JPH05247241A - Method of bonding thermoplastic saturated norbornene resin and formation of hard coating layer - Google Patents

Abstract

PURPOSE:To bond firmly a thermoplastic saturated norbornene resin molding to an adherend or to bond firmly a hard coating layer to the surface of a thermoplastic saturated norbornene resin molding. CONSTITUTION:The surface of a thermoplastic saturated norbornene resin molding is coated with a solution of a halohydrocarbon polymer, desirably a halogenated propylene polymer, and the solvent is evaporated to form a primer layer. When it is bonded, the molding is coated with an adhesive and then bonded to an adherend. When a hard coating layer is formed on the molding, it is coated with a coating agent, and the solvent is evaporated to obtain a molding having a hard coating layer. When the coating agent is ultraviolet- curable, the curing is performed by irradiation with ultraviolet rays.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for adhering a thermoplastic saturated norbornene resin having excellent adhesiveness and a method for forming a hard coat layer.

[0002]

2. Description of the Related Art Polymethyl methacrylate (PMMA) and polycarbonate (PC) have been conventionally known as resins used for optical materials. However, PMMA is excellent in transparency, but has problems in heat resistance and humidity resistance. In addition, PC is superior in heat resistance and humidity resistance to PMMA, but has a large birefringence. Therefore, an optical material excellent in transparency, heat resistance, moisture resistance, low birefringence, etc. has been demanded.

Recently, thermoplastic saturated norbornene resins have attracted attention as optical materials excellent in transparency, heat resistance, humidity resistance and low birefringence. However, it is becoming difficult for the adhesiveness between a molded article made of a thermoplastic saturated norbornene-based resin and an adherend, and the adhesiveness between the molded article and a hard coat layer to meet the demands that increase as the technical level increases. It was

Therefore, various improvements in adhesiveness have been investigated. Among them, the method of forming the primer layer on the surface of the molded product does not require a change in the composition of the resin itself and thus can be used relatively easily. Therefore, primers having various polar groups have been tried. For example, ethylene,
Propylene, butadiene, styrene, isoprene, cyclopentadiene polymerized or copolymerized base polymer, acrylic group, carboxyl group, epoxy group,
Add polar groups such as amino group, acid anhydride group, vinyl group,
Examples thereof include those introduced by a method such as terminal modification and graft polymerization, or those obtained by polymerizing or copolymerizing a monomer having no polar group with a polar group introduced. The molecular weight, the content of polar groups, etc. were also investigated, and some improvement effect of the adhesiveness was confirmed, but the sufficient effect was not obtained.

[0005]

As a result of earnest studies, the present inventors have found that a halogenated hydrocarbon polymer primer layer is formed on a surface made of a thermoplastic saturated norbornene-based resin so as to adhere to the surface. It has been found that the adhesiveness between the agent layer or the surface and the hard coat layer becomes strong, and the present invention has been completed.

[0006]

Thus, according to the present invention, a primer layer made of a halogenated hydrocarbon polymer is formed on an adhesive surface made of a thermoplastic saturated norbornene resin or a hard coat layer forming surface. A method for adhering a thermoplastic saturated norbornene resin or a method for forming a hard coat layer is provided.

(Substrate) At least the adhesive surface or the hard coat layer forming surface of the substrate of the present invention is made of a thermoplastic saturated norbornene resin. The material and the like of the other parts are not limited.

The thermoplastic saturated norbornene-based resin is a resin known in JP-A-3-14882 and JP-A-3-122137, and specifically, a hydrogenated product of a ring-opening polymer of a norbornene-based monomer. Examples thereof include addition polymers of norbornene-based monomers, addition polymers of norbornene-based monomers and olefins, and modified products of these polymers and hydrogenated 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,
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, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene and the like; adducts of cyclopentadiene and 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, and if necessary, it may be 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.

