JPH05306378A - Ultraviolet curing composition, molding having coating layer using the same curable composition, production thereof and method for bonding using the same curing composition - Google Patents

Abstract

PURPOSE:To obtain a hard coating agent and an adhesive composed of an ultraviolet curing composition, excellent in adhesion to a thermoplastic saturated norbornene-based resin and having high hardness after the curing. CONSTITUTION:The ultraviolet curing composition is composed of a monofunctional acrylate such as n-butyl acrylate or lauryl acrylate, a bi- or a trifunctional acrylate monomer such as hydrogenated tricyclo[5.2.1.0<2>,<6>] decanyl diacrylate, a tetra- or a polyfunctional acrylate such as dipentaerythritol hexaacrylate and a photopolymerization initiator and contains >=40wt.% total amount of a long-chain aliphatic monofunctional acrylate monomer, an alicyclic monofunctional acrylate monomer and an alicyclic bifunctional acrylate monomer.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an ultraviolet curable composition,
A molded article having a coat layer using the curable composition, a method for producing the same, and an adhesion method using the curable composition, more specifically, a monofunctional acrylate monomer, 2
Alternatively, an ultraviolet curable composition comprising a trifunctional acrylate monomer, a tetrafunctional or higher functional acrylate monomer, and a photopolymerization initiator, a method for producing a molded article having a coat layer using the curable composition, and the curable composition are provided. An adhesive method for use is provided.

[0002]

2. Description of the Related Art Generally, in an optical information recording medium element such as a compact disc or a laser vision disc, the information reading accuracy and the transparency are deteriorated due to the scratches on the surface. Since the information itself may be lost when the recording metal film or the like is damaged, a coat layer is provided to increase the surface hardness. A hard coat layer is used to increase the surface hardness of a resin substrate, and a protective coat layer is used to protect a metal film.

General-purpose coating agents can be roughly classified into silicone coating agents and organic coating agents. The silicone-based coating agent is a partial hydrolyzate of a silane compound, and requires heat-curing treatment at a relatively high temperature of about 120 ° C. for about 1 hour. Cannot be used when required.

On the other hand, organic coating agents include a type in which melamine-based, alkyd-based, urethane-based, and acrylic-based coating materials are heat-cured, and a multifunctional acrylic coating material is UV-cured. The former is easier to handle,
Inferior in hardness and weather resistance. The latter is excellent in hardness and productivity, and because it is cured by ultraviolet rays, the influence of heating on the resin is small. Therefore, a UV-curable polyfunctional acrylic coating agent is suitable as the coating agent used for the molded article of the optical material resin.

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. Moreover, these are also used as an ultraviolet curable adhesive.

Polymethyl methacrylate (PMMA) and polycarbonate (PC) have been conventionally known as resins used for optical materials. In the case of these resins, alcohol-based solvents such as isopropyl alcohol, glycol ether-based solvents such as ethylene glycol monomethyl ether, ester-based solvents such as ethyl acetate, and ketone-based solvents such as acetone are used as the solvent for the ultraviolet curable coating agent. Has been.

However, although PMMA is excellent in transparency, it has problems in heat resistance and moisture resistance.
Is superior to PMMA in heat resistance and moisture resistance, but has problems such as large birefringence. Therefore, an optical material excellent in transparency, heat resistance, moisture resistance, low birefringence, etc. is required. It was

Recently, thermoplastic saturated norbornene resins have been attracting attention as optical materials excellent in transparency, heat resistance, moisture resistance and low birefringence. However, a molded article whose surface is made of a thermoplastic saturated norbornene-based resin has a problem in that it is poorly wetted with a general-purpose coating agent, its adhesion is insufficient, and the coating layer after curing peels off from the molded article. It was
Further, since the chemical resistance is high, it is difficult to perform a surface treatment with good workability, and it is also difficult to improve the adhesiveness.

Therefore, conventionally, a UV curable composition excellent in adhesiveness to a molded article made of a thermoplastic saturated norbornene resin, and a molded article made of a thermoplastic saturated norbornene resin having a coat layer having good adhesiveness are produced. The method was unknown.

Further, in other optical materials, it is known that the coating layer contains an antistatic agent to prevent the surface from being charged. However, since the antistatic agent generally lowers the adhesiveness, the coating layer used for the thermoplastic saturated norbornene-based resin which originally has insufficient adhesiveness,
It has been considered difficult to include the required amount of antistatic agent.

Further, the ultraviolet-curing type coating agent is also used as an ultraviolet-curing type adhesive, but stronger adhesion has been required for adhesion of the thermoplastic saturated norbornene resin.

[0012]

DISCLOSURE OF THE INVENTION The inventors of the present invention have earnestly studied the problem of adhesion between a cured product and a molded article made of a thermoplastic saturated norbornene resin, and as a result, a monofunctional acrylate monomer, a difunctional trifunctional acrylate monomer, or a trifunctional acrylate monomer. The present invention has been completed by discovering that a molded product made of a thermoplastic saturated norbornene-based resin and a cured layer can be firmly adhered by using an ultraviolet-curable composition composed of a tetrafunctional or higher functional acrylate monomer. In the present invention, the hard coat layer in the case of coating and the adhesive layer in the case of adhesion are referred to as the cured layer.

