lack of surface treatment up to this point on the coating film has led to the discovery of the present invention.

Specifically, the present invention provides a flexible organic polymer film in which the bottom layer of a laminate having an image forming layer on one side is an evocrylate resin or a copolymerized polyester having two or more acryloyl and/or methacryloyl groups in the molecule. It is made of a resin composition containing a resin aminosilanized fraction, and the uppermost layer has 8 or more acrylic molecules in the molecule, and has excellent scratch resistance 2 and surface hardness. In addition, because of the ultraviolet curing method, there is no thermal deformation of the laminate that can be cured at low temperature, and productivity can be greatly improved.6 The flexible organic polymer film of the present invention is particularly suitable for polyester, polypropylene, polyethylene,.

There are films made of polyvinylidene chloride, polycarbonate, cellulose acetate, nitrocellulose, etc.Although polymer films can be used in unstretched form, stretching, especially biaxial stretching, improves mechanical properties. , thermal properties and dimensional stability are improved, which is preferable. There is no particular limit to the thickness of the polymer film, or approximately 5 to 500 mm.
? rn s Preferably about 200 μm ◎ The image provided on at least one side of the child film refers to characters,
This is a layer in which images such as lines and halftone dots are patterned. Image-forming materials include water-sensitive emulsions and non-silver salt-based agents containing dyes and pigments. The thickness of the image forming layer is not particularly limited, but is usually about 1 x 100 pm, preferably about 1 to 60 Prr.
Specific examples of the laminate of the present invention include printing original drawings, 211X diagrams, lithography, labels, etc., plate-making materials, optical masks, circuit wiring, display boards, phototypesetting, etc. Examples include image forming materials such as machine dials, photoresist films, etc.

According to the present invention, a laminate in which at least two-layer liquid eIL is applied to the surface of the image forming layer of the laminate using an ultraviolet curable resin includes an ultraviolet curable layer that forms the bottom layer on the surface of the image forming layer of the laminate. After applying the mold resin composition ft and irradiating it with ultraviolet rays, the ultraviolet rays that form the top layer □1 □□□1, Iyayawa, E, Sho 4 Isu dry tree invention 2 have an intermediate layer between the top layer and the bottom layer. Although layers may be provided, a two-layer coating method is generally adopted. The epoxy acrylate resin having two or more acryloyl groups or Fi/C or methacryloyl groups in the molecule used in the present invention refers to (meth)acrylate compounds of epoxy compounds having two or more epoxy groups in one molecule ( All methacrylate compounds and acrylate compounds are shown.

The aircraft will be abbreviated below. ), the starting material of the epoxy compound has an epoxy f of 100 to 4,000,
Preferably it is 100-1.000.

Typical photopolymerizable epoxy (meth)acrylate resins include (1) (meth)acrylate compounds of polyglycidyl ethers of divalent or higher polyhydric phenols, such as bisphenol A, bisphenol F, halogenated bisphenol A, etc. Bisphenol-type epoxy resins that are diglycidyl ethers, and (meth)acrylate compounds of novolac-type epoxy resins that are polyglycidyl ethers such as phenol novolak and cresol novolak, (II) Polyglycidyls of dihydric or higher polyhydric alcohols Ether (meth)acrylate compounds, such as ethylene glycol, globylene glycol, neopentyl glycol, 1,4-butanediol,
1. (Meth)acrylate compounds of polyglycidyl ethers of dihydric or higher aliphatic alcohols such as 6-hexanediol and trimethylolpropane, etc. (IH)
:(meth)acrylate compounds of polyglycidyl esters of divalent or higher polyvalent carboxylic acids such as y taric acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and adipic acid, nitrogen such as aniline, isocyanuric acid, etc. (meth)acrylate compounds of polyglycidyl ether in which the active hydrogen bonded to the atom is replaced with a glycidyl group, (v) vinyl 7-chlorohexene dieboxide obtained by epoxidizing the olefin bond in the molecule, 3.4 −
Ring group polyepoxy compounds such as epoxycyclohexylmethyl-8,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxy)cyclohexyl-515-spiro(8,4-epoxy)cyclohexane-m-dioxane, etc. (meth)acrylate compounds, (v
l) N, N・N', N'-tetraglycidyl metaxylene diamine, N, N, N', N'-tetraglycidyl-1,8-bis(aminomethyl)cyclohexane, etc. (meth) ) acrylate compounds, etc. These epoxy acrylate resins may be used alone or in combination of two or more.