The molecular weight is GP using cyclohexane as a solvent.
The number average molecular weight measured by C (gel permeation chromatography) analysis is suitably from 1 to 200,000. Further, from the viewpoint of light deterioration resistance and weather resistance, it is preferable that it is saturated, and therefore hydrogenation may be performed. In that case, the hydrogenation rate is usually 90% or more, preferably 95% or more, It is preferably 99% or more.

If desired, the thermoplastic saturated norbornene-based resin may include a phenol-based or phosphorus-based antiaging agent; a phenol-based thermal deterioration inhibitor; a benzophenone-based ultraviolet stabilizer; an amine-based antistatic agent. Various additives such as lubricants such as esters of aliphatic alcohols, partial esters and partial ethers of polyhydric alcohols, and the like may be added. Further, other resins and the like may be mixed and used as long as the purpose of use of the molded article after adhesion 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 thermoplastic saturated norbornene-based resin of the present invention is not particularly limited, and general molding methods for thermoplastic resins such as injection molding, melt extrusion, hot pressing, solvent casting and stretching are used. You can

(Primer) The primer of the present invention comprises a halogenated hydrocarbon polymer and usually has a molecular weight of 5,0.
00-200,000, preferably 10,000-15
10,000, more preferably 20,000 to 100,0
00. Examples of such a halogenated hydrocarbon polymer include halogenated hydrocarbon-based polymers obtained by polymerizing or copolymerizing hydrocarbon-based monomers such as ethylene, propylene, butadiene, isoprene and styrene, or vinyl chloride and benylidene chloride. , Halogen-containing monomers such as chloroprene are polymerized or copolymerized. 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 the UV-curable hard coat layer is formed, a photopolymerizable monomer, a photopolymerizable oligomer, etc., which will be described later, particularly 2 to 20 monofunctional acrylate monomers are used.
Addition by weight% is preferable because it improves the adhesiveness between the primer layer formed between the adhesive surface and the cured layer, the adhesive surface, and the hard coat layer.

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 made of a thermoplastic saturated norbornene resin or a hard coat layer forming surface and sufficiently removing volatile components in the solvent. To be done. 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 surface or the hard coat layer forming surface. Generally, 12 so that there is no thermal deformation of the molded product
The conditions may be determined at 0 ° C. or lower and so that the removal can be sufficiently performed. Specifically, it is suitable to leave it at 60 to 120 ° C. for about 3 to 60 minutes. After removing the volatile components 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.

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.

(Coating Agent) The coating agent used when forming the hard coat layer may be a silicone-based coating agent or an organic-based coating agent. Silicone-based coating agents are partial hydrolysates of silane compounds, and organic-based coating agents include coating agents that heat-cure melamine-based, alkyd-based, urethane-based, and acrylic-based coating materials, and polyfunctional acrylic-based coating agents. There is an ultraviolet curable coating agent that cures monomers and the like with ultraviolet light. The ultraviolet-curable coating agent is preferable in that it can be cured under the condition that the thermoplastic saturated norbornene-based resin is not easily deformed by heat, and that it has sufficient hardness and weather resistance.

The UV-curable coating agent of the present invention contains a reactive monomer and / or a reactive oligomer, a photopolymerization initiator and other additives, and is solvent-free or diluted with a solvent.

Acrylates are mainly used as the reactive monomer, and specifically, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate, phenoxypropyl acrylate, Other monofunctional acrylate monomers such as higher alkyl acrylates; Other monofunctional monomers such as styrene and vinylpyrrolidone; ethylene glycol, diethylene glycol, tripropylene glycol, butylene glycol, hexanediol, trimethylolpropane, tetramethylolpropane, penta Examples thereof include polyfunctional acrylate monomers in which two or more acrylates are bound to polyols such as erythritol.

As the reactive oligomer, polyester acrylate having an acroyl group at the terminal, epoxy acrylate or polyurethane acrylate having an epoxy group in the molecular chain and an acroyl group at the terminal, unsaturated polyester having a double bond in the molecular chain, Mention may be made of 1,2-polybutadiene and other oligomers having epoxy groups or vinyl ether groups.