[0013]

Thus, according to the present invention, an ultraviolet curable composition comprising a monofunctional acrylate monomer, a difunctional or trifunctional acrylate monomer, a tetrafunctional or higher functional acrylate monomer, and a photopolymerization initiator, and the ultraviolet ray A molded article made of a thermoplastic norbornene-based resin having a coat layer obtained by curing a curable composition, the surface of the molded article made of a thermoplastic saturated norbornene-based resin,
A method for producing a molded article having a coat layer, which comprises applying the ultraviolet-curable composition and irradiating with an ultraviolet ray, and bonding the molded article having an adhesive surface made of a thermoplastic saturated norbornene resin and an adherend, The adhesive surface of the molded product and the adhesive surface of the adherend are bonded together via the ultraviolet curable composition,
Provided is a method for adhering a molded article and an adherend, wherein an adhesive surface is made of a thermoplastic saturated norbornene-based resin, characterized in that the ultraviolet curable composition is irradiated with ultraviolet rays.

(Substrate) In the present invention, the substrate on which the cured layer is formed is a molded product in which at least the surface on which the cured layer is formed is made of a thermoplastic saturated norbornene resin.

The thermoplastic saturated norbornene resin used in the present invention is disclosed in JP-A-3-14882 and JP-A-3-122.
No. 137, JP-A-4-63807, and the like. Specific examples thereof include a hydrogenated product of a ring-opening polymer of a norbornene-based monomer, an addition-type polymer of a norbornene-based monomer, and a norbornene-based monomer. Examples thereof include addition polymers of monomers and olefins, and modified products of these polymers.

The norbornene-based monomer is also a monomer known in the above publications, JP-A-2-227424 and JP-A-2-276842, and examples thereof include norbornene, its alkyl, alkylidene and aromatic substituted derivatives. And halogens, hydroxyl groups of these substituted or unsubstituted olefins,
Polar group substituents such as ester group, alkoxy group, cyano group, amide group, imide group and silyl group, for example, 2-norbornene, 5-methyl-2-norbornene, 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 and the like; multimers of CPD, derivatives and substitution products similar to the above, for example, dicyclopentadiene (hereinafter referred to as DCP), 2,3-dihydrodicyclopentadiene, 1,4: 5,8-dimethano -1, 2, 3,
4,4a, 5,8,8a-2,3-cyclopentadienonaphthalene, 6-ethyl-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, 1
0,10a-dodecahydro-2,3-cyclopentadienoanthracene and the like; an adduct of cyclopentadiene and tetrahydroindene and the like, derivatives and substituents similar to the above, for example, 1,4-methano-1,4,4. 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;
Etc.

The norbornene-based monomer may be polymerized by a known method, and if necessary, it is a thermoplastic saturated norbornene-based resin by copolymerizing with another copolymerizable monomer or by hydrogenation. It can be a thermoplastic norbornene-based polymer hydrogenated product. Further, a polymer or a polymer hydrogenated product is subjected to a method known in JP-A-3-95235 or the like to obtain an α, β-unsaturated carboxylic acid and / or derivative thereof, a styrene-based hydrocarbon, an olefin-based unsaturated bond and a hydrolyzed product. It may be modified by using an organosilicon compound having a decomposable group or an unsaturated epoxy monomer.

GP has a molecular weight of cyclohexane as a solvent.
The number average molecular weight measured by C (gel permeation chromatography) analysis is suitably from 1 to 200,000. In addition, in the case of hydrogenation, the hydrogenation rate is 90% or more, preferably 95% or more, more preferably 99% or more in order to improve the light resistance and weathering resistance.

If desired, the thermoplastic saturated norbornene-based resin used in the present invention may be a phenol-based or phosphorus-based antioxidant, a phenol-based heat deterioration inhibitor, a benzophenone-based ultraviolet stabilizer, an amine-based resin, or the like. Various additives such as an antistatic agent, a lubricant such as an ester of an aliphatic alcohol, a partial ester of a polyhydric alcohol and a partial ether; Further, other resins and the like can be mixed and used as long as the object of the present invention is not impaired. Further, if it is a molded article that does not require transparency, various fillers can be used for the purpose of improving strength and the like.

The method for molding the molded article used in the present invention is as follows:
It is not particularly limited. General molding methods for thermoplastic resins such as injection molding, melt extrusion, hot pressing, solvent casting, and stretching can be used. The surface on which the hardened layer is formed may be made of a thermoplastic saturated norbornene-based resin, and the other portion may be made of another resin or may be formed integrally by inserting metal or the like. ..

(Primer) In the present invention, a specific ultraviolet curable composition is applied to the surface of a thermoplastic saturated norbornene resin, and the ultraviolet curable composition is irradiated with ultraviolet rays to form a cured layer. In order to strengthen the adhesion between the thermoplastic saturated norbornene resin and the cured layer, a primer may be applied prior to the application of the ultraviolet curable composition.

The primer of the present invention comprises a halogenated hydrocarbon polymer, and usually has a molecular weight of 5,000 to 200,
000, preferably 10,000 to 150,000, and more preferably 20,000 to 100,000. As such a halogenated hydrocarbon polymer, ethylene, propylene, butadiene, isoprene, halogenated hydrocarbon polymers obtained by polymerizing or copolymerizing hydrocarbon monomers such as styrene, or vinyl chloride, vinylidene chloride, Examples thereof include those obtained by polymerizing or copolymerizing halogen-containing monomers such as chloroprene. Among these, chlorinated hydrocarbon polymers are preferable, and chlorinated polypropylene is particularly preferable.

