JP2003160617A - Uv curable composition for use in optical disk and optical disk using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a UV curable composition for use in an optical disk that can be cured in a short time by UV and form a resin film having good adhesiveness to both a reflecting film composed of a metal or a silicon compound and a resin substrate, and to provide, in particular when applied on the substrate of an amorphous polyolefin resin without special pretreatment, the UV curable composition for use in the optical disk that can form the resin film having good adhesiveness to both the amorphous polyolefin resin substrate and the reflecting film. <P>SOLUTION: This UV curable composition for use in the optical disk comprises at least a monofunctional methacrylic compound and (meth)acrylic compound having a bisphenol A structure in a molecule and two or more (meth) acryloyl group, and also a (meth)acrylic compound having a phosphoric acid group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable composition for optical disks, and more particularly to an ultraviolet curable composition having excellent adhesion to an optical disk using an amorphous polyolefin resin substrate.

[0002]

2. Description of the Related Art In recent years, an amorphous polyolefin resin has been attracting attention as a transparent thermoplastic resin having heat resistance. Amorphous polyolefin resin has high transparency,
It has excellent mechanical and optical properties such as low birefringence, heat resistance, and low moisture absorption. Taking advantage of these properties, the development of various industrial applications, such as use as optical disk substrates, is considered as an alternative to polymethylmethacrylate (PMMA) and polycarbonate (PC), which are typical conventional transparent thermoplastic resins. Has been done. However, since there was no protective coating agent having good adhesion to the amorphous polyolefin resin, there were few opportunities for industrial use as a substitute for PMMA and PC.

An amorphous polyolefin resin is also called a cyclic polyolefin resin and has an aliphatic main chain and is characterized by having an aliphatic polycyclic ring structure in the main chain.

As a means for improving the adhesion of the ultraviolet curable protective coating agent to such an amorphous polyolefin resin, there is a method of activating the resin surface.
For example, there are pretreatment methods such as a flame treatment method, a corona treatment method, an oxidation treatment method and a sandblast method. However, these treatment methods are effective in improving adhesion, but cause problems such as coloring and surface roughening, impairing optical characteristics, or problems such as increase in equipment cost due to increase in production process, etc. However, it is not practical as a means for improving adhesion.

By the way, when an amorphous polyolefin resin is used for an optical disk substrate, a protective coating agent made of an ultraviolet curable resin composition is used to protect the information recording layer on the substrate. Further, a reflective film made of a metal or a silicon compound is provided on the uppermost layer of the information recording layer, but the cured coating formed by the protective coating agent does not have the information recording layer on the substrate (that is, Needless to say, it must strongly adhere to the amorphous polyolefin resin substrate itself (where the reflective film is not formed), and also strongly adheres to the reflective film, which is the uppermost layer of the information recording layer formed on the substrate. It is necessary to. However, the existing UV-curable composition for optical disks has insufficient adhesion to an amorphous polyolefin substrate. An example of an ultraviolet curable resin composition having good adhesion to an amorphous polyolefin substrate is disclosed in Japanese Patent No. 3030953, and the composition is a reflective film formed on a substrate of an optical disk and made of a metal or a silicon compound. No specific technique has been disclosed with respect to the adhesiveness with, and an ultraviolet-curable composition for an optical disk having good adhesiveness with respect to both the amorphous polyolefin substrate and the reflective film has not yet been put to practical use.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. It is cured by ultraviolet rays in a short time and is excellent for both a reflective film made of a metal or a silicon compound and a resin substrate. An object of the present invention is to provide an ultraviolet-curable composition for optical discs, which is capable of forming a resin film exhibiting adhesion. In particular, an optical disk capable of forming a resin film that exhibits excellent adhesion to both the amorphous polyolefin resin substrate and the reflective film even when applied to a substrate using an amorphous polyolefin resin that has not been specially pretreated. It is an object of the present invention to provide a UV-curable composition for use in a car.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that among (meth) acrylic compounds, particularly monofunctional methacrylic compounds have a bisphenol A structure in the molecule. And a (meth) acryl compound having two or more (meth) acryloyl groups is used in combination, and a (meth) acrylic compound having a phosphoric acid group is further used to form an amorphous polyolefin resin substrate and a metal or silicon compound. The present inventors have completed the present invention by finding that particularly remarkable adhesion is obtained with respect to a reflective film.

