JP3377301B2 - Thermoplastic norbornene-based resin molded article having hard coat layer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic norbornene-based resin molded article having a hard coat layer obtained by curing a specific ultraviolet-curable composition, and more specifically, it has excellent adhesion to the molded article, The present invention relates to a thermoplastic norbornene-based resin molded article having a hard coat layer having excellent wear resistance, chemical resistance, heat resistance, and surface appearance, and a method for producing the same.

[0002]

2. Description of the Related Art Thermoplastic norbornene resins have excellent properties such as transparency, heat resistance and chemical resistance.
It is used in various fields including optical materials. However, a molded article made of a thermoplastic norbornene-based resin may be scratched on the surface depending on the application, and improvement in wear resistance has been demanded. In general, as a method for preventing scratches on a synthetic resin molded product, there is a method of providing a hard coat layer on the surface of the molded product. As a hard coating agent used for providing such a hard coating layer, a silicone or organic coating agent is generally used. However,
When a silicone-based coating agent is used, a hard coat layer having excellent surface hardness can be formed, but the adhesiveness to the surface of the thermoplastic norbornene-based resin molded product is poor, so that there is a problem of easy peeling.

Known organic coating agents include melamine-based, alkyd-based, urethane-based, and acrylic-based heat-curable coating materials, and multifunctional acrylic-based ultraviolet-curable coating materials. The former heat-curable coating material is easy to handle, but the hardness and weather resistance of the hard coat layer are inferior, and furthermore, the resin molded article may be deformed or the resin may deteriorate during heat curing. The latter UV-curable coating material has excellent hardness and productivity, and since it is UV-curable, there is no problem of adverse effects on the resin molded product due to heating. Therefore, it can be said that the UV-curable polyfunctional acrylic coating agent is more suitable than the thermosetting coating material as the coating agent used for the thermoplastic norbornene-based resin molded product. The UV-curable polyfunctional acrylic coating agent contains a polyfunctional acrylate monomer and / or oligomer, a photopolymerization initiator and other additives, and is solvent-free or diluted with a solvent.

However, when a general-purpose UV-curable polyfunctional acrylic coating agent is applied to a molded article made of a thermoplastic norbornene-based resin to form a hard coat layer,
There is a problem that the adhesion between the hard coat layer and the surface of the molded product is insufficient, and the hard coat layer after curing is easily peeled off from the molded product. In order to improve the adhesion with the hard coat layer, there is a method of surface-treating the molded product. However, since the thermoplastic norbornene-based resin has excellent chemical resistance, surface treatment with good workability may be performed. It was difficult.

Recently, an ultraviolet-curable hard coating agent comprising a monofunctional acrylate monomer, a bifunctional or trifunctional acrylate monomer, a tetrafunctional or higher functional acrylate monomer, and a photopolymerization initiator is coated on the surface of a thermoplastic norbornene resin molded article. A method of forming a hard coat layer having excellent hardness and adhesion by curing has been proposed (Japanese Patent Laid-Open No. 5-306378). However, the thermoplastic norbornene-based resin molded product having a hard coat layer formed by this method may have insufficient wear resistance and adhesion depending on the application, and a hard coat layer having more excellent wear resistance and adhesion. There has been a demand for the development of a thermoplastic norbornene-based resin molded product having the above.

[0006]

The object of the present invention is to provide a hard coat layer having excellent adhesion, abrasion resistance, chemical resistance, heat resistance, appearance, etc. on the surface of a molded article made of a thermoplastic norbornene resin. It is to provide a molded article provided with and a manufacturing method thereof. The present inventors have earnestly studied the problems of strong adhesion and surface hardness of a hard coat layer for a thermoplastic norbornene resin molded product, and as a result, by using an ultraviolet curable composition having a specific composition, a thermoplastic norbornene resin is obtained. It was found that a resin molded product and a hard coat layer are firmly adhered to each other, and a resin molded product excellent in surface hardness, abrasion resistance, chemical resistance, heat resistance and surface appearance is obtained, and the present invention has been completed. It was

[0007]

Thus, according to the present invention, (A) a polyfunctional monomer (a-1) 20 to 10 having three or more (meth) acryloyloxy groups in one molecule.
0% by weight and 1 to 2 functional monomer (a-2) 80 having 1 to 2 (meth) acryloyloxy groups in one molecule.
10 to 90 parts by weight of a monomer mixture consisting of
(B) 5 to 80% by weight of a coating resin composed of a homopolymer or copolymer of a vinyl monomer containing 10% by weight or more of at least one monomer selected from (meth) acrylic acid esters Parts, and (C) a photopolymerization initiator 0.1 to 15
Provided is a thermoplastic norbornene-based resin molded article having a hard coat layer obtained by curing an ultraviolet curable composition consisting of parts by weight. Further, according to the present invention, the above-mentioned ultraviolet-curable composition is applied to the surface of a molded article formed of at least a norbornene-based resin, and the composition is characterized by being irradiated with ultraviolet rays to be cured to form a hard coat layer. A method for producing a thermoplastic norbornene-based resin molded article is provided.

As a preferred embodiment of the present invention, there is provided a thermoplastic norbornene resin molded article having a hard coat layer formed by curing the following ultraviolet curable composition, and a method for producing the molded article. (1) In the component (A), (a-1) / (a-
2) A molded article having a hard coat layer obtained by curing the above-mentioned UV-curable composition having a proportion of 30 to 100/70 to 0 (wt%), and a method for producing the molded article. (2) In the component (A), (a-1) / (a-
2) 50-100 / 50-0 (wt%) A molded article having a hard coat layer obtained by curing the above ultraviolet-curable composition, and a method for producing the molded article. (3) In the component (A), (a-1) / (a-
2) A molded article having a hard coat layer obtained by curing the above-mentioned ultraviolet-curable composition having a proportion of 30 to 75/70 to 25 (% by weight), and a method for producing the molded article. (4) The above-mentioned component (B) is a coating resin comprising a homopolymer or copolymer of a vinyl monomer containing (meth) acrylic acid esters in a proportion of 20 to 100% by weight. A molded article having a hard coat layer obtained by curing an ultraviolet curable composition, and a method for producing the molded article.

(5) The component (B) comprises 20 to 100% by weight of (meth) acrylic acid esters and styrene derivative 0.
To 80% by weight, and a molded article having a hard coat layer obtained by curing the above-mentioned UV-curable composition, which is a resin for paints made of a homopolymer or copolymer of a vinyl-based monomer, and the molding. Method of manufacturing goods. (6) The ultraviolet curable composition as described above, wherein the component (B) is a coating resin composed of a homopolymer or copolymer of vinyl monomers containing 10% by weight or more of (meth) acrylic acid esters. A molded article having a hard coat layer obtained by curing a cured article, and a method for producing the molded article. (7) The ratio (A) / (B) / (C) of each component is 4
A molded product having a hard coat layer obtained by curing the ultraviolet curable composition having a weight ratio of 0 to 85/8 to 60/1 to 13 and a method for producing the molded product. (8) A hard coat layer obtained by curing the ultraviolet curable composition, wherein the components (A), (B), and (C) are uniformly dissolved in an organic solvent at a concentration of 20% by weight or more. And a method for producing the molded article. (9) A molded article having a hard coat layer obtained by curing the above-mentioned ultraviolet-curable composition having a halogenated hydrocarbon polymer primer layer, and a method for producing the molded article.