The content of halogen is 15 to 55% by weight,
Preferably 20-45% by weight, more preferably 25-3
It is 5% by weight. 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. Further, if the halogen content is too low or too high, the adhesiveness will be poor.

When a photopolymerizable monomer, a photopolymerizable oligomer, etc., which will be described later, particularly a monofunctional acrylate monomer is added to the primer in an amount of 2 to 20% by weight, the primer is formed between the adhesive surface or the coated surface and the cured layer. Layers and adhesive surfaces,
It is preferable because the adhesion between the coated surface and the cured layer is improved.

The primer is used as a primer solution by dissolving it in a solvent. The solvent is not particularly limited as long as it is a substantially poor solvent for the thermoplastic saturated norbornene resin. For example, toluene is a good solvent for the thermoplastic saturated norbornene-based resin, but if it is diluted to 70% by weight or less with methyl isobutyl ketone, erosion becomes small even when applied to the thermoplastic saturated norbornene-based resin, so that the present invention It can be used as a solvent for a primer. Further, when forming a UV-curable hard coat layer, a monofunctional acrylate such as n-butyl methacrylate or isoamyl methacrylate is also a poor solvent for the thermoplastic saturated norbornene-based resin, and the photopolymerizable monomer to be added to the above-mentioned primer is used. Since it is a reactive diluent having the effect as above, it is preferable.

The concentration of the primer solution is 1 to 30% by weight,
It is preferably 2 to 20% by weight, more preferably 3 to 10% by weight.

(Method for Forming Primer Layer) The primer layer of the present invention is formed by applying it to an adhesive surface or a coated surface made of a thermoplastic saturated norbornene resin and sufficiently removing volatile components in the solvent. Note that, for example, when only the above reactive diluent is used as the solvent for the primer, the removing operation is not necessary.

The method of applying the primer solution is not particularly limited, and for example, spraying, dipping, spin coating, roll coater and the like are possible. Further, 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 vary depending on the type of solvent used, the coating amount, and the shape of the adhesive or coated surface, but the thermal deformation of the molded product with the adhesive or coated surface. Therefore, the conditions may be determined to be approximately 120 ° C. or lower and to be sufficiently removed. Specifically 6
It is suitable to leave it at 0 to 120 ° C. for about 3 to 60 minutes. After removing the volatile components at high temperature,
It is preferable to perform cooling for about 10 seconds to approximately room temperature.

The amount to be applied 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 coating, it is preferable that the above thickness be obtained after sufficient removal. If the coating amount of the primer is small, the effect of the primer is small, and if it is too large, it may be difficult to dry or sufficient adhesiveness may not be obtained.

(UV-Curable Composition) The UV-curable composition of the present invention comprises a monofunctional acrylate monomer, 2 or 3
It is composed of a functional acrylate monomer, a tetrafunctional or higher functional acrylate monomer, and a photopolymerization initiator.

In the present invention, among the photopolymerizable monomers, those having an acrylate group are referred to as a monofunctional acrylate monomer, a bifunctional acrylate monomer, a trifunctional acrylate monomer, etc., depending on the number of acrylate groups. Further, in the present invention, the acrylate group includes a methacrylate group, an ethacrylate group, etc. in addition to the acrylate group in the narrow sense.

Examples of the monofunctional acrylate monomer include n-butyl acrylate, isoamyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate and phenoxypropyl acrylate. Among them,
In order to prevent the curing reaction from being hindered by radical oxygen, those having only a acrylate group in a narrow sense without having a methacrylate group or the like are preferable, and in order to reduce the curing shrinkage of the ultraviolet curable composition, the number of carbon atoms is 4 to 6 Those having a degree of side chains are preferable. Further, in order to improve the adhesiveness with the thermoplastic saturated norbornene resin, as described later,
It is also preferable to use a long-chain aliphatic monofunctional acrylate monomer or an alicyclic monofunctional acrylate monomer. The long-chain aliphatic monofunctional acrylate monomer preferably has an aliphatic moiety having 5 to 18 carbon atoms, and more preferably 8 to 16 carbon atoms. If the carbon number is too small, the adhesion will be poor, and if the carbon number is too large, it will be difficult to crosslink and the strength will be poor. As the long-chain aliphatic monofunctional acrylate monomer, specifically,
Examples thereof include lauryl acrylate, stearyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate and the like. Specific examples of the alicyclic monofunctional acrylate monomer include tricyclo [5,2,1,0 ^2,6 ] decanyl acrylate, hydrogenated products thereof, isobornyl acrylate, cyclohexyl acrylate, and the like.

Examples of the bifunctional or trifunctional acrylate monomer include ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, hexanediol, tremethylolpropane, tetramethylolpropane, pentaerythritol and dipentaerythritol. Examples include polyols in which 2 or 3 acrylic acids are esterified, and bisphenol F-type epoxy acrylate. Further, in order to improve the adhesiveness with the thermoplastic saturated norbornene-based resin, it is preferable to use an alicyclic bifunctional acrylate monomer as described later. Specific examples of the alicyclic bifunctional acrylate monomer include tricyclo [5,2,1,0 ^2,6 ] decanyl diacrylate, hydrogenated products thereof, isobornyl diacrylate, cyclohexyl diacrylate and the like. It

Examples of tetrafunctional or higher functional acrylate monomers include, for example, polyols such as tetramethylolpropane, pentaerythritol, and dipentaerythritol.
It is an esterified product of 4 or more, preferably 4 to 8 acrylic acid. In particular, a 4- to 6-functional acrylate monomer that is generally easily available is preferable.