As the photopolymerization initiator, acetophenones such as 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone and chlorinated acetophenone; benzophenones; benzyl, methylorthobenzoylbenzoate, benzoin alkyl ether And the like; 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, dibenzoyl disulfide; and the like.

In the present invention, a UV-curable coating agent comprising a monofunctional acrylate monomer, a bifunctional or trifunctional acrylate monomer, a tetrafunctional or higher functional acrylate monomer, and a photopolymerization initiator is preferable.

In the present invention, photopolymerizable monomers having one acrylate group are called monofunctional acrylate monomers, and those having two acrylate groups are called bifunctional acrylate monomers.

Examples of monofunctional acrylate monomers include n-butyl acrylate, isoamyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-ethylhexyl methacrylate, phenoxyethyl acrylate, phenoxypropyl acrylate and other higher alkyls. Examples thereof include acrylate. In order to reduce the curing shrinkage rate of the ultraviolet curable coating agent, an acrylate having a side chain of about 4 to 6 carbon atoms is preferable.

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. It is a polyol in which 2 or 3 acrylates are bonded.

Examples of the tetrafunctional or higher functional acrylate monomer include polyols such as tetramethylolpropane, pentaerythritol and dipentaerythritol.
One or more acrylates are bonded.

The mixing ratio of these is usually 25 to 60% by weight, preferably 30 to 40% by weight, of the monofunctional acrylate monomer, or the difunctional or trifunctional acrylate, based on the total weight of the acrylate monomer and the photopolymerization initiator. The monomer is 10 to 40% by weight, preferably 15 to 30% by weight, and the tetrafunctional or higher functional acrylate monomer is 20 to 50% by weight, preferably 25 to 40% by weight, and the photopolymerization initiator is 1 to
It is 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 hard coat 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 reduced, and the amount of the bifunctional or trifunctional acrylate monomer is decreased, so that the flexibility of the hard coat layer is reduced, which causes cracks. Further, in order to improve the adhesiveness, it is preferable that the amount of the bifunctional or trifunctional acrylate monomer is large.

Further, appropriate additives may be added as long as the adhesiveness and hardness of the hard coat layer are satisfied. For example, by adding a suitable surfactant, for example, a nonionic surfactant having good compatibility with an ultraviolet curing agent, particularly an amine surfactant or other antistatic agent, the surface chargeability can be improved. Alternatively, by adding a fluorine-based nonionic surfactant, wetting of the substrate and surface smoothness after the effect can be improved. Further, by adding an appropriate thermoplastic resin, the viscosity can be adjusted and the adhesiveness can be improved. As the thermoplastic resin for improving the adhesiveness, in the case of a thermoplastic saturated norbornene-based resin, a thermoplastic norbornene-based resin or a resin having a structure similar to that of the thermoplastic norbornene-based resin, for example, a ring-opening polymer of a norbornene-based monomer or dicyclopentadiene is used. Examples thereof include petroleum resins such as a system, a diene system, an aliphatic system, and a water white system, or hydrogenated products thereof.

These mixtures can be used as they are as a UV-curable coating agent, 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, chlor solvents It may be dissolved in a solvent such as a solvent to a concentration of 80% by weight or more to be used as an ultraviolet curable coating agent.

(Method of Forming Hard Coat Layer) To form the hard coat layer of the present invention, an ultraviolet curable coating agent is applied to the above-mentioned hard coat forming surface which has been subjected to the primer treatment and is irradiated with ultraviolet rays to be cured. When the UV-curable coating agent is dissolved in a solvent and used, the volatile components are sufficiently removed after the application of the UV-curable coating agent and before the next step. When the UV-curable coating agent is cured while containing a large amount of solvent, cracks tend to occur in the coating film,
It also causes the failure to obtain a coating film with high hardness.