That is, the present invention provides at least a monofunctional methacrylic compound, a (meth) acrylic compound having a bisphenol A structure in the molecule and having two or more (meth) acryloyl groups, and a phosphoric acid group. A UV-curable composition for optical discs, which comprises a (meth) acrylic compound having

An information recording layer having a reflective film made of a metal or a silicon compound as an uppermost layer is provided on a resin substrate, and the ultraviolet curable composition according to claim 1 is further provided on the reflective film. An optical disk provided with a cured film of a material is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As the monofunctional methacrylic compound used in the present invention, there is methacrylic acid or its derivative. In the present invention, an methacrylic acid ester compound represented by the following formula (1) is used. It is preferable. Formula (1)

[0011]

[Chemical 2] (In the formula, X represents a methyl group, R represents a linear or branched alkyl group or a derivative thereof, an aliphatic group having a cyclic structure or a derivative thereof, or a cyclic ether group or a derivative thereof.)

Examples of such ester compounds include methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, octyl, nonyl, dodecyl, isodecyl, lauryl, stearyl, hexadecyl and octadecyl as R in the formula (1). , Benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl, tetrahydrofurfuryl, nonylphenoxy A meta-group having a group such as ethyltetrahydrofurfuryl, caprolactone-modified tetrahydrofurfuryl, cyclohexyl, dicyclopentenyl, isobornyl, dicyclopentenyloxyethyl, etc. Acrylate, and the like.

The monofunctional methacrylate monomer represented by the above formula (1) is polymethyl methacrylate (PMM).
A) and polycarbonate (PC) are effective in improving the adhesion to a substrate for optical disks, but specifically improve the compatibility of the amorphous polyolefin resin and the ultraviolet curable composition, It is effective in improving the adhesion between cured coatings formed by the composition. The blending amount of the monofunctional methacrylate monomer is 5 to 5 in the composition of the present invention.
It is 30% by mass, preferably 10 to 25% by mass.

Particularly preferred compounds of the above formula (1) are those in which R in the formula (1) has 5 to 20 carbon atoms.
A straight-chain or branched alkyl group, or having 5 carbon atoms
10 to 10 are compounds having an aliphatic group having a monocyclic ring structure or a cyclic ether group.

As such examples, lauryl methacrylate, stearyl methacrylate, isodecyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate and the like can be mentioned. These compounds not only improve the adhesion between the cured coating film and the resin substrate, especially the resin substrate using amorphous polyolefin, but also have the effect of removing the strain generated during curing of the ultraviolet curable composition. However, if it is used in the composition of the present invention in an amount of more than 30% by mass, the pencil hardness and the curing speed of the cured film will be reduced, which is not preferable.

In the ultraviolet-curable composition for optical disks of the present invention, a resin is obtained by using a (meth) acrylic compound having a bisphenol A structure in the molecule and having two or more (meth) acryloyl groups. Adhesion between a substrate, especially a resin substrate using amorphous polyolefin is improved. In particular, in the present invention, the effect becomes remarkable by using the monofunctional methacrylic compound in combination.

The compounding amount of the (meth) acrylic compound having a bisphenol A structure in the molecule and having two or more (meth) acryloyl groups is 25 to 8 in the composition of the present invention.
It is 5% by mass, preferably 30 to 80% by mass.

Specific examples of the (meth) acrylic compound having a bisphenol A structure in the molecule and having two or more (meth) acryloyl groups include, for example, 2 mol of ethylene oxide or propylene oxide per 1 mol of bisphenol A. Di (meth) of diol obtained by addition
Examples thereof include acrylate and di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A.