As the photopolymerization initiator, acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone and chlorinated acetophenone; benzophenones; benzyl, methylorthobenzoylbenzoate, benzoin alkyl ether Azo compounds such as α, α′-azobisisobutyronitrile, 2,2′-azobispropane and hydrazone; Organic peroxides such as benzoyl peroxide and ditertiary butyl peroxide; Diphenyldiene Diphenyl disulfides such as sulfide, dibenzyl disulfide, dibenzoyl disulfide; and the like.

The mixing ratio of these is usually 15 to 65% by weight, preferably 25 to 60% by weight, more preferably 30 to 60% by weight, based on the total weight of the acrylate monomer and the photopolymerization initiator. 55% by weight, 5 to 50% by weight of the di- or trifunctional acrylate monomer, preferably 6 to 40% by weight, more preferably 8 to
30 wt%, tetrafunctional or higher acrylate monomer 10
60% by weight, preferably 12 to 50% by weight, more preferably 15 to 45% by weight, and the photopolymerization initiator is 1 to 10% by weight, preferably 2 to 6% by weight. If the amount of the tetrafunctional or higher functional acrylate monomer is too large, the curing shrinkage will increase, and if it is too small, the hardness of the cured layer will decrease, and the curing speed will also decrease. When the amount of the monofunctional acrylate monomer is small, the viscosity becomes high and the workability becomes poor. Further, when the amount of the monofunctional acrylate monomer is large, the curing shrinkage is decreased, and the amount of the bifunctional or trifunctional acrylate monomer is decreased, so that the flexibility of the cured layer is decreased, which causes cracks. Also,
In order to improve the adhesiveness, it is preferable that the amount of the bifunctional or trifunctional acrylate monomer is large.

The UV-curable composition of the present invention contains 40 or more kinds of monomers selected from a long-chain aliphatic monofunctional acrylate monomer, an alicyclic monofunctional acrylate monomer, and an alicyclic bifunctional acrylate monomer. weight%
It is preferably contained in the above amount, more preferably 45% by weight or more, and particularly preferably 50% by weight or more. Long-chain aliphatic monofunctional acrylate monomer,
The higher the content of one or more monomers selected from the alicyclic monofunctional acrylate monomer and the alicyclic bifunctional acrylate monomer, the more the adhesiveness of the ultraviolet curable composition of the present invention to the thermoplastic saturated norbornene resin. improves.

Appropriate additives may be added to the UV-curable composition as long as the adhesiveness and hardness of the cured layer are satisfied. For example, by adding a fluorine-based nonionic surfactant, wetting of the substrate and surface smoothness after the effect can be improved. In addition, the viscosity can be adjusted and the adhesiveness can be improved by adding an appropriate thermoplastic resin. As a thermoplastic resin that improves adhesiveness,
Thermoplastic saturated norbornene-based resin or resin similar in structure to it, for example, ring-opening polymer of norbornene-based monomer, dicyclopentadiene-based, diene-based, aliphatic-based, water-white based petroleum resin or its hydrogen Examples include additives.

(Antistatic Agent) In the ultraviolet-curable composition of the present invention, an antistatic agent is preferably added in order to prevent the cured layer from being charged, especially when used as a hard coating agent. The antistatic agent is not particularly limited and may be a general antistatic agent, but a nonionic antistatic agent is preferably an acrylate monomer. This is preferable because the nonionic antistatic agent has excellent compatibility with the acrylate monomer, and a uniform ultraviolet curable composition can be obtained, so that the adhesiveness and the antistatic effect are uniform.

When the hardened layer is required to be antistatic, the surface electric resistance value of the hardened layer is 5 × 10 ¹³ Ω or less, preferably 2 × 1.
It is set to 0 ¹³ Ω or less, more preferably 10 ¹³ Ω or less. For that purpose, the antistatic agent may be added in an amount of 1 to 7% by weight, preferably 1.5 to 5% by weight. Even when an antistatic agent is added to the ultraviolet curable composition of the present invention in an amount sufficiently lowering the surface electric resistance value, a cured layer having adhesiveness that can withstand use in a molded article composed of a thermoplastic norbornene resin is obtained. Can be formed. In particular, when adhesion is a problem, it is preferable to form the primer layer using the primer composition as described above.

These mixtures can be used as they are as an ultraviolet-curable composition, but depending on the need of operability, an aromatic hydrocarbon solvent such as toluene, xylene or chlorobenzene; cyclohexane or methyl. Alicyclic hydrocarbon solvents such as cyclohexane; ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone and acetone; ether solvents such as n-butyl ether, diethyl ether; etc., ester solvents, cellosolve solvents, chloro solvents, etc. An ultraviolet curable composition may be prepared by dissolving it in a solvent or the like at a concentration of 80% by weight or more and using it.

(Formation of Cured Layer) In the present invention, the ultraviolet curable composition of the present invention is applied to the surface of the thermoplastic saturated norbornene-based resin for forming the cured layer of the molded article of the present invention, and ultraviolet rays are applied. It is irradiated and cured to form a cured layer.

The coating method is not particularly limited, and for example, spraying, dipping, spin coating, roll coater and the like are possible. When a solvent is used, it is dried sufficiently after coating so that the solvent is substantially not contained. The drying method is not particularly limited.

