JP3334189B2 - UV curable composition, molded article having a coat layer using the curable composition, method for producing the same, and bonding method using the curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ultraviolet curable composition,
The present invention relates to 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.
Or an ultraviolet curable composition comprising a trifunctional acrylate monomer, a tetrafunctional or higher 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. An adhesion method to be used is provided.

[0002]

2. Description of the Related Art In general, in optical information recording medium elements such as compact discs and laser vision discs, scratches on the surface cause problems such as poor information reading accuracy and transparency. Since the information itself is lost due to the damage of the recording metal film or the like, the hardness of the surface is increased by providing a coat layer. A material that increases the surface hardness of a resin substrate is called a hard coat layer, and a material that protects a metal film or the like is called a protective coat layer.

[0003] General-purpose coating agents can be broadly classified into silicone coating agents and organic coating agents. The silicone-based coating agent is a partial hydrolyzate of a silane compound and requires a heat curing treatment at a relatively high temperature of about 1 hour at 120 ° C., so that the base material is liable to be slightly thermally deformed, and the accuracy is low. 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 coatings are cured by heating, and a type in which a polyfunctional acrylic-based coating is cured by ultraviolet rays. The former is easy to handle,
Poor in hardness and weather resistance. The latter is excellent in hardness and productivity, and hardly affects the resin by heating due to ultraviolet curing. Therefore, as a coating agent used for a molded article of an optical material resin, an ultraviolet curable polyfunctional acrylic coating agent is suitable.

The ultraviolet-curable polyfunctional acrylic coating agent contains a polyfunctional acrylate monomer and / or oligomer, a photopolymerization initiator, and other additives, and is a solvent-free or diluted with a solvent. They are also used as UV-curable adhesives.

Hitherto, polymethyl methacrylate (PMMA) and polycarbonate (PC) have been known as resins used for optical materials. In the case of these resins, alcohol solvents such as isopropyl alcohol, glycol ether solvents such as ethylene glycol monomethyl ether, ester solvents such as ethyl acetate, and ketone solvents such as acetone are used as solvents for the ultraviolet curing coating agent. Have been.

However, although PMMA is excellent in transparency, it has problems in heat resistance, moisture resistance, and the like.
Is superior in heat resistance and moisture resistance to PMMA, but has problems such as large birefringence, and optical materials excellent in all of transparency, heat resistance, moisture resistance, low birefringence, etc. are required. Was.

[0008] Recently, thermoplastic saturated norbornene resins have attracted attention as optical materials having excellent 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 that the wettability with a general-purpose coating agent is poor, the adhesion is insufficient, and the cured coating layer is peeled off from the molded article. Was.
In addition, it is difficult to perform surface treatment with good workability due to high chemical resistance, and it is also difficult to increase the adhesiveness.

Therefore, conventionally, an ultraviolet curable composition having excellent adhesion 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 adhesion. The method was unknown.

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

The ultraviolet-curable coating agent is also used as an ultraviolet-curable adhesive. However, stronger adhesion has been required for bonding a thermoplastic saturated norbornene resin.

[0012]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies on the problem of adhesion between a molded article made of a thermoplastic saturated norbornene-based resin and a cured layer. As a result, a monofunctional acrylate monomer, a difunctional or trifunctional acrylate monomer was obtained. It has been found that a molded article composed of a thermoplastic saturated norbornene-based resin and a cured layer can be firmly bonded to each other by using an ultraviolet-curable composition from an acrylate monomer having four or more functional groups, and the present invention has been completed. In the present invention, a hard coat layer in the case of coating, an adhesive layer in the case of adhesion, and the like are referred to as a cured layer.