The present invention will be described in detail below. Thermoplastic Norbornene-based Resin The thermoplastic norbornene-based resin used in the present invention is, for example, JP-A-1-168725 and JP-A-1-190.
No. 726, No. 3-14882, No. 3
It is a known resin disclosed in JP-A-122137, JP-A-4-63807 and the like. Typical examples of the thermoplastic norbornene-based resin include ring-opening polymers of norbornene-based monomers, hydrogenated products thereof, addition-type polymers of norbornene-based monomers, and norbornene-based monomers and olefins. Examples thereof include addition type copolymers. The norbornene-based monomer is described in each of the above publications and JP-A-2-22742.
It is a known monomer disclosed in JP-A No. 4 and JP-A No. 2-276842.

Examples of the norbornene-based monomer include
Norbornene, its alkyl, alkylidene, aromatic substituted derivatives, and substituted or unsubstituted norbornene halogens, hydroxyl groups, ester groups, alkoxy groups, cyano groups, amide groups, imide groups, polar group substitution products such as silyl groups, etc. is there. Specific examples of these include 2-norbornene, 5-methyl-2-norbornene, and 5,5-
Dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-
Norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5
-Phenyl-2-norbornene, 5-phenyl-5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-octadecyl-2-norbornene and the like can be mentioned.

Further, as the norbornene type monomer,
(1) A monomer in which one or more cyclopentadiene is added to norbornene, a derivative or a substitution product similar to the above, for example, 1,4: 5,8-dimethano-1,2,3,4,4.
a, 5,8,8a-2,3-cyclopentadienooctahydronaphthalene, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a- Octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a, 6,9,9a,
(2) A monomer having a polycyclic structure, which is a multimer of cyclopentadiene, such as 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, and derivatives and substitution products similar to the above, for example, dicyclopentadiene. , 2,3-dihydrodicyclopentadiene and the like, (3) adducts of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-1,
4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a,
5,8,8a-octahydro-2,3-cyclopentadienonaphthalene and the like can be mentioned.

The number average molecular weight of the thermoplastic norbornene-based resin used in the present invention is GPC using a toluene solvent.
It is usually 10,000 in terms of polystyrene measured by (gel permeation chromatography) method.
~ 200,000, preferably 15,000-100,
000, more preferably 20,000 to 50,000. When the thermoplastic norbornene-based resin has an unsaturated bond in the main chain structure like a ring-opening polymer of a norbornene-based monomer, it can be hydrogenated to be a saturated thermoplastic norbornene-based resin. it can. in this case,
The hydrogenation rate is usually 90% or more, preferably 95% or more, more preferably 99% or more. When the hydrogenation rate is low and the proportion of unsaturated bonds in the main chain structure is large, the thermoplastic norbornene-based resin is inferior in light deterioration resistance, etc.,
When used in applications where it is directly exposed to wind and rain, problems such as loss of transparency and strength tend to occur.

The glass transition temperature (Tg) of the thermoplastic norbornene-based resin is preferably 110 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. If the Tg of the resin is too low, the heat resistance of the molded product decreases. Various additives may be added to the thermoplastic norbornene-based resin as long as the object of the present invention is not impaired. Examples of the additives include antioxidants such as phenolic and phosphorus-based antioxidants; thermal degradation inhibitors such as phenolic antioxidants; UV stabilizers such as benzophenone-based antioxidants; antistatic agents such as amine-based antioxidants; Lubricants such as partial esters and partial ethers of polyhydric alcohols; and the like.

Molding Method of Thermoplastic Norbornene Resin The molding method of the thermoplastic norbornene resin is not particularly limited, and a general thermoplastic resin molding method can be adopted. For example, various molding methods such as injection, melt extrusion, hot pressing, solvent casting and stretching can be used.

UV-Curable Composition The UV-curable composition used in the present invention comprises (A) a polyfunctional monomer (a-1) 20 having 3 or more (meth) acryloyloxy groups in one molecule. Monomer mixture 10% to 100% by weight and 80 to 0% by weight of 1 to 2 functional monomer (a-2) having 1 to 2 (meth) acryloyloxy groups in one molecule. Resin for coating 5 to 80 consisting of homopolymer or copolymer of vinyl monomer simple substance containing 90 parts by weight of 10% by weight or more of a monomer selected from (B) (meth) acrylic acid esters Parts by weight, and 0.1 to 15 parts by weight of the photopolymerization initiator (C).

Component (A) A polyfunctional monomer (a-1) having three or more (meth) acryloyloxy groups in one molecule of the component (A) of the ultraviolet curable composition used in the present invention. A monomer mixture composed of 1 to 2 functional monomers (a-2) having 1 to 2 (meth) acryloyloxy groups in one molecule has high polymerization activity upon irradiation with active energy rays. It is a component for forming a hard coat layer having excellent abrasion resistance, chemical resistance, heat resistance and surface appearance on a thermoplastic norbornene resin molded product.

Examples of the polyfunctional monomer (a-1) having three or more (meth) acryloyloxy groups in one molecule of the component (A) include, for example, trimethylolpropane tri (meth). ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) Acrylate, tripentaerythritol octa (meth) acrylate. Among these, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate are particularly preferable in terms of abrasion resistance, chemical resistance, and heat resistance. These polyfunctional monomers can be used alone or in combination of two or more.

Among the component (A), examples of the 1-2 functional monomer (a-1) having 1-2 or (meth) acryloyloxy groups in one molecule include, for example, methyl (meth). )
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl acrylate, isooctyl (meth ) Acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, n-nonyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, hydrogen thereof Additive, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl acrylate, phenoxyethyl (meth) acrylate, Phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate,
Monofunctional (meth) acrylate monomers such as (meth) acrylic acid and (meth) acryloylmorpholine; ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-heptanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 2-butyne-1,4-di (Meth) acrylate, cyclohexane-1,4-dimethanol di (meth) acrylate, hydrogenated bisphenol A
Di (meth) acrylate, 1,5-pentanedi (meth)
Acrylate, trimethylolethane di (meth) acrylate, tricyclodecanyl di (meth) acrylate,
The hydrogenated product, trimethylolpropane di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 2,2-bis- (4- (meth) acryloxypropoxy. Phenyl) propane, 2,2-bis- (4-
Examples thereof include difunctional (meth) acrylate monomers such as (meth) acryloxy (2-hydroxypropoxy) phenyl) propane and bis- (2-methacryloyloxyethyl) phthalate.