Among these, preferred epoxy acrylate resins include diglycidyl ether of bisphenol A, phenol novolac type polyepoxy compounds, cresol novolak type polyepoxy compounds, and (meth)acrylate compounds of polyhydric alcohol polyepoxy compounds. Ru.

Further, (meth)acrylate compounds of epoxy compounds having one epoxy group r in the molecule, such as allyl glycidyl ether and phenyl glycidyl ether, can also be used in combination.

The copolyester used in the present invention is a copolyester synthesized from at least one saturated polycarboxylic acid 2 and its derivatives and at least 1& polyhydric alcohol.

Saturated polycarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalene dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, l,
Aliphatic or alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and phosphoric acid, as well as sulfonic acids such as 5-sodium sulfoisophthalic acid and 4-sodium sulfophthalic acid. Aromatic and aromatic dicarboxylic acids containing metal bases, etc.

As the aromatic dicarboxylic acid component, terephthalic acid and/or isophthalic acid are particularly preferable, and 20 to 100 mole of the saturated polycarboxylic acid component, preferably 40 to 40 mole of the saturated polycarboxylic acid component.
10000000000000000000000000000000.

In addition, sulfonic acid metal salt base M aromatic dicarboxylic acids are useful for adhesive properties as well as for saturated polyhydric carboxylic acid components.
．． It is also possible to copolymerize in a range of 5 to 20 mol, preferably 1.0 to 10 mol.

As the saturated polycarboxylic acid component, in addition to the above-mentioned compounds, it is also possible to use polycarboxylic acids with octafunctionality or more, such as trimellitic acid and pyromellitic acid, in which case #'
It is desirable that it be less than iIOmolti.

Examples of polyhydric alcohol components include ethylene glycol, propylene glycol, 1,4-butanediol,
Alkylene glycols such as 1.6-hexanediol, 1.5-bentanediol, neopentyl glycol,
Diethylene glycol, triethylene, glycol, polyoxyallene glycol such as polyethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, halogenated alkylene glycol such as dibromoneopentyl glycol, 1,4-cyclohexanediol, Bisphenol A ethylene oxide or/
and propylene oxide adducts, l,4-cyclohexane dimetatool, etc. These glycol components may be used alone or in combination.

In addition to the above-mentioned glycol components, polyhydric alcohol components include polyhydric alcohols with a valence of 8 or higher, such as trimethylolpropane, trimethylolethane, and pentaerythritol.
It is also possible to use them together in an amount of 0 mol or less. In addition to the above-mentioned saturated polycarboxylic acid 2 and polyhydric alcohol, monohydric carboxylic acid and monohydric alcohol may be used as necessary. It may also be used in small amounts.

The method for producing the copolyester of the present invention is not particularly limited, and methods such as transesterification and direct esterification may be used. If necessary, tetra-n-butyl titanate, stannous oxalate, acetic acid, etc. Known catalysts such as zinc and antimony trioxide are used.

Examples of preferred components of the copolymerized polyester used in the present invention include, as the acid component, a binary system of terephthalic acid and isophthalic acid, a ternary system of terephthalic acid, isophthalic acid, and adipic acid, and a ternary system of terephthalic acid and adipic acid. There are two-component systems of acids, two-component systems of terephthalic acid and sebacic acid, three-component systems of terephthalic acid, isophthalic acid, and sebacic acid, and there are also cases where the above-mentioned aromatic dicarboxylic acids containing sulfonic acid metal bases are copolymerized. In that case, the polyhydric carboxylic acid component will be a ternary or more component system. Examples of the polyhydric alcohol component include a two-component system of ethylene glycol and propylene glycol, a two-component system of ethylene glycol and 1,6-hexanediol, and a two-component system of ethylene glycol and neopentyl glycol.

The amount of copolymerized polyester used in the present invention is
It is preferable that the copolyester/epoxy acrylate resin be added in a weight ratio of 5/95 to 70,780.