[0013]

According to the present invention, there is provided an ultraviolet-curable composition comprising a monofunctional acrylate monomer, a difunctional or trifunctional acrylate monomer, an acrylate monomer having four or more functional groups, and a photopolymerization initiator. 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,
The method for producing a molded article having a coat layer characterized by applying the ultraviolet-curable composition and irradiating ultraviolet rays, and bonding the molded article made of a thermoplastic saturated norbornene-based resin to an adherend with an adhesive surface, Adhering the adhesive surface of the molded article and the adhesive surface of the adherend via the ultraviolet-curable composition,
There is provided a method of bonding a molded article and a body to be bonded, wherein the bonding surface is characterized by irradiating the ultraviolet-curable composition with ultraviolet light, the bonding surface comprising a thermoplastic saturated norbornene-based resin.

(Substrate) In the present invention, the substrate on which the cured layer is formed is a molded article whose surface on which at least 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.
137 and JP-A-4-63807. 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. And an olefin addition polymer, and modified products of these polymers.

The norbornene-based monomer is also a monomer known in the above publication, JP-A-2-227424, JP-A-2-276842, etc., for example, norbornene, its alkyl, alkylidene, and aromatic substituted derivatives. And halogens, hydroxyl groups of these substituted or unsubstituted olefins,
Polar group substituents such as an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a 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 substituents similar to the above, for example, dicyclopentadiene (hereinafter, referred to as DCP), 2,3-dihydrodicyclopentadiene, 1,4: 5,8-dimetano −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; adducts of cyclopentadiene with tetrahydroindene and the like, derivatives and substituents 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;
And the like.

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

The molecular weight is determined by GP using cyclohexane as a solvent.
The number average molecular weight measured by C (gel permeation chromatography) analysis is suitably from 100,000 to 200,000. In addition, when hydrogen is added, the hydrogenation rate is 90% or more, preferably 95% or more, and more preferably 99% or more, in order to improve light deterioration resistance and weather resistance deterioration.

The thermoplastic saturated norbornene-based resin used in the present invention may optionally include a phenol-based or phosphorus-based antioxidant; a phenol-based thermal degradation inhibitor; a benzophenone-based ultraviolet stabilizer; an amine-based or the like. And various additives such as antistatic agents; esters of aliphatic alcohols, partial esters and partial ethers of polyhydric alcohols; and the like. Further, other resins and the like can be mixed and used as long as the object of the present invention is not impaired. Further, as long as the molded article does not require transparency, various fillers can be used for the purpose of improving the strength and the like.

The method for molding the molded article used in the present invention is as follows.
There is no particular limitation. General thermoplastic resin molding methods 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 a metal or the like. .

(Primer) In the present invention, a specific ultraviolet curable composition is applied to the surface of a thermoplastic saturated norbornene-based resin, and the ultraviolet curable composition is irradiated with ultraviolet rays to form a cured layer. In order to further strengthen the adhesion between the thermoplastic saturated norbornene resin and the cured layer, a primer may be applied before applying 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, more preferably 20,000 to 100,000. Such a halogenated hydrocarbon polymer, ethylene, propylene, butadiene, isoprene, halogenated hydrocarbon polymer obtained by polymerizing or copolymerizing a hydrocarbon monomer such as styrene, or vinyl chloride, vinylidene chloride, Examples thereof include those obtained by polymerizing or copolymerizing a halogen-containing monomer such as chloroprene. Of these, those obtained by chlorinating a hydrocarbon polymer are preferred, and chlorinated polypropylene is particularly preferred.

The halogen content is 15 to 55% by weight,
Preferably from 20 to 45% by weight, more preferably from 25 to 3% by weight.
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 coating workability will be poor. On the other hand, if the content of halogen is too small or too large, the adhesion becomes poor.

When a primer, such as a photopolymerizable monomer or a photopolymerizable oligomer described below, particularly a monofunctional acrylate monomer, of 2 to 20% by weight is added to the primer, the primer formed between the adhesive surface or the coated surface and the cured layer is added. Layers and adhesive surfaces,
This is preferable because the adhesion to the coated surface and the cured layer is improved.