Among the above, long-chain aliphatic functional monomers and alicyclic 1-2 functional monomers are preferable from the viewpoint of adhesiveness with the thermoplastic norbornene-based resin. Specifically, lauryl acrylate, stearyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, tricyclodecanyl acrylate, hydrogenated products thereof, 2-ethylhexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, tricyclodecanyl. Diacrylate, hydrogenated product thereof, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-dicyclopentenoxyethyl acrylate, isobornyl diacrylate, hydrogenated bisphenol A diacrylate, cyclohexane-1,4-dimethanol Diacrylate is particularly preferable as the component (A). These mono- and bifunctional monomers are each independently
Alternatively, two or more kinds can be used in combination.

Among the component (A), the polyfunctional monomer (a-1) having three or more (meth) acryloyloxy groups in one molecule and one or two (meth) in one molecule. The proportion of the acryloyloxy group-containing 1 to 2 functional monomer (a-2) used is 100% by weight of the monomer mixture which is the component (A), and the polyfunctional monomer (a-1). / 1-2 functional monomer (a-2) = 20 to 100/0 to 80 (wt%), preferably 30 to 100/70 to 0 (wt%), more preferably 50 to It is 100 / 50-0 (weight%). In particular, from the viewpoint of the balance of wear resistance, chemical resistance, heat resistance, adhesion, and surface appearance of the hard coat layer,
The range of (a-1) / (a-2) = 30 to 75/70 to 25 (% by weight) is preferable. The proportion of component (A) used is
10 to 9 in 100 parts by weight of the total amount of the components (A) to (C).
It is 0 part by weight, preferably 40 to 85 parts by weight. In the ultraviolet curable composition containing a small amount of this ratio, sufficient abrasion resistance, chemical resistance, and heat resistance cannot be obtained in the hard coat layer,
When the amount of the ultraviolet curable composition is large, the adhesion of the hard coat layer to the surface of the molded article is lowered.

Component (B) The coating resin of component (B) used in the present invention is
It is a component that has good compatibility with the component (A) and that reduces the curing shrinkage of the ultraviolet curable composition to improve the adhesion between the hard coat layer and the surface of the molded article.
The component (B) is a homopolymer or copolymer of a vinyl monomer and can be obtained by a solution polymerization method, a bulk polymerization method, an emulsion polymerization method or the like in the presence of a radical polymerization initiator. The component (B) contains 10% by weight or more, preferably 20% by weight or more, and more preferably at least one monomer selected from (meth) acrylic acid esters in view of compatibility with the component (A). It is preferably contained in a proportion of 30% by weight or more. The molecular weight of the component (B) is usually 5,000.
0 to 200,000, preferably 10,000 to 15
30,000, more preferably 20,000 to 100,0
00.

Examples of (meth) acrylic acid esters used to obtain the component (B) used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate. , N
-Butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (Meta)
Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, penzyl (meth) acrylate, tricyclodecanyl (meth) acrylate, its hydrogenated product, dicyclopentanyl (meth) acrylate, di Cyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, isobornyl (meth)
Acrylate, methoxyethyl (meth) acrylate,
Acrylic esters such as ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and other hydroxyalkyl (meth) acrylates; 2
2-hydroxyethyl (such as an adduct of hydroxyethyl (meth) acrylate and ethylene oxide, an adduct of 2-hydroxyethyl (meth) acrylate and propylene oxide, an adduct of 2-hydroxyethyl (meth) acrylate and ε-caprolactone). Examples thereof include hydroxyl group-containing vinyl monomers such as adducts of (meth) acrylate and organic lactones.

Among the above, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl (meth) acrylate are preferred in view of compatibility with the component (A). Of these, long-chain aliphatic (meth) acrylic acid esters and alicyclic (meth) acrylic acid esters are preferable from the viewpoint of adhesion with the thermoplastic norbornene-based resin. Specifically, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth)
Acrylate, tricyclodecanyl (meth) acrylate, hydrogenated product thereof, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) ) Acrylate, 2-dicyclopentenoxyethyl (meth) acrylate and the like are particularly preferable. These monomers may be used alone or in combination of two or more.

Examples of other vinyl monomers used for copolymerization with (meth) acrylic acid esters, if necessary, include styrene, α-methylstyrene, p-tertiarybutylstyrene and vinyltoluene. Styrene derivatives; unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid; polymerizable unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) Polymerizable amides such as acrylamide and butoxy (meth) acrylamide; unsaturated carboxylic acid esters such as diethyl maleate, dibutyl maleate, dibutyl fumarate, diethyl itaconate and dibutyl itaconic acid; vinyl esters such as vinyl acetate and vinyl propionate And the like;

These monomers can be used alone or in combination of two or more. Among the above, styrene derivatives such as styrene, α-methylstyrene, p-tert-butylstyrene and vinyltoluene are preferable in terms of adhesion to the thermoplastic norbornene-based resin molded product. The use ratio (solid content) of the coating resin (B) component is 5 to 80 parts by weight, preferably 8 to 60 parts by weight, in 100 parts by weight of the total amount of the components (A) to (C). With the ultraviolet curable composition containing the component (B) in an amount smaller than the use range amount, sufficient adhesion cannot be obtained between the hard coat layer and the surface of the molded article, and with the ultraviolet curable composition containing a large amount, Abrasion resistance, heat resistance and surface appearance of the hard coat layer deteriorate.

Component (C) Examples of the photopolymerization initiator of the component (C) used in the present invention include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxy. Acetophenone, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenyl glyoxylate, ethylphenyl glyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Carbonyl compounds such as 2-ethylanthraquinone, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, 2,
An acylphosphine oxide such as 4,6-trimethylbenzoylphenylphosphine oxide can be used.

These may be used alone or in combination of two or more. Among these (C) components, benzophenone and methylphenylglyoxylate are more preferable. The proportion of the component (C) used is from (A) to
0.1 to 15 parts by weight, preferably 1 to 13 parts by weight, and more preferably 2-1 to 100 parts by weight of the total amount of the component (C).
0 parts by weight. An ultraviolet-curable composition containing the component (C) in an amount smaller than the range of use will cause insufficient curing of the hard coat layer, and an ultraviolet-curable composition containing a large amount of the component (C) will
Adhesion between the hard coat layer and the surface of the molded article decreases.

Optional Ingredients Appropriate additives may be added to the UV-curable composition as long as the adhesiveness, hardness and abrasion resistance of the hard coat layer are not substantially reduced. For example, the addition of a fluorine-based nonionic surfactant improves the surface smoothness after wetting with a thermoplastic norbornene-based resin molded product and after curing. The addition of an antistatic agent can suppress the absorption of dust. In addition, by adding a suitable thermoplastic resin, the viscosity can be adjusted and the adhesion can be improved. As the thermoplastic resin for improving the adhesiveness, a thermoplastic norbornene-based resin or a resin having a structure similar to that,
Examples thereof include ring-opened polymers of norbornene-based monomers, dicyclopentadiene-based, diene-based, aliphatic-based, water-white-based petroleum resins, and hydrogenated products thereof.