Further, examples of the (meth) acrylic compound having a phosphoric acid group used in the present invention include ethylene oxide-modified phosphoric acid (meth) acrylate and ethylene oxide-modified alkylated phosphoric acid (meth) acrylate. The content of the (meth) acrylate having a phosphoric acid group is 0.01 to 5% by mass, preferably 0.05 to 3% by mass in the composition of the present invention. 0.01 mass%
If it is less than the above range, sufficient adhesive force with the reflective film cannot be obtained.
Further, if it exceeds 5% by mass, signal characteristics are deteriorated during a high temperature and high humidity durability test, which is not preferable.

In the present invention, the following acrylate monomers can be used as long as the adhesiveness to the resin substrate, particularly the amorphous polyolefin substrate is not impaired. Examples of the monofunctional acrylate include methyl, ethyl, propyl, butyl, amyl, cyclohexyl, 2-ethylhexyl, octyl, nonyl, dodecyl, isodecyl, lauryl, stearyl, hexadecyl, octadecyl, benzyl, methoxyethyl, butoxyethyl, as a substituent. Phenoxyethyl, nonylphenoxyethyl, glycidyl, 2-hydroxyethyl, 2-
Hydroxypropyl, 3-chloro-2-hydroxypropyl, dimethylaminoethyl, diethylaminoethyl,
Examples thereof include acrylates having a group such as tetrahydrofurfuryl, nonylphenoxyethyl tetrahydrofurfuryl, caprolactone-modified tetrahydrofurfuryl, isobornyl, dicyclopentanyl, dicyclopentenyloxyethyl and the like. Among these acrylates, lauryl acrylate, stearyl acrylate, isodecyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate and the like are preferable as the acrylate used in combination.

Examples of polyfunctional (meth) acrylates include 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecanedimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
Di (meth) acrylates such as tripropylene glycol and polypropylene glycol, di (meth) acrylates of tris (2-hydroxyethyl) isocyanurate,
Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, and obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane. Examples thereof include di- or tri (meth) acrylate of triol, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and poly (meth) acrylate of dipentaerythritol.

Further, what can be used together with the polymerizable monomer is a polymerizable oligomer, specifically,
Polyester (meth) acrylate, polyether (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like can be used as appropriate.

As the photopolymerization initiator used in the present invention, any known and conventional one can be used. As the photopolymerization initiator, a molecular cleavage type or a hydrogen abstraction type is suitable for the present invention.

Examples of the photopolymerization initiator that can be used in the present invention include benzoin isobutyl ether and 2,4-
Diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 1-hydroxycyclohexyl phenyl ketone, benzoin ethyl ether, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one and 2-methyl-1- (4-methylthiophenyl) -2
-Molecular cleavage type such as morpholinopropan-1-one,
Hydrogen abstraction type photopolymerization initiators such as benzophenone, 4-phenylbenzophenone, isophthalphenone, and 4-benzoyl-4′-methyl-diphenyl sulfide can be used.

Of these photopolymerization initiators, thioxanthone compounds are preferable in terms of adhesiveness to the resin substrate, particularly to the amorphous polyolefin substrate. The amount of the photopolymerization initiator used is 0.1 to 20% by mass, preferably 0.5 to 10% by mass in the composition composition of the present invention.

As the sensitizer for the above photopolymerization initiator, for example, trimethylamine, methyldimethanolamine, triethanolamine, p-diethylaminoacetophenone, ethyl p-dimethylaminobenzoate, p-
Isoamyl dimethylaminobenzoate, N, N-dimethylbenzylamine and 4,4′-bis (diethylamino)
It is also possible to use together with the above-mentioned polymerizable components such as benzophenone and amines that do not cause an addition reaction. Of course, it is preferable to select and use the above-mentioned photopolymerization initiator or sensitizer that has excellent solubility in an ultraviolet-curable compound and does not impair ultraviolet transmittance.