The method of applying the ultraviolet curable coating agent is not particularly limited, and for example, spraying, dipping, spin coating, roll coater and the like are possible. The method for removing the solvent is also not particularly limited. The temperature and time required to substantially remove the solvent by volatilization differ depending on the type of solvent used, the coating amount, and the shape of the hard coat layer forming surface, but there is no thermal deformation of the thermoplastic saturated norbornene resin. As described above, the conditions may be determined so that the temperature is approximately 120 ° C. or lower and the volatile components can be sufficiently removed. Specifically, 60 to 120
A removal method at 3 ° C for about 3 to 60 minutes is suitable. After removing the solvent at a high temperature, it is preferable to perform cooling at room temperature for about 10 seconds to 10 minutes, and to cool it to near room temperature. In addition, when the solvent is not used, the removing operation by volatilization is unnecessary.

It is preferable that the coating amount be about 2 to 300 μm. When the solvent is removed, it is preferable that the above-mentioned thickness is obtained after the removal. If the coating amount of UV curable coating agent is small,
A hard coat layer having high strength cannot be obtained, and a sufficient effect of improving surface hardness cannot be obtained. When the amount is large, it takes time to remove the solvent and the curing reaction, resulting in poor productivity, and when the curing is insufficient and the hardness is low, or the hard coat layer lacks flexibility and may be cracked.

Then, by irradiating with 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 hard coat layer having high hardness is formed. The irradiation dose of ultraviolet rays varies depending on the reactivity of the photopolymerizable monomer and the photopolymerization initiator, but in the case of a high pressure mercury lamp, it is usually cured at an irradiation intensity of 150 mJ / cm ² in a short time of about 5 to 10 seconds. You can also

(Adherend) In the case of adhesion, the adherend is not particularly limited, but it is preferable that the adhered surface is made of a thermoplastic saturated norbornene-based resin like the adhesive surface of the substrate. When the adhered surface is made of a thermoplastic saturated norbornene-based resin, it is preferable to form the primer layer similarly to the adhesive surface.

(Adhesive) The adhesive used in the bonding method of the present invention is a thermosetting resin adhesive such as an epoxy resin adhesive or a silicone resin adhesive, a thermoplastic resin adhesive such as an acrylic adhesive, Elastomer adhesives such as NBR adhesives, UV curable adhesives, etc., but not limited to, thermoplastic saturated norbornene resins and components that dissolve the material of the adherend, such as thermoplastic saturated norbornene resins It is preferable that the solvent does not contain a large amount of solvent, and a monofunctional acrylate monomer, a bifunctional trifunctional acrylate monomer, or a monofunctional acrylate monomer having the same composition as that of the ultraviolet curable adhesive, particularly the aforementioned ultraviolet curable coating agent, from the viewpoint of adhesive strength. A UV-curable adhesive composed of a functional or higher acrylate monomer and a photopolymerization initiator is preferable.

(Adhesion Method) In the present invention, the adhesive is applied to the adhesive surface of the adhesive body having the primer layer or the adherend surface of the adherend.

The method of applying the adhesive, the amount of application, etc. may be determined by a method and amount suitable for the adhesive used. For example, the ultraviolet curable adhesive can be applied by spraying, dipping, spin coating, a roll coater or the like, and when it is necessary to remove the volatile component, the volatile component is sufficiently volatilized and removed. The applied amount is preferably about 10 to 400 μm, and when the volatile components are removed, it is preferable that the above thickness is obtained after the volatile components are sufficiently removed. When the coating amount is small, the adhesiveness is insufficient, and when the coating amount is large, it takes time to remove the volatile components and the curing reaction, resulting in poor productivity.

After application, the adhesive surface and the adherend surface are adhered to each other depending on the method of use of the adhesive used. For example,
In the case of a UV curable adhesive, UV irradiation is performed in the same manner as the above UV curable coating agent.

[0044]

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

(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 at intervals of 1 mm by a cutter to make 100 1-mm square crosses 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%.

Reference Example 1 Thermoplastic saturated norbornene resin (ZEONEX 28
0, manufactured by Nippon Zeon Co., Ltd.) 0.2 part by weight of a phenolic antioxidant pentaerythrityl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl)). 0.2 parts by weight of propionate) was added and pelletized by the melt extrusion method.