The UV-curable composition used in the present invention can be used as it is, but depending on the need for operability in the coating operation, an aromatic hydrocarbon solvent such as toluene, xylene or chlorobenzene; cyclohexane. Alicyclic hydrocarbon solvents such as methylcyclohexane; alcohol solvents such as isopropyl alcohol and isobutyl alcohol; ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone and acetone; n-butyl ether,
An ether-based solvent such as diethyl ether; or an organic solvent such as an ester-based solvent, a cellosolve-based solvent, and a chloro-based solvent, which is usually dissolved at a concentration of 20% by weight or more, and preferably 30% by weight or more Good.

Formation of Hard Coat Layer In the present invention, a primer layer is optionally formed on the surface of a thermoplastic norbornene resin molded article, and the ultraviolet curable composition is applied thereon and irradiated with ultraviolet rays. Harden to form a hard coat layer. The thermoplastic norbornene-based resin molded product may be a molded product of the resin alone, or may be a composite with another material or a molded product. The hard coat layer is formed on the surface formed of the thermoplastic norbornene-based resin, and is the entire surface or the surface portion requiring particularly abrasion resistance.

Formation of Primer and Primer Layer In the present invention, a specific ultraviolet curable composition is applied to the surface of a thermoplastic norbornene resin molded article, and the ultraviolet curable composition is irradiated with ultraviolet rays to be cured, Although the hard coat layer is formed, a primer may be applied prior to the application of the ultraviolet curable composition in order to make the adhesion between the thermoplastic norbornene resin and the hard coat layer stronger. As the primer used in the present invention, a halogenated hydrocarbon polymer is preferable. Such halogenated hydrocarbon polymers include halogenated hydrocarbon-based polymers obtained by polymerizing or copolymerizing hydrocarbon-based monomers such as ethylene, propylene, butadiene, isoprene and styrene, or vinyl. Examples thereof include those obtained by polymerizing or copolymerizing halogen-containing monomers such as chloride, vinylidene chloride and chloroprene. Of these, chlorinated hydrocarbon polymers are preferred,
Chlorinated polypropylene is particularly preferable.

The molecular weight of the halogenated hydrocarbon polymer is usually 5,000 to 200,000, preferably 10.0.
00 to 150,000, more preferably 20,000 to
It is 100,000. If the molecular weight is too small, the strength of the primer layer will be low, and if it is too large, the viscosity will be too high and the coating workability will be poor. The halogen content of the halogenated hydrocarbon polymer is usually 15 to 55% by weight, preferably 20 to 45% by weight, more preferably 25 to 35% by weight.
Is. If the content of halogen is too low or too high,
Adhesion between the hard coat layer and the surface of the molded product deteriorates.

A photopolymerizable monomer, a photopolymerizable oligomer, etc., which will be described later, may be added to the primer as a reactive diluent. In particular, a monofunctional acrylate monomer of 2 to 2 may be added.
Addition in a proportion of 0% by weight improves the adhesion between the hard coat layer and the primer layer and between the primer layer and the surface of the resin molded product, and makes it difficult for the hard coat layer to peel from the molded product, which is preferable. . The primer is preferably dissolved in a solvent and used as a primer solution. The solvent is not particularly limited as long as it is a substantially poor solvent for the thermoplastic norbornene-based resin. For example, toluene is
It is a good solvent for thermoplastic norbornene-based resins, but if it is diluted with methyl isobutyl ketone to 70% by weight or less, erosion will be small even if it is applied to a thermoplastic norbornene-based resin molded product, so the solvent for the primer used in the present invention Can be used as

Monofunctional acrylates such as n-butyl methacrylate and isoamyl methacrylate are also reactive solvents that are poor solvents for thermoplastic norbornene resins and have the effect as photopolymerizable monomers added to the primer as described above. Since it is an agent, it is preferable. The solid content concentration of the primer solution is usually 1 to 30.
%, Preferably 1.5 to 20% by weight, more preferably 2 to 10% by weight. The primer layer is formed by applying the primer solution to the surface of the thermoplastic norbornene-based resin molded article and sufficiently removing the volatile components in the primer solution. However, when only the reactive diluent as described above is used as the solvent of the primer, the operation of removing the volatile component is unnecessary.

The method of applying the primer solution to the coated surface is not particularly limited, and for example, spraying, dipping, spin coating, roll coater and the like can be adopted. The method for removing the volatile component in the primer solution is not particularly limited. The volatilization temperature and time required to substantially remove the solvent of the primer solution vary depending on the type of solvent used, the amount of primer solution applied, and the shape of the molded product on the coated surface, but thermoplastic norbornene resin molding The conditions may be determined at about 100 ° C. or lower so as to prevent thermal deformation of the product, and sufficient removal. Specifically, 60 to 100
It is suitable to leave it at ℃ for 3 to 60 minutes.
After removing volatile components at high temperature, 10 seconds to 10 seconds at room temperature
It is preferable to perform cooling for about a minute so that the temperature is cooled to about room temperature.

The coating amount of the primer solution is not particularly limited, but it is preferable that the thickness is about 1 to 10 μm, particularly about 2 to 5 μm. When it is necessary to remove the volatile components after the application of the primer solution, it is preferable to adjust the thickness to the above-mentioned value after sufficiently removing the volatile components. When the coating amount of the primer solution is small, the effect of the primer solution is small, and when the coating amount is too large, it is difficult to remove the volatile component, and the hard coat layer is easily peeled off from the molded product.

Method for forming hard coat layer A primer layer is formed on the surface of the thermoplastic norbornene resin molded article, if necessary, and then the ultraviolet curable composition used in the present invention is applied. This coating method is not particularly limited, and for example, a coating method such as spraying, dipping, spin coating, or roll coater can be adopted. When the UV curable composition is used by dissolving it in a solvent, it is sufficiently dried after coating so that the solvent is substantially not contained. The drying method for removing the solvent is not particularly limited.

The thickness of the hard coat layer made of the ultraviolet curable composition after coating is preferably 2 to 300 μm. If a solvent is used, it should have this thickness after drying. When the thickness of the hard coat layer is thin, the strength is insufficient and sufficient surface hardness and adhesiveness cannot be obtained. When the thickness of the hard coat layer is large, it takes time for the curing reaction and drying of the composition, the productivity of the molded article of the present invention is deteriorated, and the curing of the composition is insufficient so that the hard coat layer May have a low hardness, or the hard coat layer may lack flexibility and crack.