The aminosilane compounds used in the present invention include aminemethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyltri-n-propoxysilane,
Aminomethyltrirn-butoxysilane, aminoethyltriethoxysilane, aminoethyltriethoxysilane, aminoethyl) IJ-n-propoxysilane, aminoethyltrirn-butoxysilane, amino-n-propyltrimethoxysilane, Amino-n-propyltriethoxysilane, amino-n-propylt 17-fi
-propoxysilane, amino-n-propyltri-n
-Butoxysilane, N-aminomethyl-aminoethyltriethoxy7rane, N-aminomethyl-aminomethyltriethoxysilane, N-aminomethyl-aminomethyltriethoxysilane, Roboxysilane, N-aminomethyl-aminomethyltriethoxysilane, N-aminomethyl-aminomethyltriethoxysilane, N-aminomethyl-aminomethyltriethoxysilane, n-butoxysilane, N-β-aminoethyl-β-aminoethertrimethoxysilane, N-
β-Aminoethyl-β-amineethyltriethoxysilane, N-β-aminoethyl-β-aminoethyl-n-propoxysilane, N-β-aminoethyl-β-aminoethyltri-n-butoxysilane, N-γ -ami/-n-
Globy-γ-amino-n-propyltrimethoxysilane, N-1-amino-n-probyl-tsamino-n-
Propyltriethoxysilane, N-γ-amino-n-propyl-γ-amino-n-propyltri-n-propoxysilane, N-7-amino-n-propyl-γ-amino-n-propyltributoxysilane, N-aminomethyl -β-aminoethyltrimethoxysilane, N-aminomethyl-β-aminoethyltri-n-butoxysilane, N
-Aminoethyl-7-amino-n-propyltrimethoxysilane, N-aminomethyl-γ-amino-n-propyltri-n-butoxysilane, N-β-7minoethylaminemetheltrimethoxysilane, N-β- Aminoether-aminomethyltri-n-butoxysilane, H-aminomethyl-7-amino-n-propyltrimethoxysilane, N-aminothimero-amino-n-probiltri-n-butoxysilane, N-γ-amino-n-propyl- Aminomethyltrimethoxysilane, N-γ-amino-n-propyl-aminomethyltri-n-butoxysilane, N-di-amino-n-propyl-β-aminoethyltrimethoxysilane, he-γ-amino-n-prohy-β
-aminoethyltri-n-butoxysilane, N-β-aminoethyl-γ-amino-n-propyltrimethoxysilane, N-β-aminoethyl-γ-amino-n-propyltri-n-butoxysilane, etc. . A particularly preferred one is N-β-aminoethyl-γ-amino-n-propyltrimethoxysilane.

0.05 to 4o1rt part, preferably 0.1 to aO*
This is Sobe.

Examples of photopolymerizable compounds having eight or more acryloyl groups and/or methacryloyl groups in the molecule used in the present invention include (1)) rimeterolpropane tri(meth)acrylate, trimethylolethanetri (
7 acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)
Φ to acrylate, dipentaerythritol (meth)
Poly(meth)acrylates of aliphatic polyhydric alcohols with 3fflI or more such as acrylates, poly(meth)acrylates of halogen-substituted aliphatic polyhydric alcohols with 8 or more valences, tris(meth)acryloyloxyethyl isocyanurate, tris( Examples include tris(meth)acryloyl alkyl isocyanurates such as meth)acryloyloxypropyl isocyanurate and tris(meth)acryloyloxybutyl isocyanurate.

These trifunctional or higher functional (meth)acrylate compounds may be used alone or in combination of two or more. Further, various other oligomers, polymer di- and (meth)acrylate monomers having less than two functional groups may be used in combination as required.