The primer is 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 saturated norbornene-based resin. For example, toluene is a good solvent for a thermoplastic saturated norbornene resin, but when diluted with methyl isobutyl ketone to 70% by weight or less, erosion is reduced even when applied to a thermoplastic saturated norbornene resin. It can be used as a solvent for a primer. Further, when forming an ultraviolet-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 resin, and the photopolymerizable monomer to be added to the above-mentioned primer is used. It is a reactive diluent having the effect as described above, and is therefore preferred.

The concentration of the primer solution is 1 to 30% by weight,
Preferably it is 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 to a bonding surface or a coating surface made of a thermoplastic saturated norbornene resin and sufficiently removing volatile components in a solvent. For example, when only the above-mentioned reactive diluent is used as a solvent for the primer, the removal operation is not required.

The method for 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 volatile components 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 amount applied, and the shape of the adhesive surface or the coated surface, but the thermal deformation of the molded article having the adhesive surface or the coated surface It is sufficient to determine the conditions so that the temperature can be reduced to about 120 ° C. or lower and sufficiently removed. Specifically, 6
It is appropriate to leave at 0 to 120 ° C. for about 3 to 60 minutes. After removing volatile components at high temperature, 10
It is preferable to perform cooling for about 10 seconds to about 10 minutes, and to cool to about 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 volatile components after coating, it is preferable that the above thickness be obtained after sufficient removal. If the amount of the primer applied is small, the effect of the primer is small, and if it is too large, drying is difficult or sufficient adhesiveness cannot be obtained.

(Ultraviolet curable composition) The ultraviolet curable composition of the present invention comprises a monofunctional acrylate monomer, 2 or 3
It is composed of a functional acrylate monomer, an acrylate monomer having four or more functional groups, and a photopolymerization initiator.

In the present invention, among the photopolymerizable monomers, those having an acrylate group are referred to as monofunctional acrylate monomers, difunctional acrylate monomers, and trifunctional acrylate monomers, depending on the number of acrylate groups. In the present invention, the acrylate group includes a methacrylate group, an ethacrylate group and the like in addition to the acrylate group in a 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. Above all,
In order to prevent the curing reaction from being inhibited by radical oxygen, those having only acrylate groups in a narrow sense without having a methacrylate group or the like are preferable. Further, in order to reduce curing shrinkage of the ultraviolet curable composition, the number of carbon atoms is preferably 4-6. Those having a certain number of side chains are preferred. Further, in order to improve the adhesiveness with the thermoplastic saturated norbornene-based resin, as described below,
It is also preferable to use a long-chain aliphatic monofunctional acrylate monomer or an alicyclic monofunctional acrylate monomer. As the long-chain aliphatic monofunctional acrylate monomer, an aliphatic moiety having 5 to 18 carbon atoms is preferable, and one having 8 to 16 carbon atoms is more preferable. If the carbon number is too small, the adhesiveness is poor, and if the carbon number is too large, crosslinking is difficult and the strength is poor. As the long-chain aliphatic monofunctional acrylate monomer, specifically,
Examples thereof include lauryl acrylate, stearyl acrylate, octyl acrylate, isooctyl acrylate, decyl acrylate, and isodecyl acrylate. Specific examples of the alicyclic monofunctional acrylate monomer include tricyclo [5,2,1,0 ^2,6 ] decanyl acrylate, a hydrogenated product thereof, isobonyl acrylate, and cyclohexyl acrylate.

Examples of the bifunctional or trifunctional acrylate monomer include ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, hexanediol, tremethylolpropane, tetramethylolpropane, pentaerythritol, dipentaerythritol and the like. Examples include polyols in which two or three acrylic acids are esterified, and bisphenol F type epoxy acrylate. 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, a hydrogenated product thereof, isobonyl diacrylate, and cyclohexyl diacrylate. You.

Examples of the acrylate monomer having four or more functional groups include polyols such as tetramethylolpropane, pentaerythritol, and dipentaerythritol.
Four or more, preferably four to eight acrylic acids are esterified. In particular, generally available 4- to 6-functional acrylate monomers are preferred.