The coating film of the ultraviolet curable composition after coating, if necessary, needs to be sufficiently dried before being cured. If it is cured while containing a large amount of solvent, cracks are likely to occur in the hard coat layer, and this may cause a hard coat layer having a high hardness to not be obtained. The drying temperature and time required for substantially removing the solvent before curing the ultraviolet curable composition of the present invention vary depending on the type of solvent used, the coating amount of the composition, and the shape of the coated surface. However, the conditions may be determined so as not to cause thermal deformation of the molded product and to be sufficiently dried at about 100 ° C. or less. Specifically, drying at 60 to 80 ° C. for about 3 to 5 minutes is suitable. After drying at a high temperature, it is preferable to perform cooling at room temperature for about 30 seconds to 3 minutes to cool to near room temperature. If no solvent is used, no drying is necessary.

Thereafter, the composition layer is cured in a short time by irradiating the composition layer with ultraviolet rays from a light source that efficiently produces ultraviolet rays such as a high pressure mercury lamp, and a hard coat layer having high hardness is formed. The irradiation dose of ultraviolet rays varies depending on the reactivity of the photopolymerizable monomer and the photopolymerization initiator, but usually,
In the case of a high pressure mercury lamp of 80 W / cm, it can be cured in a short irradiation time of about 5 to 15 seconds. In this case, the integrated light amount at the wavelength of 340 nm to 380 nm is 750 to
This corresponds to 1500 mJ / cm ² .

The hard coat layer formed of the ultraviolet curable composition of the present invention has excellent adhesion to a thermoplastic norbornene resin molded product, has a good appearance, and has a high surface hardness. The pencil hardness of the thermoplastic norbornene resin molded product is
Usually, it is about 1H, but in the case of the molded article having the hard coat layer of the present invention, it is improved to about 2 to 3H. The molded product having the hard coat layer of the present invention showed no peeling in the peeling test by the cross-cut test described below, and was 9 in the peeling test by the cross-cut test after the durability test under high temperature and high humidity conditions.
It shows a high adhesion such that 5 to 100% remains. Furthermore, the molded article having the hard coat layer of the present invention has an increased haze value in the range of 0 to 0.5 after the abrasion resistance test, which will be described later, and is hardly scratched.

[0043]

EXAMPLES The present invention will be described more specifically below with reference to Reference Examples, Examples, and Comparative Examples. In addition, part and%
Is by weight unless otherwise noted.

<Methods for measuring physical properties> Methods for measuring various physical properties are as follows. (1) Appearance Evaluation Method of Hard Coat Layer Surface The appearance of the hard coat layer surface after coating and curing the ultraviolet curable composition was visually observed and evaluated according to the following criteria. Good: Smooth and transparent. Insufficient: unevenness and unevenness. Bad: Not smooth, but whitening and clouding are observed. (2) Pencil hardness measurement method According to JIS K-5400, the measurement was performed with a load of 1 kg. (3) Abrasion resistance measurement method #ooo steel wool was attached to the tip of a cylinder with a diameter of 25 mm, and brought into contact with the hard coat surface placed horizontally.
After being reciprocally worn 50 times under a load of kg, the diffuse transmittance (haze value) was measured, and the wear resistance was determined according to the following criteria. Increased haze value = 0 to less than 0.5: Almost no scratch. Increased haze value = 0.5 to less than 3.0: Slightly scratched. Increased haze value = 3.0 or more: severely scratched. (4) Cross-cut peeling test From the top of the coat layer formed on the surface of the molded product, make 11 vertical and horizontal cuts at 1 mm intervals with a cutter to make 100 1-mm square cross-cuts. A cellophane adhesive tape (manufactured by Sekisui Chemical Co., Ltd.) is attached, and the adhesive tape is peeled in the 90 ° direction. The test results are shown by the number of the remaining meshes in 100 cross-cuts without peeling, which is expressed in%. In addition, a cross-cut peeling test was also performed after a durability test under high temperature and high humidity conditions of 80 ° C., 90% RH (relative humidity) and 500 hours.

[Reference Example 1] Thermoplastic norbornene resin (manufactured by Zeon Corporation,
Zeonex 280; a ring-opened polymer hydrogenated product, hydrogenation rate of 98% or more) was injection molded under the following conditions to prepare a substrate having a thickness of 3 mm, a length of 55 mm and a width of 55 mm. It was H when the pencil hardness of this substrate was measured. Molding machine: clamping pressure 65 tons resin temperature: 325 ° C. Mold temperature: 110 ° C. (fixed side), 100 ° C. (movable side)

[Example 1] Resin (B-1) for coating material A four-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer was charged with 50 parts of toluene, and the internal temperature of the flask was 80 ° C. The temperature was raised to. Then, a mixed solution of 50 parts of methyl methacrylate and 0.8 part of azobisisobutyronitrile was added dropwise over 3 hours. After 1 hour and 2 hours, 0.3 parts of azobisisobutyronitrile was added, and the mixture was further stirred for 4 hours and cooled to obtain a coating resin (B-1) toluene solution having a heating residue of 50%. It was The ratio of the (meth) acrylic acid esters constituting the coating resin (B-1) is 100%.

UV curable composition ( 1) Toluene solution 2 of coating resin (B-1) thus obtained
N-butyl acrylate 8 parts to 0 parts (solid content 10 parts)
Parts, 22 parts of isoamyl acrylate, 25 parts of trimethylolpropane triacrylate, 30 parts of dipentaerythritol hexaacrylate, 5 parts of benzophenone, 100 parts of toluene, and 100 parts of isobutyl alcohol are mixed to give a fluorine-containing nonionic surfactant (Sumitomo 3M Limited). Manufactured by Florard FC-171) was added to 500 ppm to prepare an ultraviolet curable composition (1) solution.

The composition ratio of each component in the solution of the ultraviolet curable composition (1) is (A) :( B) :( C) = 85: 1.
It is 0: 5 (weight ratio). In the component (A), (a-
1) :( a-2) = 65: 35 (weight ratio). This solution of UV-curable composition (1) was spray-coated on the substrate prepared in Reference Example 1 and dried at 60 ° C. for 5 minutes to remove toluene and isobutyl alcohol. The film thickness of the ultraviolet curable composition after drying was 10 μm. Ultraviolet irradiation (peak irradiation intensity on the substrate surface: 150 mW / cm ² , cumulative light intensity 1500 mJ / cm ² , irradiation time 10 seconds) from an 80 mW high pressure mercury lamp was applied to this substrate to cure the ultraviolet curable composition, A substrate on which a hard coat layer was formed was obtained. The appearance of the substrate surface was good, and the hardness was 3H in terms of pencil hardness. The result of the abrasion resistance test was an increased haze value of 0.3, which was a level at which there was almost no damage. The result of cross-cut peeling test is 100%
It was 95% even after the high temperature and high humidity durability test.