The thickness of the UV-curable composition is 2 to 300 μm for coating and 10 to 4 for adhesion.
It is preferably about 00 μm. If a solvent is used, it should have this thickness after drying. When the thickness is thin, a hardened layer having high strength cannot be obtained, and sufficient effect of improving surface hardness and adhesiveness cannot be obtained. If it is thick, the drying and curing reaction will take time, resulting in poor productivity.
If the curing is insufficient and the hardness is low, the cured layer may lack flexibility and crack.

The coated surface needs to be sufficiently dried if necessary. If it is cured while containing a large amount of solvent, cracks are likely to occur in the coating film, and this may cause a coating film having high hardness to not be obtained. The drying temperature and time required to substantially remove the solvent depend on the type of solvent used, the coating amount,
Although it depends on the shape of the adhesive surface, the conditions may be determined so that the base material is not thermally deformed, the temperature is approximately 120 ° C. or less, and the base material can be sufficiently dried. Specifically, 60 to 1
Drying at 20 ° C. for about 3 to 60 minutes is suitable. After drying at a high temperature, it is preferable to perform cooling at room temperature for about 10 seconds to 10 minutes, and then to cool to near room temperature. In addition,
If no solvent is used, no drying is necessary.

In the case of adhesion, the adhesive surface of the base material and the adhesive surface of the adherend are further matched. The ultraviolet curable composition is applied to the adhesive surface of the adherend, and the ultraviolet curable composition is mixed with a solvent. If it is included, it must be thoroughly dried. In addition, like the substrate, it may be treated with the primer of the present invention or another primer.

Then, by irradiating ultraviolet rays from a light source that efficiently generates ultraviolet rays such as a high pressure mercury lamp, curing takes place in a short time, and a hardened layer having high hardness is formed. The irradiation amount 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 time of about 5 to 10 seconds.

[0048]

EXAMPLES The present invention will be described more specifically below with reference to reference examples, examples and comparative examples. The curing shrinkage measuring method, pencil hardness measuring method, cross-cut peeling test, and warp stress test are as follows.

(Curing shrinkage measurement method) A UV-curable composition was applied to one side of a substrate that complied with the 3.5-inch compact disc standard, and after the UV-irradiation, the surface coated with the UV-curable composition was applied. When the center of the substrate is fixed upward to the horizontal plane, the angle between the horizontal line and the straight line connecting the outermost periphery of the substrate and the stop of the substrate is measured, and the angle of curing shrinkage is represented by the angle.

(Pencil hardness measurement method) JIS K-5400
According to the above, the load was measured with a load of 1 kg.

(Cross-cut peeling test) From the hard coat layer formed on the surface of the molded product, 11 vertical and horizontal cuts were made by a cutter at intervals of 1 mm to make 100 1-mm square grids and cellophane. Adhesive tape (manufactured by Sekisui Chemical Co., Ltd.) is attached, and the outer adhesive tape is peeled off in the 90 ° direction. The test results are shown by the number of unpeeled eyes expressed in%.

(Warping stress test) A test piece (tested according to the standard of 3.5-inch compact disk was used as a fan-shaped 8
It was cut in equal parts), the inner peripheral groove was fixed while being suppressed from above, and a portion 1 cm from the outer periphery of the center line was pushed up 5 mm from one point from the bottom to apply a warp stress.

(Surface electric resistance value) Measured according to JIS K6911.

Reference Example 1 6-Methyl-1,4: 5,8-dimethano-1,4,4
Polymer obtained by hydrogenation reaction of ring-opening polymer of a, 5,6,7,8,8a-octahydronaphthalene (number average molecular weight 28,000, hydrogenation rate almost 100%, glass transition temperature 140 ° C. 0.2 parts by weight of 0.2 parts by weight of the phenolic antioxidant pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) per 100 parts by weight of Part of the mixture was added and pelletized by the melt extrusion method.

Reference Example 2 Pellets were prepared in the same manner as in Reference Example 1 except that ZEONEX 280 (thermoplastic saturated norbornene resin, manufactured by Nippon Zeon Co., Ltd.) was used instead of the polymer obtained by hydrogenation reaction of the ring-opening polymer. Got

Reference Example 3 The pellets obtained in Reference Example 1 were injection molded under the following conditions,
A substrate that complies with the standard of a compact disk with a diameter of 3.5 inches was created. It was H when the pencil hardness of this substrate was measured. Molding machine: Mold clamping pressure 65 tons Resin temperature: 325 ° C Mold temperature: 110 ° C (fixed side), 100 ° C (movable side)

Reference Example 4 A substrate was prepared in the same manner as in Reference Example 3 except that the pellet obtained in Reference Example 2 was used instead of the pellet obtained in Reference Example 1.
The pencil hardness of this substrate was H.

Example 1 10 parts by weight of n-butyl acrylate and 28 parts by weight of isoamyl acrylate, 30 parts by weight of trimethylolpropane triacrylate, 42 parts by weight of dipentaerythritol hexaacrylate, a photopolymerization initiator (manufactured by Ciba Geigy,
5 parts by weight of Irgacure 651) are mixed, and a nonionic antistatic agent (manufactured by Toho Kagaku, Anstics S)
A-300) 2 parts by weight, 5 parts of a fluorine-based nonionic surfactant (Sumitomo 3M, Florard FC-171).
The UV-curable composition was prepared by adding it so that the concentration would be 00 ppm.