Examples of the photopolymerization initiator include 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; diphenyldi Diphenyl disulfides such as sulfide, dibenzyl disulfide and dibenzoyl disulfide; and the like.

The mixing ratio of the monofunctional acrylate monomer 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 bifunctional or trifunctional acrylate monomer, preferably 6 to 40% by weight, more preferably 8 to 50% by weight.
30% by weight, 4-functional 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 acrylate monomer having four or more functional groups is too large, the curing shrinkage increases, and if it is too small, the hardness of the cured layer decreases and the curing speed decreases. If the amount of the monofunctional acrylate monomer is small, the viscosity becomes high and the workability is poor. In addition, when the amount of the monofunctional acrylate monomer is large, the curing shrinkage decreases, and in addition, the amount of the bifunctional or trifunctional acrylate monomer decreases, and the flexibility of the cured layer decreases, which causes cracks. Also,
In order to improve the adhesion, it is preferable that the amount of the bifunctional or trifunctional acrylate monomer is large.

The ultraviolet-curable composition of the present invention comprises at least one monomer selected from the group consisting of a long-chain aliphatic monofunctional acrylate monomer, an alicyclic monofunctional acrylate monomer, and an alicyclic bifunctional acrylate monomer. weight%
The content is preferably at least 45% by weight, more preferably at least 45% by weight, and particularly preferably at least 50% by weight. A long-chain aliphatic monofunctional acrylate monomer,
As the content of one or more monomers selected from the alicyclic monofunctional acrylate monomer and the alicyclic bifunctional acrylate monomer increases, the adhesiveness of the ultraviolet-curable composition of the present invention to the thermoplastic saturated norbornene-based resin increases. improves.

An appropriate additive may be added to the ultraviolet 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 with the substrate and surface smoothness after the effect can be improved. In addition, by adding an appropriate thermoplastic resin, the viscosity can be adjusted and the adhesiveness can be improved. As a thermoplastic resin that improves adhesion,
Thermoplastic saturated norbornene-based resin or a resin having a structure similar thereto, for example, a ring-opening polymer of a norbornene-based monomer, a petroleum resin such as a dicyclopentadiene-based, diene-based, aliphatic-based, water-white-based resin, or hydrogen thereof. Additives.

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

When it is necessary to prevent the cured layer from being charged, the cured layer has a surface electric resistance of 5 × 10 ¹³ Ω or less, preferably 2 × 10 ¹³ Ω or less.
0 ¹³ Ω or less, more preferably 10 ¹³ Ω or less. For this purpose, the antistatic agent is added in an amount of 1 to 7% by weight, preferably 1.5 to 5% by weight. Even when the UV curable composition of the present invention is used by adding an antistatic agent in an amount that sufficiently lowers the surface electric resistance, a cured layer having an adhesive property that can withstand use in a molded article made of a thermoplastic norbornene resin is used. Can be formed. In particular, when adhesion is a problem, it is preferable to form a primer layer using the primer composition as described above.

These mixtures can be used as such as an ultraviolet-curable composition, but if necessary, for example, an aromatic hydrocarbon solvent such as toluene, xylene, or chlorobenzene; cyclohexane, 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 and diethyl ether; ester solvents; cellosolve solvents; It may be dissolved in a solvent or the like at a concentration of 80% by weight or more and used to form an ultraviolet curable composition.

(Formation of Cured Layer) In the present invention, the ultraviolet curable composition of the present invention is applied to the surface of a thermoplastic saturated norbornene resin to form a cured layer of the molded article of the present invention, and ultraviolet rays are applied. Irradiate and cure 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 sufficiently dried after coating so that the solvent is not substantially contained. The drying method is not particularly limited.