[Example 2] Ultraviolet curable composition (2) Resin for paint (B-1) 100 parts of toluene solution (solid content: 5)
(0 part), 45 parts of dipentaerythritol hexaacrylate, 5 parts of benzophenone, 75 parts of toluene, and 75 parts of isobutyl alcohol are mixed to give a fluorine-based nonionic surfactant (Sumitomo 3M, Florard FC-17).
1) was added so that it might become 500 ppm, and the ultraviolet curable composition (2) solution was prepared.

The composition ratio of each component in the solution of the ultraviolet curable composition (2) is (A) :( B) :( C) = 45: 5.
It is 0: 5 (weight ratio). In the component (A), (a-
1) :( a-2) = 100: 0 (weight ratio). A substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1 by using the solution of the ultraviolet curable composition (2). The appearance of the substrate surface is good, and its hardness is 3H in terms of pencil hardness.
Met. The result of the abrasion resistance test is that the increased haze value is 0.4.
So, it was a level that was hardly damaged. The result of the cross-cut peeling test was 100%, and it was 98% even after the high temperature and high humidity durability test.

[Example 3] Resin (B-2) for coating material A four-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer was charged with 50 parts of toluene, and the internal temperature of the flask was 80 ° C. The temperature was raised to. Then, a mixed solution of 15 parts of methyl methacrylate, 15 parts of styrene, 20 parts of isobornyl methacrylate, and 1 part of azobisisobutyronitrile was added dropwise over 3 hours. After 1 hour and 2 hours, 0.3 parts of azobisisobutyronitrile was added,
The mixture was further stirred for 4 hours and cooled to obtain a coating resin (B-2) toluene solution having a heating residue of 50%. The ratio of the (meth) acrylic acid esters constituting the coating resin (B-2) is 70%.

Ultraviolet curable composition (3) Coating resin (B-2) toluene solution 2 thus obtained
N-butyl acrylate 8 parts to 0 parts (solid content 10 parts)
Parts, 22 parts of isoamyl acrylate, 25 parts of trimethylolpropane triacrylate, 30 parts of dipentaerythritol hexaacrylate, 5 parts of benzophenone, 100 parts of toluene, and 100 parts of isobutyl alcohol are mixed to give a fluorine-containing nonionic surfactant (Sumitomo 3M Limited). Manufactured by Florard FC-171) was added to 500 ppm to prepare an ultraviolet curable composition (3) solution.

The composition ratio of each component in the solution of the ultraviolet curable composition (3) is (A) :( B) :( C) = 85: 1.
It is 0: 5 (weight ratio). In the component (A), (a-
1) :( a-2) = 65: 35 (weight ratio). A substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1 by using the solution of the ultraviolet curable composition (3). The appearance of the substrate surface is good, and its hardness is 3H in terms of pencil hardness.
Met. The result of the abrasion resistance test shows that the increased haze value is 0.3.
So, it was a level that was hardly damaged. The result of the cross-cut peeling test was 100%, and it was 98% even after the high temperature and high humidity durability test.

[Example 4] Ultraviolet curable composition (4) Coating resin (B-2) Toluene solution 100 parts (solid content 5
(0 part), 45 parts of dipentaerythritol hexaacrylate, 5 parts of benzophenone, 75 parts of toluene, and 75 parts of isobutyl alcohol are mixed to give a fluorine-based nonionic surfactant (Sumitomo 3M, Florard FC-17).
1) was added so that it might become 500 ppm, and the ultraviolet curable composition (4) solution was prepared.

The composition ratio of each component in the solution of the ultraviolet curable composition (4) is (A) :( B) :( C) = 45: 5.
It is 0: 5 (weight ratio). In the component (A), (a-
1) :( a-2) = 100: 0 (weight ratio). A substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1 using this solution of the ultraviolet curable composition (4). The appearance of the substrate surface is good, and its hardness is 3H in terms of pencil hardness.
Met. The result of the abrasion resistance test is that the increased haze value is 0.4.
So, it was a level that was hardly damaged. The result of the cross-cut peeling test was 100%, and it was 98% even after the high temperature and high humidity durability test.

[Example 5] Ultraviolet curable composition (5) Resin for paint (B-2) 100 parts of toluene solution (solid content: 5)
(0 part), 48 parts of dipentaerythritol hexaacrylate, 2 parts of methylphenylglyoxylate, 75 parts of toluene, and 75 parts of isobutyl alcohol are mixed to give a fluorine-based nonionic surfactant (Sumitomo 3M, Florade FC-171). ) Was added so that it might become 500 ppm, and the ultraviolet curable composition (5) solution was prepared.

The composition ratio of each component in the solution of the ultraviolet curable composition (5) is (A) :( B) :( C) = 48: 5.
It is 0: 2 (weight ratio). In the component (A), (a-
1) :( a-2) = 100: 0 (weight ratio). Using this solution of the ultraviolet curable composition (5), a substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1. The appearance of the substrate surface is good, and its hardness is 3H in terms of pencil hardness.
Met. The result of the abrasion resistance test is that the increased haze value is 0.4.
So, it was a level that was hardly damaged. The result of the cross-cut peeling test was 100%, and it was 98% even after the high temperature and high humidity durability test.

[Example 6] UV curable composition (6) Resin for coating (B-2) 48 parts of toluene solution (solid content: 24)
Part), n-butyl acrylate 3 parts, isoamyl acrylate 18 parts, neopentyl glycol diacrylate 10 parts, dipentaerythritol hexaacrylate 42 parts, methylphenyl glyoxylate 3 parts, toluene 75 parts, isobutyl alcohol 75 parts. Then, a fluorinated nonionic surfactant (Sumitomo 3M, Florard FC-171) was added to 500 ppm to prepare an ultraviolet curable composition (6) solution.

The composition ratio of each component in the solution of the ultraviolet curable composition (6) is (A) :( B) :( C) = 73: 2.
It is 4: 3 (weight ratio). In the component (A), (a-
1) :( a-2) = 58: 42 (weight ratio). Using this solution of the ultraviolet curable composition (6), a substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1. The appearance of the substrate surface is good, and its hardness is 3H in terms of pencil hardness.
Met. The result of the abrasion resistance test is that the increased haze value is 0.4.
So, it was a level that was hardly damaged. The result of the cross-cut peeling test was 100%, and it was 98% even after the high temperature and high humidity durability test.

[Example 7] Ultraviolet curable composition (7) Coating resin (B-2) Toluene solution 70 parts (solid content 35)
15 parts lauryl acrylate, hydrogenated tricyclodecanyl acrylate (manufactured by Hitachi Chemical, FA-51).
3A) 10 parts, tricyclodecanyl diacrylate hydrogenated product (manufactured by Kyoeisha Oil & Fat, light acrylate DCP-
A) 10 parts, 20 parts of dipentaerythritol hexaacrylate, 10 parts of benzophenone, 75 parts of toluene, and 75 parts of isobutyl alcohol are mixed to obtain a fluorine-based nonionic surfactant (Sumitomo 3M, Florard FC-
171) was added so that it might become 500 ppm, and the ultraviolet curable composition (7) solution was prepared.