Examples of the photoinitiator that promotes the photopolymerization reaction of the ultraviolet curable resin of the present invention include ketals such as benzyl dimethyl ketal, penzointimel ether, benzoin ethyl ether, penzoin-1-propyl ether,
Benzoin a such as benzoin, a-methylbenzoin
, 9. Anthraquinones such as 10-anthraquinone, l-chloroanthraquinone, 2-chloroanthraquinone, and 2-ethylanthraquinone, benzophenones such as benzophenone, P-chlorobenzophenone, and P-dimethylaminobenzophenone, 2-hydroxy-2-methyl Globiophenobens such as propiophenone, 1-(4-iapropylphenyl)-2-hydroxy-2-methylpropiophenone, sperones such as dicanthosuberone, diphenyl disulfide, tetramethylthiuram disulfide, thioxanthone, etc. Sulfur-containing compounds, methylene blue,
Colors such as eosin and fluorescein are included.
, and n et al. may be used alone or in combination of two or more.

The amount of photoinitiator added is 0.05 to 20% by weight, preferably Vio.5 to 10% by weight, based on the resin component of the ultraviolet curable resin forming the bottom layer or the top layer.

The surface treatment agent of the present invention can also be used after being diluted with a compatible organic solvent, and examples of such diluents include slag, alcohol, ether, ester, and ketone. type, aromatic hydrocarbon type, chlorinated hydrocarbon type,
There are solvents such as polyhydric alcohol derivatives. The diluent is 1
Each species may be used alone, or two or more species may be used in combination.

Furthermore, if necessary, the surface treatment agent of the present invention may include a surface smoothing agent.
Various additives such as antistatic agents, antifoaming agents, surfactants, and colorants may be added.

In 2 of the present invention, in order to remove dust etc. adhering to the laminate before surface treatment of the laminate, pretreatment such as blowing with a clean blow or ultrasonic cleaning with ion-exchanged water is performed. is common.

The method of applying ultraviolet curable resin to the laminate is the usual method.
That is, it can be applied by a dipping method, a spray method, a spin code method, a roll coat method, a bar code method, or the like.

The thickness of the coating layer is 0.1 to 20PrrL as the bottom layer.
.

Preferably, the coating thickness is 0.3 to 1 Q pm, and the top layer is preferably 0.5 to 30 pm, preferably 1 to 20 pm. If the thickness of the bottom layer is less than 0.1 part m, the adhesion with the top layer will be insufficient, and
If it exceeds pm, cracks tend to occur in the coating film, which is not preferable. Furthermore, if the thickness of the top layer is less than 0.5 μm, the scratch resistance and surface hardness will be insufficient;
If it exceeds 0 pm″r, cracks and peeling of the coating film tend to occur, which is not preferable.

To cure the applied ultraviolet curable resin of the present invention,
A method of irradiating ultraviolet rays in the wavelength range of 200 to 450 nm is used. When curing a coating film by irradiating ultraviolet rays, it is preferable to cure the coating film under an atmosphere of an inert gas such as nitrogen gas or carbon dioxide. A preferred method is to apply a curable resin and then cure it by irradiating it with ultraviolet rays, and then apply an ultraviolet curable resin that forms the top layer and then cure it by irradiating it with ultraviolet rays.

(Effects of the Invention) In the present invention, the surface treatment not only improves light transmittance and surface smoothness, but also improves adhesion, scratch resistance, and surface properties. Because of its excellent durability, it is possible to obtain a laminate that prevents scratches on the laminate, facilitates cleaning of the laminate, and can accurately form a desired image. On the other hand, since UV curing is used, curing can be performed at low temperatures, so the laminate does not deform due to heat, the curing time can be greatly shortened, and productivity can be greatly improved.

(Example) The following describes the present invention based on examples. Please explain in more detail or
The present invention is not limited to these examples in any way.

The measurement method in the examples was as follows.

Scratch resistance test 'D Steel Cool No. 5oooo was used to test the load of IKf. The surface was rubbed 30 times over a length of 11 inches, and the degree of damage was then measured.

Adhesion test (JISDO202): Place 11 vertical and horizontal scars (cross cut) on the coated surface at 1 square intervals, adhere cellophane tape on top of this, and forcefully peel it off in the 45° direction, leaving a square that does not peel off. The coating was strongly pressed against the coated surface at an angle of 45° using a t-shirt to rub the coated surface, and the presence or absence of scratches was measured. In Examples and Comparative Examples, parts are by weight.