The thickness of the ultraviolet curable composition is 2 to 300 μm for coating and 10 to 4 for adhesion.
It is preferably about 00 μm. When a solvent is used, the thickness is adjusted to this thickness after drying. When the thickness is small, a hardened layer having high strength cannot be obtained, and a sufficient surface hardness improving effect and adhesiveness cannot be obtained. If it is thick, the drying and curing reaction takes time, and the productivity becomes poor.
When the curing is insufficient and the hardness is low, or the cured layer lacks flexibility and may be cracked.

The painted surface must be sufficiently dried as required. If the coating is cured while containing a large amount of solvent, cracks are likely to occur in the coating film, and it also becomes a cause that a coating film with high hardness cannot be obtained. The drying temperature and time required to substantially remove the solvent depends on the type of solvent used, coating amount,
Although it differs depending on the shape of the bonding surface, the conditions may be determined so that the substrate is not more than 120 ° C. and sufficiently dried so that the substrate is not thermally deformed. Specifically, 60-1
Drying at 20 ° C. for about 3 to 60 minutes is appropriate. After drying at a high temperature, it is preferable to perform cooling at room temperature for about 10 seconds to 10 minutes, and cool to almost room temperature. In addition,
If no solvent is used, drying is not required.

In the case of bonding, the bonding surface of the base material and the bonding surface of the object to be bonded are further matched, but the ultraviolet curable composition is also applied to the bonding surface of the object to be bonded, and the solvent is applied to the ultraviolet curable composition. If it does, it must be sufficiently dried. Moreover, you may treat with the primer of this invention or another primer similarly to a base material.

Thereafter, by irradiating ultraviolet rays from a light source such as a high-pressure mercury lamp that efficiently generates ultraviolet rays, curing occurs in a short time and a hardened layer having high hardness is formed. Although the irradiation amount of the ultraviolet ray varies depending on the reactivity of the photopolymerizable monomer and the photopolymerization initiator, the curing can be usually performed in a short time of about 5 to 10 seconds in the case of a high-pressure mercury lamp of 80 W / cm.

[0048]

The present invention will be described more specifically with reference to the following Reference Examples, Examples and Comparative Examples. The curing shrinkage measuring method, pencil hardness measuring method, cross-cut peeling test, and warpage stress test are as follows.

(Measurement Method for Curing Shrinkage) An ultraviolet-curable composition was applied to one surface of a substrate conforming to a 3.5-inch compact disk, irradiated with ultraviolet light, and then the surface coated with the ultraviolet-curable composition was exposed. When the center of the substrate is fixed 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 indicates the degree of cure shrinkage.

(Pencil hardness measurement method) JIS K-5400
Was measured under a load of 1 kg according to the above.

(Cross-cut peeling test) From the hard coat layer formed on the surface of the molded product, 11 cuts each of length and width were made at intervals of 1 mm with a cutter to make 100 cross-cuts of 1 mm square, and An adhesive tape (manufactured by Sekisui Chemical Co., Ltd.) is attached, and the outer adhesive tape is peeled off in a 90 ° direction. The test results indicate the number of eyes that did not peel off in%.

(Warping stress test) A test piece (a piece conforming to the standard of a 3.5-inch compact disk was
The groove was cut into equal parts), the inner peripheral groove was fixed from above, and the portion 1 cm from the outer periphery of the center line was pushed upward 5 mm upward from one point to apply a warping stress.

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

Reference Example 1 6-methyl-1,4: 5,8-dimethano-1,4,4
a, 5, 6, 7, 8, 8a-Polymer obtained by hydrogenating a ring-opening polymer of octahydronaphthalene (number-average molecular weight: 28,000, hydrogenation ratio: almost 100%, glass transition temperature: 140 ° C) )), And 0.2 parts by weight of a phenolic antioxidant pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) in an amount of 0.2 part by weight based on 100 parts by weight of And then pelletized by melt extrusion.