The UV curable composition was applied to a spin coater (5
The pellets of Reference Example 1 were applied to the substrate obtained in Reference Example 3 at 000 rpm for 10 seconds), left to stand at room temperature for 10 minutes, and dried sufficiently. The thickness of the film of the ultraviolet curable composition after drying was 6 μm. This substrate was irradiated with ultraviolet light from a high-pressure mercury lamp of 80 mW (peak irradiation intensity on the surface of the substrate: 150 mW / cm ² , integrated light intensity 1500 mJ / cm 2
² , the irradiation time was 10 seconds) to cure the ultraviolet curable composition to form a hard coat layer.

The surface electric resistance value was 9.1 × 10 ¹² Ω. The curing shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 3H in terms of pencil hardness. As a result of the warp stress test, no crack was generated. The result of the cross-cut peeling test was 96%, and it was 93% even after the high-temperature and high-humidity durability test at 80 ° C., 90% RH and 500 hours.

Example 2 A coat layer was formed on the substrate obtained in Reference Example 1 in the same manner as in Example 1 except that the antistatic agent was not added to the ultraviolet curable composition.

The surface electric resistance value was 6.1 × 10 ¹⁵ Ω. The curing shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 3H in terms of pencil hardness. As a result of the warp stress test, no crack was generated. The result of the cross-cut peeling test was 97%, and it was 92% even after the high-temperature and high-humidity durability test at 80 ° C., 90% RH and 500 hours.

Example 3 The same UV-curable composition as in Example 1 was used in the same manner as in Example 1 except that the substrate obtained in Reference Example 4 was used in place of the substrate obtained in Reference Example 3, and the substrate surface was hardened. A coat layer was formed.

The surface electric resistance value was 9.1 × 10 ¹² Ω. The surface hardness of the coated substrate was 3H in terms of pencil hardness. The result of the cross-cut peeling test was 96%, and it was 90% after the high temperature and high humidity durability test of 80 ° C., 90% RH and 500 hours.

Example 4 A coating layer was formed on the substrate obtained in Reference Example 4 in the same manner as in Example 3 except that the antistatic agent was not added to the UV effect agent.

The surface electric resistance value was 5.8 × 10 ¹⁵ Ω. The surface hardness of the coated substrate was 3H in terms of pencil hardness. As a result of the warp stress test, no crack was generated. The result of cross-cut peeling test is 95%, 80 ° C, 90% R
It was 92% even after H, 500-hour high temperature and high humidity endurance test.

Example 5 5 parts by weight of n-butyl acrylate and 32 parts by weight of isoamyl acrylate, 20 parts by weight of neopentyl glycol diacrylate, 48 parts by weight of dipentaerythritol hexaacrylate, photopolymerization initiator (manufactured by Ciba Geigy, Irgacure 651) ) 5 parts by weight are mixed, and a fluorine-based nonionic surfactant (Sumitomo 3M, Florade FC-171) is further added so as to be 500 ppm,
A coating agent was prepared, and the ultraviolet curable composition was used to form a coating layer on the substrate obtained in Reference Example 1 in the same manner as in Example 1.

The surface electric resistance value was 3.3 × 10 ¹⁵ Ω. The curing shrinkage was 4 milliradians, and the hardness of the coated substrate surface was 3H in terms of pencil hardness. No crack was generated when a warp stress was applied to the substrate. The result of cross-cut peeling test is 95%, 80 ° C, 90% RH, 500
It was 94% even after the high temperature and high humidity endurance test of time.

Example 6 3 parts by weight of chlorinated polypropylene (Hardlen MLJ-13, manufactured by Toyo Kasei, molecular weight 45,000, chlorine content of about 27.3% by weight) was dissolved in 35 parts by weight of toluene and 65 parts by weight of methyl isobutyl ketone. Then, it was used as a primer solution.

A spin coater (5
It was applied to the substrate obtained in Reference Example 3 at 000 rpm for 10 seconds), and left at room temperature for 1 minute to dry. The thickness of the primer film after drying was 2 μm.

The same UV curable composition as in Example 1 was applied to this substrate by a spin coater (5000 rpm, 10 seconds).
Then, it was applied to the substrate obtained in Reference Example 1 and left to dry at room temperature for 10 minutes. The thickness of the coating film after drying was 5 μm. This substrate was irradiated with ultraviolet rays from a 80 mW high-pressure mercury lamp (peak irradiation intensity on the substrate surface: 150 mW /
cm ² , integrated light intensity 1500 mJ / cm ² , irradiation time 10
Second) to cure the coating agent and form a coating layer.

The curing shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 3H in terms of pencil hardness. No cracks were generated. The result of the cross-cut peeling test is 100% for both the hard coat layer, 80 ° C. and 90%.
RH, 10 even after 500 hours of high temperature and high humidity endurance test
It was 0%.

Example 7 A coat layer was formed on a substrate in the same manner as in Example 6 except that the substrate obtained in Reference Example 4 was used instead of the substrate obtained in Reference Example 3.

The thickness of the primer film after drying is 2 μm,
The surface hardness of the coated substrate was 3H in terms of pencil hardness. No cracks were generated. The result of the cross-cut peeling test was 100%, and further it was 100% after the high temperature and high humidity durability test of 80 ° C., 90% RH, and 500 hours.