The composition ratio of each component in the solution of the ultraviolet curable composition (7) is (A) :( B) :( C) = 55: 3.
It is 5:10 (weight ratio). In the component (A), (a
-1) :( a-2) = 36: 64 (weight ratio). A substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1 using this solution of the ultraviolet curable composition (7). The appearance of the substrate surface is good, and its hardness is 2 in terms of pencil hardness.
It was H. The result of the abrasion resistance test was that the increased haze value was 0.
At 4, it was a level that was hardly damaged. The result of the cross-cut peeling test was 100%, and was 100% even after the high temperature and high humidity durability test.

[Example 8] Resin (B-3) for coating material A four-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer was charged with 50 parts of toluene and the internal temperature of the flask was 80 ° C. The temperature was raised to. Then, a mixed solution of 10 parts of methyl methacrylate, 40 parts of styrene, and 1 part of azobisisobutyronitrile was added dropwise over 3 hours. After 1 hour and 2 hours, 0.3 part of azobisisobutyronitrile was added, and the mixture was further stirred for 4 hours and cooled to obtain a coating resin (B-3) toluene solution having a heating residue of 50%. It was The ratio of the (meth) acrylic acid esters constituting the coating resin (B-3) is 20%.

Ultraviolet curable composition (8) Resin for coating material (B-3) toluene solution 2 thus obtained
N-butyl acrylate 8 parts to 0 parts (solid content 10 parts)
Parts, 22 parts of isoamyl acrylate, 25 parts of trimethylolpropane triacrylate, 30 parts of dipentaerythritol hexaacrylate, 5 parts of benzophenone, 100 parts of toluene, and 100 parts of isobutyl alcohol are mixed to give a fluorine-containing nonionic surfactant (Sumitomo 3M Limited). Manufactured by Florard FC-171) was added to 500 ppm to prepare an ultraviolet curable composition (8) solution.

The composition ratio of each component in the solution of the ultraviolet curable composition (8) is (A) :( B) :( C) = 85: 1.
It is 0: 5 (weight ratio). In the component (A), (a-
1) :( a-2) = 65: 35 (weight ratio). Using this ultraviolet curable composition (8) solution, a substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1. The appearance of the substrate surface is good, and its hardness is 3H in terms of pencil hardness.
Met. The result of the abrasion resistance test shows that the increased haze value is 0.3.
So, it was a level that was hardly damaged. The result of the cross-cut peeling test was 100%, and it was 98% even after the high temperature and high humidity durability test.

Example 9 Primer Chlorinated polypropylene (Hardlen MJL-13, manufactured by Toyo Kasei, molecular weight 45,000, chlorine content 27.3%) 3
Part was dissolved in 35 parts of toluene and 65 parts of methyl isobutyl ketone to obtain a primer solution. This primer solution was applied by spray coating to the substrate prepared in Reference Example 1 and left at room temperature for 1 minute to dry. The thickness of the primer layer after drying was 2 μm.

The same ultraviolet curable composition (2) solution as in Example 2 was used for this substrate, and a substrate having a hard coat layer formed was obtained in the same manner as in Example 1. The appearance of the substrate surface is
The hardness was good, and the pencil hardness was 3H. The result of the abrasion resistance test was an increased haze value of 0.3, which was a level at which there was almost no damage. The results of the cross-cut peeling test are
100%, 100 even after high temperature and high humidity endurance test
%Met.

[Comparative Example 1] UV curable composition (9) Coating resin (B-1) Toluene solution 8 parts (solid content 4 parts)
And dipentaerythritol hexaacrylate 91
Part, benzophenone 5 parts, toluene 75 parts, and isobutyl alcohol 75 parts are mixed to give a fluorine-based nonionic surfactant (Sumitomo 3M, Florade FC-171).
The was added to a concentration of 500 ppm, an ultraviolet ray-curable composition (9) was prepared.

The composition ratio of each component in the solution of the ultraviolet curable composition (9) is (A) :( B) :( C) = 91: 4:
5 (weight ratio). In the component (A), (a-
1) :( a-2) = 100: 0 (weight ratio). A substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1 except that this solution of the ultraviolet curable composition (9) was used. The appearance of the substrate surface was not smooth and was at an insufficient level. The hardness was 3H in terms of pencil hardness. The result of the abrasion resistance test was an increased haze value of 0.1, which was a level at which there was almost no damage. The result of cross-cut peeling test is 30%
It was 12% after the high temperature and high humidity durability test.

[Comparative Example 2] 170 parts by weight of ultraviolet curable composition (10) coating resin (B-1) toluene solution (solid content 8)
5 parts), dipentaerythritol hexaacrylate 1
0 parts, 5 parts of benzophenone, 75 parts of toluene, and 75 parts of isobutyl alcohol are mixed to obtain a fluorine-based nonionic surfactant (Sumitomo 3M, Florade FC-17).
1) was added so that it might become 500 ppm, and the ultraviolet curable composition (10) solution was prepared.

The composition ratio of each component in the solution of the ultraviolet curable composition (10) is (A) :( B) :( C) = 10: 8.
It is 5: 5 (weight ratio). In the component (A), (a-
1) :( a-2) = 100: 0 (weight ratio). A substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1 except that this solution of the ultraviolet curable composition (10) was used.
The appearance of the substrate surface was not smooth and was at an insufficient level. The hardness was H in terms of pencil hardness. The result of the abrasion resistance test was an increased haze value of 5.8, which was a level at which the scratch was severely scratched. The result of the cross-cut peeling test was 100%, and it was 95% even after the high temperature and high humidity durability test.

[Comparative Example 3] UV curable composition (11) Resin for paint (B-2) 48 parts of toluene solution (solid content 24
Part), 5 parts of n-butyl acrylate, 34 parts of isoamyl acrylate, 23 parts of neopentyl glycol diacrylate, 11 parts of dipentaerythritol hexaacrylate, 3 parts of methylphenylglyoxylate, 75 parts of toluene, and 75 parts of isobutyl alcohol. Then, a fluorine-based nonionic surfactant (Sumitomo 3M, Fluorad FC-171) was added so as to have a concentration of 500 ppm to prepare an ultraviolet curable composition (11) solution.

The composition ratio of each component in the solution of the ultraviolet curable composition (11) is (A) :( B) :( C) = 73: 2.
It is 4: 3 (weight ratio). In the component (A), (a-
1) :( a-2) = 15: 85 (weight ratio). Using this solution of the ultraviolet curable composition (11), a substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1. The appearance of the substrate surface is good, and its hardness is H in terms of pencil hardness.
Met. The result of the abrasion resistance test shows that the increased haze value is 3.4.
So, it was a seriously scratched level. The result of the cross-cut peeling test is 100%, which is 98
%Met.