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 hydrogenating the ring-opening polymer. I got

Reference Example 3 The pellet obtained in Reference Example 1 was injection molded under the following conditions.
Substrates were made to meet the 3.5 inch diameter compact disc specification. It was H when the pencil hardness of this substrate was measured. Molding machine: Mold clamping pressure 65 ton 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, 28 parts by weight of isoamyl acrylate, 30 parts by weight of trimethylolpropane triacrylate, 42 parts by weight of dipentaerythritol hexaacrylate, a photopolymerization initiator (Ciba-Geigy,
5 parts by weight of Irgacure 651) and further mixed with a nonionic antistatic agent (Ansticks S, manufactured by Toho Chemical Co., Ltd.)
A-300) 2 parts by weight, a fluorine-based nonionic surfactant (Fluorad FC-171, manufactured by Sumitomo 3M Limited) in 5 parts
The ultraviolet curable composition was adjusted to be 00 ppm.

The ultraviolet curable composition was applied to a spin coater (5
(000 rpm, 10 seconds) using the pellets of Reference Example 1 to apply to the substrate obtained in Reference Example 3, 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. The substrate was irradiated with ultraviolet light from a high-pressure mercury lamp of 80 mW (peak irradiation intensity on the substrate surface: 150 mW / cm ² , integrated light amount 1500 mJ / cm).
² , irradiation time of 10 seconds) to cure the ultraviolet curable composition to form a hard coat layer.

The surface electric resistance was 9.1 × 10 ¹² Ω. The degree of cure shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 3H in 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 was 93% even after a high-temperature high-humidity endurance test of 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 no antistatic agent was added to the ultraviolet curable composition.

The surface electric resistance was 6.1 × 10 ¹⁵ Ω. The degree of cure shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 3H in 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 was 92% even after a high-temperature high-humidity durability test at 80 ° C., 90% RH and 500 hours.

Example 3 The same ultraviolet 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 instead of the substrate obtained in Reference Example 3. A coat layer was formed.

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

Example 4 A coat layer was formed on the substrate obtained in Reference Example 4 in the same manner as in Example 3 except that no antistatic agent was added to the ultraviolet light effect agent.

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

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

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

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

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

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

The degree of curing shrinkage was 3 milliradians, and the hardness of the coated substrate surface was 3H in pencil hardness. There were no cracks. The results of the cross-cut peeling test are 100% for the hard coat layer, and 80 ° C., 90%
RH, 10 hours after high-temperature, high-humidity endurance test for 500 hours
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 dried primer film is 2 μm,
The hardness of the coated substrate surface was 3H in pencil hardness. There were no cracks. The result of the cross-cut peel test was 100%, and was 100% even after the high-temperature high-humidity endurance test at 80 ° C., 90% RH and 500 hours.

Example 8 40 parts by weight of lauryl acrylate, tricyclo [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 Fat acrylate, light acrylate DCP-A)
20 parts by weight, 20 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of a photopolymerization initiator (manufactured by Ciba-Geigy, Irgacure 651), and 2 parts by weight of an antistatic agent (manufactured by Toho Chemical, Anstics SA-300) are mixed. The UV curable composition was prepared.

The ultraviolet curable composition was applied to a spin coater (5
(000 rpm, 10 seconds) using the pellets of Reference Example 2 to apply to the substrate obtained in Reference Example 4, 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. The substrate was irradiated with ultraviolet light from a high-pressure mercury lamp of 80 mW (peak irradiation intensity on the substrate surface: 150 mW / cm ² , integrated light amount 1500 mJ / cm).
² , irradiation time of 10 seconds) to cure the ultraviolet curable composition to form a hard coat layer.

The surface electric resistance was 9.5 × 10 ¹² Ω. The degree of cure shrinkage was 3 milliradians, 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. The result of the cross-cut peel test was 100%, even after the high-temperature, high-humidity endurance test at 80 ° C., 90% RH and 500 hours.

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

The surface electric resistance was 4.6 × 10 ¹⁵ Ω. The degree of cure shrinkage was 3 milliradians, 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. The result of the cross-cut peel test was 100%, even after the high-temperature, high-humidity endurance test at 80 ° C., 90% RH and 500 hours.