Synthesis Example 1 In a stainless steel autoclave equipped with a stirrer, 2 thermometers, and a partial reflux condenser, 194 parts of dimethyl terephthalate, 194 parts of dimethyl isophthalate, 191 g of ethylene glycol, and 16 g of 1,6-hexanediol were added.
6 parts 2 and 0.25 parts of tetra-n-butyl titanate) were added, the temperature was gradually raised until the reaction temperature reached 220°C, and the reaction was carried out at 220°C for 2 hours. Then, gradually reduce the pressure to 1
A saturated copolymerized polyester (A) was obtained by reacting for 1 hour at a temperature of 260°C under a reduced pressure of 0a)(f).The molecular weight of the obtained saturated copolymerized polyester was 8.700.

The composition measured by NMR was as follows.

Polyhydric carboxylic acid component: Terephthal #1 50 moles Isophthalic acid 50 moles Polyhydric alcohol component: Ethylene glycol 40 moles 1.6-hex/diol 60 moles Synthesis Example 2 Dimethyl terephthalate 19 was placed in the same reaction vessel as Synthesis Example 1.
4 parts of dimethyl isophthalate, 194 parts of ethylene glycol, 220 parts of neo-ethylene glycol, 2 parts of zinc acetate, and 0.2 parts of antimony trioxide, and esterified over 3 hours at 140°C to 220°C. The exchange reaction was carried out, and then the pressure was gradually reduced to 10 mHf for 2 hours.
The reaction was carried out at 60°C for 1 hour. The molecule i of the obtained saturated copolymerized polyester (B) was 2,800. NMR
The composition measured was as follows.

Polyhydric carboxylic acid component: Terephthal #50 mole Isophthalic acid 50 mole Polyhydric alcohol component: Ethylene glycol 40 mole Neohentyl glycol 60 mole Synthesis Example 8 Equipped with a stirrer, a thermometer and a partial speed cooling tube.

Dimethyl terephthalate 18634, dimethyl isophthalate 18
6 parts, 191 parts of ethylene glycol, 156 parts of 1,6-hexanediol, and 0.25 parts of tetra-n-butyl titanate. In addition, the temperature was gradually raised until the reaction temperature reached 220°C, and the reaction was carried out at 220°C for 2 hours. Then 5-
) 22 parts of IJumsulfoiphthalic acid added to 1 part
After reacting at 20 to 260°C for 1 hour, the reaction was continued for 1 hour at 260°C under a reduced pressure of 1O-Hf to obtain a saturated copolymerized polyester (C)k. The molecule t of the obtained saturated copolymerized polyester (C) was 8.200. N Ni
The composition measured by R was as follows.

Polyhydric carboxylic acid component: Terephthalic acid 48 mol Isophthalic acid 48 mol 5-sodium sulfoisophthalic acid 4 mol Polyhydric alcohol component: Ethylene f 17 = r-L A 40 mol type photosensitive emulsion was coated to form a patterned image. Lipoxy 5P-5003 (manufactured by Showa Kobunshi), which is a bisphenol A type epoxy acrylate resin, was applied to the Shiri IJ film.
5 parts, 5 parts of copolymerized polyester (A) obtained in Synthesis Example 1,
2 parts of tetrahydrofurfuryl acrylate, 2 parts of diacrylate of 4-1-yl ethylene oxide adduct of bisphenol A, N-β-7minoethyl-γ-amino-n-
1 part propyltrimethoxysilane, 2-hydroxy-2
- Apply an ultraviolet curable resin consisting of methylpropiophenone o, ai, 80 parts of methyl cellosolve, 80 parts of toluene, and 80 parts of ethyl acetate using a spinner, and heat at 60°C for 50 minutes.
After drying with hot air for 80W/cI under an inert gas atmosphere.
n's water-cooled high-pressure mercury lamp? Irradiate for 40 seconds at a distance of 15 mm to harden.

Next, 40 parts of pentaerythritol tetraacrylate, 2-hydroxy 2-methylglobiophenone Lg
Similarly, an ultraviolet curable resin consisting of m and 60 parts of toluene was applied using a spinner and cured by irradiation for 20 seconds in the same manner. The measurement results of the surface treated film were as follows.

Adhesion: 100/100 Scratch resistance: A lithium film was surface treated in the same manner as in Example 1 except that copolymerized polyester (13) was used instead of scratch resistance. The measurement results of the surface-treated lithium film were as follows.