Further, the composition of the present invention may further contain other additives as necessary, such as thermal polymerization inhibitors, antioxidants typified by hindered phenols, hindered amines, phosphites, plasticizers and epoxies. A silane coupling agent typified by silane, mercaptosilane, (meth) acrylsilane and the like can be added for the purpose of improving various characteristics. As these, those having excellent solubility in the ultraviolet curable compound and those not inhibiting the ultraviolet transmittance are selected and used.

Next, an embodiment of an optical disk using the ultraviolet-curable composition of the present invention will be described with reference to an example using a substrate made of amorphous polyolefin. First, pits corresponding to signals are formed on a circular transparent substrate made of amorphous polyolefin. A substrate having a light reflection layer formed thereon is prepared. Further, instead of the pits, a substrate in which a recording layer made of an organic dye, a phase change recording material or the like is provided and a light reflection layer is laminated thereon may be used.

The light reflecting layer is made of aluminum, silver, gold,
It can be obtained by forming a thin film of a metal such as copper or an alloy thereof, or a silicon compound by a method such as sputtering or vapor deposition.

The organic dye that can be used in the recording layer is not particularly limited as long as it can form pits by a laser beam used for recording, and examples thereof include cyanine-based, phthalocyanine-based, azo-based, and naphthalocyanine. System, anthraquinone system, triphenylmethane system,
Examples thereof include pyrylium or thiapyrylium salt-based, squarylium-based, croconium-based, formazan-based, and metal complex dye-based systems.

Further, the dye may be mixed with a singlet oxygen quencher. As the quencher, acetylacetonate-based, bisdithiol-based such as bisdithio-α-diketone-based and bisphenyldithiol-based, thiocatechol-based, salicylaldehyde oxime-based, and thiobisphenolate-based metal complexes are preferable. Further, amine compounds having a nitrogen radical cation and amine quenchers such as hindered amines are also suitable.

GeSbTe and AgInSbT are available as the phase change recording material that can be used for the recording layer.
Examples include chalcogen alloys such as e.

Next, the ultraviolet-curable composition of the present invention is applied onto the above-mentioned light-reflecting layer, and a coating film is formed by a spin coating method or the like so that the film thickness after curing becomes 3 to 20 μm. The optical disk of the present invention can be obtained by irradiating ultraviolet rays to cure the coating film.

As means for irradiating ultraviolet rays, for example, a continuous irradiation type ultraviolet irradiation apparatus such as a high pressure mercury lamp or a metal halide lamp, or a flash irradiation type ultraviolet irradiation apparatus such as a xenon flash can be used.

Further, the optical disk of the present invention may be one in which reproduction / recording of information by a laser beam is carried out through a substrate as in the prior art, or one which is carried out through a cured film of the ultraviolet curable composition according to the present invention. May be

[0036]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following examples, "part" means "part by mass".

[0037] Example 1 80 parts of ethylene oxide modified bisphenol A diacrylate (* Add an average of 4 moles of ethylene oxide to bisphenol A. A compound in which acrylic acid is added to, and so on. ) Lauryl methacrylate 6.5 parts Trimethylolpropane ethoxytriacrylate 4.1 parts Bis (methacryloxyethyl) phosphate 0.1 parts 1-hydroxycyclohexyl phenyl ketone 3.5 parts 2,4-diethylthioxanthone, 4.5 parts p-Dimethylaminoacetophenone 1 part Ethyl p-dimethylaminobenzoate 0.2 parts Methoquinone 0.1 part The above components were mixed, heated and dissolved at 65 ° C. for 2 hours, and then an ultraviolet curable composition was prepared.