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

30 parts by weight of lauryl acrylate, 30 parts by weight of hydrogenated tricyclo [5,2,1,0 ^2,6 ] decanyl acrylate (FA-513A, manufactured by Hitachi Chemical), 10 parts by weight of bisphenol F type epoxy acrylate , 30 parts by weight of dipentaerythritol hexaacrylate, a photopolymerization initiator (Irgacure 651, manufactured by Ciba Geigy)
10 parts by weight and 2 parts by weight of an antistatic agent (manufactured by Toho Kagaku, Ansticks SA-300) were mixed to prepare an ultraviolet curable composition.

Example 8 Using This UV-Curable Composition
A hard coat layer was formed on the substrate treated with the primer in the same manner as in Example 1.

The surface electric resistance was 9.6 × 10 ¹² Ω. The degree of cure shrinkage was 3 milliradians, 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. The result of the cross-cut peel test was 98% even after the high-temperature high-humidity durability test at 100%, 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 no antistatic agent was added to the ultraviolet curable composition.

The surface electric resistance was 5.5 × 10 ¹⁵ Ω. The degree of cure shrinkage was 3 milliradians, 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. The result of the cross-cut peel test was 100%, even after the high-temperature, high-humidity endurance test at 80 ° C., 90% RH and 500 hours.

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

The surface electric resistance was 5.3 × 10 ¹⁵ Ω. The curing shrinkage was 3 milliradians, 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 grid-cut peel test was 61%, and after the high-temperature high-humidity endurance test at 80 ° C., 90% RH and 500 hours, it was 21%.

Comparative Example 2 As an ultraviolet curable composition, an acrylic coating agent (SD
-17) A coat layer was applied to the substrate obtained in Reference Example 1 in the same manner as in Example 1 except that an ultraviolet curable composition in which 2 parts by weight of an antistatic agent (Anstics SA-300) was added to 115 parts by weight was used. Was formed.

The surface electric resistance was 9.4 × 10 ¹² Ω. The curing shrinkage was 3 milliradians, 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 after the high-temperature high-humidity endurance test at 80 ° C., 90% RH and 500 hours, it was 0%. 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 Reference Example 3 to obtain a plate-shaped 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 made at one position of m to obtain two test pieces.

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 as to have a thickness of 5 μm after drying the primer solution of Example 4 with 25 mm square at one end opposite to the hole of the test piece as an adhesive surface. And left to dry for 1 minute. Then, Example 1 was applied to one of the adhesive surfaces.
The UV curable composition of the above is applied with a brush to a thickness of 20 μm,
The adhesive surfaces were stuck together and fixed such that the perforated sides were opposite to each other, and ultraviolet irradiation was performed with a high-pressure mercury lamp of 80 mW (peak irradiation intensity on the surface of the test piece: 150 mW).
/ Cm ² , integrated light quantity 3000 mJ / cm ² , irradiation time 20
S) and adhered.

After bonding, the test piece was hung using one hole and a 30 kg weight was hung using the other hole. However, even after 10 minutes after the load was applied, the bonded surface did not peel off.
Good adhesion was shown.

Example 13 Test pieces were adhered to each other 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 bonding, the test piece was hung using one hole and a 30 kg weight was hung using the other hole. However, even after 10 minutes after the load was applied, the bonded surface did not peel off.
Good adhesion was shown.

Example 13 3 parts by weight of chlorinated polypropylene (Hardlen MLJ-13) were mixed with 35 parts by weight of toluene and 6 parts by weight of methyl isobutyl ketone 6
It was dissolved in 5 parts by weight to obtain a primer solution. Reference example 6
25m at one end opposite to the hole of the test piece
The primer solution is applied to this adhesive surface using a spin coater (5000 rpm, 10 seconds) with the m squares as the adhesive surface,
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 of the adhesive surfaces with a brush to a thickness of 20 μm, and the adhesive surfaces were bonded and fixed so that the perforated sides were opposite to each other. UV irradiation by a lamp (peak irradiation intensity on the surface of the test piece: 150 mW / c
m ² , integrated light amount 3000 mJ / cm ² , irradiation time 20 seconds)
And adhered.