Adhesion: 100/100 Scratch resistance: No scratches Surface hardness: 5H Example 8 The color of copolymerized polyester (A) in Example 1 and 2. K Copolymerized polyester (C)! The surface of the lith film 4 was treated in the same manner as in Example 1, except that it was used in Example 1. The measurement results of the surface-treated lithium film were as follows.

Adhesion: 100/100 Scratch resistance: Intact surface f & degree = 5H Comparative Example 1 40 parts of pentaerythritol tetraacrylate and N-β-aminoethyl-r were added to the same lith film as in Example 1.
-Amino-n-propyltrimethoxysilane 2 parts, 2-
A wire-curing resin consisting of 1 or 2 parts of hydroxy-2-methylglohiophenone and 60 parts of toluene? After applying the coating with a Schiner and drying with hot air at 60°C for 5 minutes, a water-cooled high-pressure mercury lamp of 80 W/crs was applied under an inert gas atmosphere.
It was irradiated for 40 seconds at a distance of 5 cfR and cured. The measurement results of the surface-treated lithium film were as follows.

Density U: 0/100 Scratch resistance: No damage Surface hardness = 5H Comparative Example 2 The same lithium film as in Example 1 was subjected to the surface treatment method of Example 1, but not added to the copolymerized polyester (A)'. Other than that, the surface treatment of Lith Film R was carried out in the same manner as in Example 1. The measurement results of the surface-treated lithium film were as follows.

Adhesion: 80/100° Scratch resistance; Undamaged surface hardness = 5H Comparative example 8 The same lithium film as in Example 1 was treated with the surface treatment of Example 1, and N-β-aminoethyl-γ-amino-n-propyl was applied to the same lithium film as in Example 1. A lithium film was surface treated in the same manner as in Example 1 except that trimethoxysilane was not added. The measurement results of the surface-treated lithium film were as follows.

Adhesion: 20/100 Scratch resistance: No scratches Surface hardness: 5H Comparative example 4 Bisphenol A type epoxy acrylate compound Lipoxy 5P-5008 (described above) was applied to the same lithium film as in Example 1 using the surface treatment method of Example 10. The surface treatment of the lithium film was carried out in the same manner as in Example 1, except that .

The measurement results of the surface-treated lithium film were as follows.

Adhesion: 0/100 Abrasion resistance: , Undamaged surface hardness: 5H Comparative example 5 The surface 9J of Example 1 was applied to the same lithium film as in Example 1.
The coating was applied using a sinter using the I4 method with the surface treatment order of the lower layer and upper layer reversed, and the coating film was cured under the same curing conditions as in Example 1. The measurement results of the surface-treated lithium film were as follows.

@ Layer property: 0/100 Scratch resistance: Scratch occurrence surface hardness 2F Comparative example 6 The same lithium film as in Example 1 was treated with the surface treatment method of Example 1, but trietherene glycol di was added instead of pentaerythritol tetraacrylate. The surface treatment of the lithium film was carried out in the same manner as in Example 1 except that acrylic (acrylic) k was used. The measurement results of the surface-treated lithium film were as follows.

Adhesion: 0/100 (Only the upper layer was peeled off) Scratch resistance: Scratch occurrence surface hardness: HB Examples 4 to 6 The glass of N-β-aminoether-T-amino-n-propyltrimethoxycrane of Example 1 The lithium film was surface treated in the same manner as in Example 1 using the aminosilane compounds listed in Table 1.

Measurement results of surface treated lith film? f - Shown in Table 1.

Table 1 Patent applicant Toyobo Co., Ltd.

Claims (1)

[Claims] An epoxy acrylate resin having two or more acryloyl groups and/or methacryloyl groups in the molecule as the bottom layer is applied to the surface of the image forming layer of a laminate in which an image forming layer is provided on at least one side of a flexible organic polymer film. It is made of a resin composition containing a polymerized polyester resin and an aminosilane compound, and the uppermost layer is made of an ultraviolet curable resin containing a photopolymerizable compound having three or more acryloyl groups and/or methacryloyl groups in the molecule. 1. A surface-treated laminate comprising at least two layers.