[0038] Example 2 EO-modified bisphenol A diacrylate 61.5 parts 25 parts of lauryl methacrylate Trimethylolpropane ethoxytriacrylate 4.1 parts Bis (methacryloxyethyl) phosphate 0.1 parts 1-hydroxycyclohexyl phenyl ketone 3.5 parts 2,4-diethylthioxanthone 4.5 parts p-Dimethylaminoacetophenone 1 part Ethyl p-dimethylaminobenzoate 0.2 parts Methoquinone 0.1 part An ultraviolet curable composition was prepared in the same manner as in Example 1 above.

[0039] Example 3 EO-modified bisphenol A diacrylate 51.5 parts Dicyclopentadiene diacrylate 10 parts 25 parts of cyclohexyl methacrylate Trimethylolpropane ethoxytriacrylate 4.1 parts Bis (methacryloxyethyl) phosphate 0.1 parts 1-hydroxycyclohexyl phenyl ketone 3.5 parts 2,4-diethylthioxanthone 4.5 parts p-Dimethylaminoacetophenone 1 part Ethyl p-dimethylaminobenzoate 0.2 parts Methoquinone 0.1 part An ultraviolet curable composition was prepared in the same manner as in Example 1 above.

[0040] Example 4 EO-modified bisphenol A diacrylate 31.5 parts Dicyclopentadiene diacrylate 30 parts Tetrahydrofurfuryl methacrylate 25 parts Trimethylolpropane ethoxytriacrylate 4.1 parts Bis (methacryloxyethyl) phosphate 0.1 parts 1-hydroxycyclohexyl phenyl ketone 3.5 parts 2,4-diethylthioxanthone 4.5 parts p-Dimethylaminoacetophenone 1 part Ethyl p-dimethylaminobenzoate 0.2 parts Methoquinone 0.1 part An ultraviolet curable composition was prepared in the same manner as in Example 1 above.

Example 5 An ultraviolet-curable composition was prepared in the same manner as in Example 1 except that lauryl methacrylate in Example 1 was replaced with dicyclopentanyl monomethacrylate.

Example 6 An ultraviolet-curable composition was prepared in the same manner as in Example 1 except that lauryl methacrylate in Example 1 was replaced with isobornyl monomethacrylate.

Example 7 An ultraviolet curable composition was prepared in the same manner as in Example 1 except that 6 parts of trimethylolpropane ethoxytriacrylate and 2 parts of bis (methacryloxyethyl) phosphate were used in Example 1.

[0044] Comparative Example 1 EO-modified bisphenol A diacrylate 85 parts Trimethylolpropane ethoxytriacrylate 6.6 parts Bis (methacryloxyethyl) phosphate 0.1 parts 1-hydroxycyclohexyl phenyl ketone 3.5 parts 2,4-diethylthioxanthone 4.5 parts Ethyl p-dimethylaminobenzoate 0.2 parts Methoquinone 0.1 part An ultraviolet curable composition was prepared in the same manner as in Example 1 above.

[0045] Comparative example 2 Tripropylene glycol diacrylate 71.5 parts Nonylphenoxy polyethylene glycol methacrylate 15 parts Trimethylolpropane ethoxytriacrylate 4.1 parts Bis (methacryloxyethyl) phosphate 0.1 parts 1-hydroxycyclohexyl phenyl ketone 3.5 parts 2,4-diethylthioxanthone 4.5 parts p-Dimethylaminoacetophenone 1 part Ethyl p-dimethylaminobenzoate 0.2 parts Methoquinone 0.1 part An ultraviolet curable composition was prepared in the same manner as in Example 1 above.

[0046] Comparative Example 3 EO-modified bisphenol A diacrylate 71.5 parts Cyclohexyl methacrylate 15 parts Trimethylolpropane ethoxytriacrylate 4.2 parts 1-hydroxycyclohexyl phenyl ketone 3.5 parts 2,4-diethylthioxanthone 4.5 parts p-Dimethylaminoacetophenone 1 part Ethyl p-dimethylaminobenzoate 0.2 parts Methoquinone 0.1 part

Comparative Example 4 An ultraviolet-curing type resin was prepared in the same manner as in Comparative Example 3 except that the EO-modified bisphenol A diacrylate in Comparative Example 3 was replaced with dicyclopentanyl diacrylate and the cyclohexyl methacrylate was replaced with dicyclopentanyl monomethacrylate. A composition was prepared. An ultraviolet curable composition was prepared in the same manner as in Example 1 above.