Reference Example 2 The pellets of Reference Example 1 were injection-molded under the following conditions to prepare a substrate having a 3.5-inch diameter compact disc standard. When the pencil hardness of this substrate was measured,
It was H. Further, aluminum was vacuum-deposited on the reflection film formation portion of the reflection film formation surface of this substrate. Molding machine: Mold clamping pressure 85 tons Resin temperature: 325 ° C Mold temperature: 110 ° C (fixed side), 100 ° C (movable side)

Reference Example 3 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 an antistatic agent (Toho Kagaku, Anstics SA-30) is further added.
0) 2 parts by weight, 500 ppm of fluorine-based nonionic surfactant (Sumitomo 3M, Florard FC-171)
And the ultraviolet curing agent was adjusted.

Example 1 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) 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 was applied to both surfaces of the substrate obtained in Reference Example 2 by a spin coater (5000 rpm,
10 seconds) and then left to dry at room temperature for 1 minute. The thickness of the primer film after drying was 2 μm.

The ultraviolet curing agent obtained in Reference Example 3 was applied to one surface of this substrate by a spin coater (5000 rpm, 10 seconds) to a film thickness of 5 μm. This substrate was irradiated with ultraviolet rays from a high-pressure mercury lamp of 80 mW (peak irradiation intensity on the surface of the substrate: 150 mW / cm ² , integrated light amount 1500 mJ / c).
m ² , irradiation time 10 seconds) to cure the ultraviolet curing agent to form a hard coat layer.

The hardness of the coated substrate surface was 3H in terms of pencil hardness. 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.

Comparative Example 1 The hard coat layer was formed by coating the substrate of Reference Example 2 with the ultraviolet curing agent of Reference Example 3 and irradiating it with ultraviolet rays in the same manner as in Example 1 except that the primer solution was not coated.

The hardness of the coated substrate surface 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.

Reference Example 4 The pellet obtained in Reference Example 1 was injection-molded under the following conditions to obtain a 100 mm × 25 mm plate-shaped molded product having a thickness of 2.5 mm. A hole having a radius of 1 mm was made at a position of 12.5 mm, and two test pieces were obtained. Molding machine: Mold clamping pressure 65 tons Resin temperature: 325 ° C Mold temperature: 110 ° C (fixed side), 100 ° C (movable side)

Example 2 The test pieces were applied to each other by brushing the primer solution of Example 1 to a thickness of 5 μm after drying, with 25 mm square at one end opposite to the holes of the test pieces as an adhesive surface, and left for 1 minute. And dried. After that, the ultraviolet curing agent of Reference Example 3 was applied to one adhesive surface by a brush with a thickness of 20 μm, and the adhesive surfaces were bonded and fixed so that the holes were opposite to each other.
Ultraviolet irradiation by a 0 mW high-pressure mercury lamp (peak irradiation intensity on the surface of the test piece: 150 mW / cm ² , integrated light quantity 3
000 mJ / cm ² and irradiation time of 20 seconds) were performed and adhered.

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.

[0059]

EFFECT OF THE INVENTION In the bonding method or the method for forming a hard coat layer of the present invention, the surface of the thermoplastic saturated norbornene resin molded product and the adherend, or the surface of the thermoplastic saturated norbornene resin molded product and the hard coat layer are firmly bonded. Can be glued to.

Claims (2)

[Claims] 1. A thermoplastic saturated norbornene-based resin characterized in that an adhesive layer or a hard coat layer is formed after forming a primer layer made of a halogenated hydrocarbon polymer on the surface of a thermoplastic saturated norbornene-based resin molded product. A resin bonding method or a hard coat layer forming method. 2. The method for adhering a thermoplastic saturated norbornene-based resin or the method for forming a hard coat layer according to claim 1, wherein the halogenated hydrocarbon polymer is a halogenated propylene polymer.