Example 8 40 parts by weight of lauryl acrylate, tricyclo [5,5]
2,1,0 ^2,6] decanyl acrylate hydrogenated product (manufactured by Hitachi Chemical Co., Ltd., FA-513A) 20 parts by weight, tricyclo [5,2,1,0 ^2,6] decanyl diacrylate hydrogenated product (Kyoeisha Oil and fat, light acrylate DCP-A)
20 parts by weight, dipentaerythritol hexaacrylate 20 parts by weight, a photopolymerization initiator (manufactured by Ciba Geigy, Irgacure 651) 10 parts by weight, and an antistatic agent (manufactured by Toho Kagaku, Anstics SA-300) 2 parts by weight are mixed. A UV curable composition was prepared.

The UV curable composition was applied to a spin coater (5
(000 rpm, 10 seconds) was applied to the substrate obtained in Reference Example 4 using the pellets of Reference Example 2, allowed to stand at room temperature for 10 minutes, and dried sufficiently. The thickness of the film of the ultraviolet curable composition after drying was 6 μm. This substrate was irradiated with ultraviolet light from a high-pressure mercury lamp of 80 mW (peak irradiation intensity on the surface of the substrate: 150 mW / cm ² , integrated light intensity 1500 mJ / cm 2
² , the irradiation time was 10 seconds) to cure the ultraviolet curable composition to form a hard coat layer.

The surface electric resistance value was 9.5 × 10 ¹² Ω. The curing shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 2H in terms of pencil hardness. As a result of the warp stress test, no crack was generated. The result of the cross-cut peeling test was 100%, and it was 100% even after the high temperature and high humidity endurance test at 80 ° C. and 90% RH for 500 hours.

Example 9 A hard coat layer was formed on a substrate in the same manner as in Example 8 except that the antistatic agent was not added to the ultraviolet curable composition.

The surface electric resistance value was 4.6 × 10 ¹⁵ Ω. The curing shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 2H in terms of pencil hardness. As a result of the warp stress test, no crack was generated. The result of the cross-cut peeling test was 100%, and it was 100% even after the high temperature and high humidity endurance test at 80 ° C. and 90% RH for 500 hours.

Example 10 3 parts by weight of chlorinated polypropylene (Hardlen MLJ-13, manufactured by Toyo Kasei, molecular weight 45,000, chlorine content of about 27.3% by weight) was dissolved in 35 parts by weight of toluene and 65 parts by weight of methyl isobutyl ketone. Then, it was used as a primer solution.
This primer solution is spin coated (5000 rp
m, 10 seconds) and applied to the substrate obtained in Reference Example 4 and left at room temperature for 1 minute to dry. The thickness of the primer film after drying was 2 μm.

30 parts by weight of lauryl acrylate, 30 parts by weight of tricyclo [5,2,1,0 ^2,6 ] decanyl acrylate hydrogenated product (FA-513A, manufactured by Hitachi Chemical), 10 parts by weight of bisphenol F type epoxy acrylate. , Dipentaerythritol hexaacrylate 30 parts by weight, photopolymerization initiator (manufactured by Ciba Geigy, Irgacure 651)
An ultraviolet curable composition was prepared by mixing 10 parts by weight and 2 parts by weight of an antistatic agent (manufactured by Toho Kagaku Co., Ltd., Anstics SA-300).

Example 8 using this UV-curable composition
A hard coat layer was formed on the substrate which had been treated with a primer in the same manner as in.

The surface electric resistance value was 9.6 × 10 ¹² Ω. The curing shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 2H in terms of pencil hardness. As a result of the warp stress test, no crack was generated. The result of the cross-cut peeling test was 100%, 98% even after the high temperature and high humidity durability test of 80 ° C., 90% RH, and 500 hours.

Example 11 A hard coat layer was formed on a substrate in the same manner as in Example 8 except that the antistatic agent was not added to the ultraviolet curable composition.

The surface electric resistance value was 5.5 × 10 ¹⁵ Ω. The curing shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 2H in terms of pencil hardness. As a result of the warp stress test, no crack was generated. The result of the cross-cut peeling test was 100%, and it was 100% even after the high temperature and high humidity endurance test at 80 ° C. and 90% RH for 500 hours.

Comparative Example 1 A substrate obtained in Reference Example 1 was used in the same manner as in Example 1 except that a commercially available acrylic coating agent (SD-17, manufactured by Dainippon Ink and Chemicals) was used as the ultraviolet curable composition. A coat layer was formed.

The surface electric resistance value was 5.3 × 10 ¹⁵ Ω. The curing shrinkage was 3 milliradian, and the hardness of the coated substrate surface was 2H in pencil hardness. As a result of the warp stress test, no crack was generated on the substrate. The result of the cross-cut peeling test was 61%, and it was 21% after the high temperature and high humidity durability test at 80 ° C., 90% RH and 500 hours.

Comparative Example 2 An acrylic coating agent (SD
-17) A coating layer was formed on the substrate obtained in Reference Example 1 in the same manner as in Example 1 except that the ultraviolet curable composition was prepared by adding 2 parts by weight of an antistatic agent (Anstics SA-300) to 115 parts by weight. Formed.

The surface electric resistance value was 9.4 × 10 ¹² Ω. The curing shrinkage was 3 milliradian, and the hardness of the coated substrate surface was 2H in pencil hardness. As a result of the warp stress test, no crack was generated on the substrate. The result of the cross-cut peeling test was 4%, and it was 0% after the high-temperature high-humidity durability test of 80 ° C., 90% RH, and 500 hours. In addition, the hard coat layer is very easily peeled off, and the reliability of the measured values of the surface electric resistance value and the pencil hardness is low.