Preparation of Sample Disc The ultraviolet-curable composition prepared in the above Examples and Comparative Examples was applied to an amorphous polyolefin substrate and an aluminum surface of an amorphous polyolefin substrate having an aluminum reflection film so that the film thickness after curing was 7 to 7. It was applied by spin coating so as to have a thickness of 10 μm, and a concentrating high-pressure mercury lamp (120 W /
cm)), and the irradiation light amount is 1 J / cm ²
Cured. A sample using an amorphous polyolefin substrate was designated as disk A, and a sample using an amorphous polyolefin substrate having an aluminum reflective film was designated as disc B.

Test Method According to the X-cut tape method of JIS K5400, the adhesion of the cured film on the disk A and the disk B was evaluated. ◎ when the coating film was not peeled off from the adhesion surface at all, ○ when it was hardly peeled off, Δ when partially peeled off,
The case where most of the film was peeled off was marked with x, and the results and the overall evaluation are shown in Table 1 as OK and NG.

[0050]

[Table 1] Table 1

As is clear from Table 1, the ultraviolet ray curable compositions for optical disks of the present invention obtained in Examples 1 to 7 showed good adhesion to both the amorphous polyolefin substrate and the metal reflective film. .

However, Comparative Example 1 containing no monofunctional methacrylate monomer represented by the formula (1), Comparative Example 2 containing no modified bisphenol A diacrylate and Comparative Example 4
Then, in Comparative Example 3 in which the coating film was peeled from the amorphous polyolefin substrate surface and did not contain (meth) acrylate having a phosphoric acid group, the coating film was peeled from the aluminum reflective film surface, and both the amorphous polyolefin substrate and the metal reflective film were removed. Good adhesion could not be obtained.

[0053]

The UV-curable composition for optical disks of the present invention exhibits good adhesion to both the resin substrate and the metal reflective film. Particularly, without impairing the excellent optical properties of the amorphous polyolefin resin, it exhibits good adhesion to both the amorphous polyolefin resin and the metal reflective film,
It is possible to provide an optical disc using as a substrate an amorphous polyolefin resin having excellent mechanical and optical properties such as high transparency, low birefringence, heat resistance, and low hygroscopicity.

Continued front page    F-term (reference) 4F006 AA12 AB24 BA01 CA01 EA03                 4J100 AL03P AL04P AL05P AL08P                       AL08R AL10P AL66Q AL66R                       BA02Q BA03P BA04P BA05P                       BA08Q BA31P BA64R BA65R                       BB01P BC04P BC08P BC28P                       BC43P BC45Q BC53P CA05                       JA01 JA36                 5D029 KA13 LA04

Claims (4)

[Claims] 1. A at least monofunctional methacrylic compound, a (meth) acrylic compound having a bisphenol A structure in the molecule and having two or more (meth) acryloyl groups, and a phosphoric acid group (meth). ) A UV-curable composition for an optical disc, which contains an acrylic compound. 2. The ultraviolet-curable composition for optical disks according to claim 1, wherein the monofunctional methacrylic compound is an ester compound represented by the following formula (1). Formula (1) (In the formula, X is a methyl group, R is a linear or branched alkyl group having 5 to 20 carbon atoms, an aliphatic group having a monocyclic cyclic structure having 5 to 10 carbon atoms, a cyclic ether group, or Represents its derivative.) 3. An ultraviolet-curable composition according to claim 1, further comprising an information recording layer formed on a resin substrate with a reflective film made of a metal or a silicon compound as an uppermost layer. An optical disk provided with a cured film of a material. 4. The optical disc according to claim 3, wherein the substrate is an amorphous polyolefin resin.