After bonding, the test piece was hung using one hole and a 30 kg weight was hung using the other hole. However, even after 10 minutes after the load was applied, the bonded surface did not peel off.
Good adhesion was shown.

[0098]

According to the present invention, there is provided an ultraviolet-curable composition which is particularly excellent in adhesion to a thermoplastic saturated norbornene-based resin and has a high hardness when irradiated with ultraviolet rays. Method for producing a thermoplastic saturated norbornene-based resin molded article having a coat layer having excellent adhesion between a coat layer and a substrate and hardness of the coat layer, and thermoplastic saturation excellent in adhesion using the ultraviolet curable composition A method for bonding a norbornene-based resin and a body to be bonded is provided. Further, the ultraviolet curable composition of the present invention has a practically usable adhesive property with a thermoplastic saturated norbornene resin even when an effective amount of an antistatic agent is added.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08J 5/12 C08J 5/12 7/00 304 7/00 304 7/04 7/04 C09D 4/02 C09D 4/02 (72 ) Inventor Yuji Kojima 1-2-1 Nightlight, Kawasaki-ku, Kawasaki-city, Kanagawa Pref. Nippon Zeon Co., Ltd. (72) Inventor Io Natsuume 1-2-1 Nightlight, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon Zeon Co., Ltd. Kenji Hara, Examiner, Research and Development Center (56) References JP-A-61-101583 (JP, A) JP-A-3-160079 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C09J 4/02 B05D 7/24 301 B05D 7/24 302 C08F 220/18 C08F 220/20 C08J 5/12 C08J 7/00 304 C08J 7/04 C09D 4/02

Claims (7)

(57) [Claims] (1) Monofunctional (meth) acrylate is
5-65 wt%, (2) 2 or 3-functional (meth) acrylate 15-65% by weight, (3) 4 or more functional groups (main
(T) An ultraviolet-curable composition comprising 10 to 60% by weight of an acrylate and (4) a photopolymerization initiator. 2. A chain aliphatic having 5 to 18 carbon atoms monofunctional (meth) acrylate, alicyclic monofunctional (meth) acrylate, and alicyclic difunctional (meth) one or more selected from acrylate ( 2. The ultraviolet-curable composition according to claim 1, which contains 40% by weight or more of ( meth) acrylate . 3. An antistatic agent comprising (meth) acrylate and
3. The ultraviolet-curable composition according to claim 1, wherein the composition contains 1 to 7% by weight based on the total weight of the photopolymerization initiator . 4. A molded article comprising a thermoplastic norbornene-based resin having a coat layer obtained by curing the ultraviolet-curable composition according to claim 1, 2, or 3. 5. The coating layer having a surface electric resistance of 5 × 10
The molded article according to claim 4, which has a resistance of ¹³ Ω or less. 6. A molded article having at least a surface formed of a thermoplastic saturated norbornene-based resin,
A method for producing a molded article having a coat layer, comprising applying the ultraviolet-curable composition according to 2 or 3, and irradiating the composition with ultraviolet light. 7. A method for adhering a molded article having an adhesive surface made of a thermoplastic saturated norbornene-based resin and an adherend,
Applying the ultraviolet-curable composition according to claim 1, 2, or 3 to an adhesive surface of a molded article and / or an adhesive surface of an adherend, and bonding the adhesive surface of the molded article to the adhesive surface of the adherend,
A method for bonding a molded article and a body to be bonded, wherein the bonding surface is made of a thermoplastic saturated norbornene-based resin, wherein the ultraviolet-curable composition is irradiated with ultraviolet rays.