Reference Example 5 The pellets obtained in Reference Example 1 were injection-molded under the same conditions as in Reference Example 3 to obtain a plate-like molded product having a thickness of 2.5 mm and a size of 100 mm × 25 mm. From 12.5m
A hole having a radius of 1 mm was opened at a position m, and two test pieces were obtained.

Reference Example 6 Two test pieces were obtained in the same manner as in Reference Example 5 except that the pellet obtained in Reference Example 2 was used instead of the pellet obtained in Reference Example 1.

Example 12 The test pieces obtained in Reference Example 5 were applied with a brush so that the primer solution of Example 4 would be 5 μm after drying, with 25 mm square at one end opposite to the holes of the test pieces as an adhesive surface. Then, it was left to dry for 1 minute. Then, Example 1 was applied to one adhesive surface.
The UV curable composition of is applied by a brush to a thickness of 20 μm,
Adhesive surfaces are attached and fixed so that the holes are opposite to each other, and UV irradiation is performed with a 80 mW high-pressure mercury lamp (peak irradiation intensity on the surface of the test piece: 150 mW
/ Cm ² , integrated light intensity 3000 mJ / cm ² , irradiation time 20
Seconds) and glued.

After the bonding, the test piece was hung using one hole and the other hole was used to hang a 30 kg weight. However, even after 10 minutes from the load, the bonded surface did not peel off.
It showed good adhesion.

Example 13 Test pieces were bonded together in the same manner as in Example 12 except that the test piece obtained in Reference Example 6 was used instead of the test piece obtained in Reference Example 5.

After the bonding, the test piece was hung using one hole and the other hole was used to hang a weight of 30 kg. However, even after 10 minutes from the load, the bonded surface did not peel off.
It showed good adhesion.

Example 13 3 parts by weight of chlorinated polypropylene (Hardlen MLJ-13), 35 parts by weight of toluene and 6 parts of methyl isobutyl ketone were added.
It was dissolved in 5 parts by weight to obtain a primer solution. Reference example 6
25m of one end of the test pieces obtained in step 1 on the side opposite to the holes of the test pieces
With the m square as the adhesive surface, the primer solution is applied to this adhesive surface with a spin coater (5000 rpm, 10 seconds),
It was left to dry at room temperature for 1 minute. The thickness of the primer film after drying was 2 μm. The ultraviolet curable composition of Example 8 was applied to one adhesive surface by a brush to a thickness of 20 μm, and the adhesive surfaces were bonded and fixed so that the holes were opposite to each other. UV irradiation by lamp (peak irradiation intensity on test piece surface: 150 mW / c
m ² , integrated light intensity 3000 mJ / cm ² , irradiation time 20 seconds)
And glued.

After adhesion, the test piece was hung using one hole and the other hole was used to hang a 30 kg weight. However, even after 10 minutes from the load, the adhesion surface did not peel off,
It showed good adhesion.

[0098]

EFFECT OF THE INVENTION The present invention provides an ultraviolet curable composition which is particularly excellent in adhesiveness with a thermoplastic saturated norbornene resin and has a high hardness when exposed to ultraviolet rays. Further, the ultraviolet curable composition is used. Method for producing a thermoplastic saturated norbornene-based resin molded article having a coat layer excellent in adhesiveness between a coat layer and a base material and hardness of the coat layer, and thermoplastic saturation excellent in adhesiveness using the ultraviolet curable composition A method for adhering a norbornene-based resin and an adherend is provided. Further, the ultraviolet curable composition of the present invention has a practical adhesiveness with a thermoplastic saturated norbornene resin even if an antistatic agent is added in an effective amount.

Front page continuation (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08F 220/20 MMV 7242-4J C08J 5/12 CER 9267-4F 7/00 304 7258-4F 7/04 CER V C09D 4/02 PDV 7921-4J // C08L 45:00 (72) Inventor Ima Natsume 1-2-1 Nikko, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Research and Development Center

Claims (7)

[Claims] 1. An ultraviolet curable composition comprising a monofunctional acrylate monomer, a difunctional trifunctional acrylate monomer, a tetrafunctional or higher functional acrylate monomer, and a photopolymerization initiator. 2. 40% by weight or more of at least one monomer selected from a long-chain aliphatic monofunctional acrylate monomer, an alicyclic monofunctional acrylate monomer, and an alicyclic bifunctional acrylate monomer. The ultraviolet curable composition as described above. 3. The ultraviolet curable composition according to claim 1, which contains 1 to 7% by weight of an antistatic agent. 4. A molded article made of a thermoplastic norbornene-based resin having a coating layer obtained by curing the ultraviolet curable composition according to claim 1. 5. The surface electric resistance value of the coating layer is 5 × 10 ¹³
The molded article according to claim 4, which has an Ω or less. 6. The surface of a molded article, at least the surface of which is formed of a thermoplastic saturated norbornene-based resin.
A method for producing a molded article having a coat layer, which comprises applying the ultraviolet-curable composition described in 2 or 3 and irradiating with ultraviolet rays. 7. A method for adhering a molded article having an adhesive surface made of a thermoplastic saturated norbornene-based resin and an adherend,
The ultraviolet-curable composition according to claim 1, 2 or 3 is applied to the adhesive surface of the molded article and / or the adhesive surface of the adherend, and the adhesive surface of the molded article and the adhesive surface of the adherend are bonded together,
A method of adhering a molded article and an adherend, wherein the ultraviolet curable composition is irradiated with ultraviolet rays, and the adhesive surface is made of a thermoplastic saturated norbornene resin.