[Comparative Example 4] Resin (B-4) for coating material A four-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer was charged with 50 parts of toluene, and the internal temperature of the flask was 80 ° C. The temperature was raised to. Then, a mixed solution of 50 parts of styrene and 1 part of azobisisobutyronitrile was added dropwise over 3 hours. After 1 hour and 2 hours, 0.3 parts of azobisisobutyronitrile was added, and the mixture was further stirred for 4 hours and cooled, and the heating residue was 50%.
4) A toluene solution was obtained. The ratio of the (meth) acrylic acid ester constituting the resin (B-4) for paint is 0%.
Is.

Ultraviolet curable composition (12) Resin (B-4) toluene solution 2 for coating thus obtained
N-butyl acrylate 8 parts to 0 parts (solid content 10 parts)
Parts, 22 parts of isoamyl acrylate, 25 parts of trimethylolpropane triacrylate, 30 parts of dipentaerythritol hexaacrylate, 5 parts of benzophenone, 100 parts of toluene, and 100 parts of isobutyl alcohol are mixed to give a fluorine-containing nonionic surfactant (Sumitomo 3M Limited). Manufactured by Florard FC-171) was added to 500 ppm to prepare an ultraviolet curable composition (12) solution.

The composition ratio of each component in the solution of the ultraviolet curable composition (11) is (A) :( B-4) :( C) = 8.
It is 5: 10: 5 (weight ratio). However, (B-4)
Is not the component (B) of the present invention. Moreover, it is (a-1) :( a-2) = 65: 35 (weight ratio) in a component (A). Using this ultraviolet curable composition (12) solution,
A substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1. The appearance of the surface of the substrate was bleached and was at a defective level. The hardness was 3H in terms of pencil hardness. The result of the abrasion resistance test was an increased haze value of 0.3, which was a level at which there was almost no damage. The result of the cross-cut peeling test is 1
It was 00% and 98% even after the high temperature and high humidity durability test.

[Comparative Example 5] Ultraviolet curable composition (13) Coating resin (B-1) 100 parts of toluene solution (solid content 5)
0 parts), dipentaerythritol hexaacrylate 49.95 parts, benzophenone 0.05 parts, toluene 7
A UV-curable composition (13) solution was prepared by mixing 5 parts and 75 parts of isobutyl alcohol and adding a fluorine-based nonionic surfactant (Sumitomo 3M, Florard FC-171) to 500 ppm. did.

The composition ratio of each component in the solution of the ultraviolet curable composition (13) is (A) :( B) :( C) = 49.9.
It is 5: 50: 0.05 (weight ratio). Further, in the component (A), (a-1) :( a-2) = 100: 0 (weight ratio)
Is. Using this solution of the ultraviolet curable composition (13), a substrate on which a hard coat layer was formed was obtained in the same manner as in Example 1. The appearance of the surface of the substrate was at a defective level, with whitening due to uncured portions. The hardness was F in terms of pencil hardness. The result of the abrasion resistance test shows that the increased haze value is 8.
The score was 1, which was a serious scratch. The result of the cross-cut peeling test is 20%, and 8% after the high temperature and high humidity durability test.
Met.

[Comparative Example 6] UV-curable composition (14) Resin for paint (B-1) 100 parts of toluene solution (solid content: 5)
(0 part), 34 parts of dipentaerythritol hexaacrylate, 16 parts of benzophenone, 75 parts of toluene, and 75 parts of isobutyl alcohol are mixed to give a fluorine-based nonionic surfactant (Sumitomo 3M, Florard FC-1).
71) was added so that it might become 500 ppm, and the ultraviolet curable composition (14) solution was prepared. The composition ratio of each component in this ultraviolet curable composition (14) solution is (A):
(B) :( C) = 34: 50: 16 (weight ratio).
In addition, in the component (A), (a-1) :( a-2) = 10
It is 0: 0 (weight ratio).

Using this solution of UV-curable composition (14), a substrate having a hard coat layer formed thereon was obtained in the same manner as in Example 1. The appearance of the substrate surface was good, and the hardness was 3H in terms of pencil hardness. The results of the abrasion resistance test are
The increased haze value was 0.4, which was a level at which there was almost no damage. The result of the cross-cut peeling test was 40%, and 8% after the high temperature and high humidity durability test. Table 1 collectively shows the compositions and heating residues of the coating resins (B-1) to (B-4) prepared in the above Examples and Comparative Examples.

[0080]

[Table 1] Table 2 collectively shows the composition and usage ratio of each component and the measurement results of physical properties in each of the above Examples and Comparative Examples. In addition,
Regarding the cross-cut test, the results after the high temperature and high humidity durability test are shown.

[0081]

[Table 2] (* 1) With primer layer.

[0082]

The present invention provides a thermoplastic norbornene-based resin molded article having a hard coat layer having excellent adhesion to a thermoplastic norbornene-based resin, hardness after curing, and abrasion resistance, and a method for producing the same. It The molded article of the present invention is useful in a wide range of fields including applications for optical materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masatoshi Yagi Masatoshi Yagi 4-chome 1-chome, Sunadabashi, Higashi-ku, Nagoya, Aichi Mitsubishi Rayon Co., Ltd. Product Development Research Center (72) Makio Kasawa 4-chome, Sunadabashi, Higashi-ku, Nagoya, Aichi No. 1-60 Mitsubishi Rayon Co., Ltd. Product Development and Research Center (72) Inventor, Ho Hosaka Akira 1-2-1, Kawasaki-ku, Kawasaki-shi, Kanagawa, Japan Zeon Co., Ltd. (72) Yuichiro Konishi Kawasaki-ku, Kawasaki-shi, Kanagawa Yokou 1-2-1, Nihon Zeon Co., Ltd. (72) Inventor Sadaji Ohara 1-2-1, Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. (56) Reference JP-A-4-323231 (JP , A) JP-A-4-89217 (JP, A) JP-A-3-106633 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , D B name) C08J 7/04-7/06

Claims (2)

(57) [Claims] 1. A multifunctional monomer (a-1) having (A) three or more (meth) acryloyloxy groups in one molecule.
20 to 100% by weight and 1 to 2 (meta) in one molecule
A 1-2 functional monomer having an acryloyloxy group (a
-2) 10-9 monomer mixture consisting of 80-0% by weight
0 parts by weight, (B) a coating resin comprising a homopolymer or copolymer of a vinyl-based monomer containing 10% by weight or more of at least one monomer selected from (meth) acrylic acid esters A thermoplastic norbornene-based resin molded article having a hard coat layer obtained by curing an ultraviolet curable composition comprising 5 to 80 parts by weight and (C) a photopolymerization initiator of 0.1 to 15 parts by weight. 2. A thermoplastic norbornene-based resin, characterized in that at least the surface of a thermoplastic norbornene-based resin molded product is coated with the ultraviolet-curable composition according to claim 1 and irradiated with ultraviolet rays to form a hard coat layer. Molded article manufacturing method.