JPH083510A - New coating material and molded article having coating layer - Google Patents

Abstract

PURPOSE:To provide a molded article having a coating layer to lower the frictional coefficient and increase the slipperiness of the surface of the article, resistant to form damage on the surface of the article even by hardly rubbing the articles with each other, free from the loss of transparency by the clouding of the friction-lowering layer even by steam sterilization, free from the dissolution of component harmful to human body from the friction-lowering layer and the molded article and usable, e.g. as a container for medical use. CONSTITUTION:A friction-lowering layer composed of a copolymer of an acrylic monomer having a >=4C hydrocarbon group (e.g. lauryl acrylate) and an acrylic monomer having an epoxy group (e.g. glycidyl methacrylate) or a modified product produced by adding a polyamine (e.g. diethyltriamine) to the above copolymer is formed on the surface of a molded article (e.g. a vial) made of a norbornenebased monomer (e.g. ethyltetradecyldodecene).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having a novel coating agent and a coating layer, and more specifically, a molding having a novel coating agent and a coating layer which reduces friction on the resin surface and does not elute impurities. Regarding goods.

[0002]

2. Description of the Related Art Thermoplastic norbornene-based resins are excellent in transparency, heat resistance, chemical resistance, solvent resistance, moisture resistance, water resistance, and low elution of organic substances. Development of resins for medical use is progressing.

[0003] When a chemical container or the like is filled in a container made of a thermoplastic norbornene resin by an automated filling system, there is a problem that the outer surface of the container is likely to be scratched due to contact with a machine or contact between containers. Therefore, a method of increasing the hardness of the outer surface of the container by forming a resin coat layer having high hardness has been attempted. However, even if the surface hardness is increased, due to the large friction of the surface, a large load is easily applied at the time of contact with a machine or between containers, for example,
In the automated encapsulation system, the containers are clogged with each other in the middle of the process, and as a result, the load exceeds the limit and the outer surface is scratched.

Furthermore, in order to use it as a medicine container for medical treatment, "a disposable blood transfusion set," which is a standard based on the provisions of Article 42, Paragraph 2 of the Pharmaceutical Affairs Law,
And the standard for infusion set "," disposable syringe set ", etc., and may be required to pass the Japanese Pharmacopoeia General Test Method, Plastic Container for Infusion Test Method. In this elution test, the amount of low molecular impurities such as an additive such as an oxidation stabilizer and a residual monomer that is eluted by dipping a strip-shaped fragment obtained by vertically cutting a container into distilled water is measured. When low-molecular impurities are eluted from the coat layer formed on the outer surface, the impurities are not eluted on the inner surface that is in contact with the enclosed chemicals, and even if it does not cause hemolysis, it is judged as a failure. And
I cannot get approval. Therefore, medical containers,
When forming a coating layer on a container used as a medicine bottle, it is necessary to use a safe coating agent that does not elute impurities. However, it has been difficult to find a coating agent that satisfies both the desired effect and safety requirements.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made diligent efforts for the purpose of reducing the friction on the outer surface of a thermoplastic norbornene resin molded product and reducing the elution of impurities, and as a result, have identified a thermoplastic norbornene resin surface. It was found that by forming the friction-reducing layer made of the above resin, the friction on the surface is reduced, and a molded product having a low impurity elution property can be obtained, and the present invention has been completed.

[0006]

Thus, according to the present invention, a copolymer of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms and an acrylic monomer having an epoxy group is used as a film forming component. Provided is a molded article having a coating agent and a coating layer formed on the surface of at least a part of a base material made of a resin by a film-forming component of the coating agent.

(Acrylic monomer having a hydrocarbon group of 4 or more carbon atoms) Acrylic monomer having a hydrocarbon group of 4 or more carbon atoms used for producing a copolymer which is a film forming component of the coating agent of the present invention. As the system monomer, butyl acrylate, butyl methacrylate, isoamyl acrylate,
Examples thereof include isoamyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate and stearyl methacrylate. Among these, those having 6 or more carbon atoms are preferable, and acrylic monomers having 8 or more hydrocarbon groups are more preferable, so that the glass transition temperature of the copolymer is 0 ° C. or less, as described later, Further, an acrylic monomer having a linear hydrocarbon group is preferable.
Specifically, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate,
Lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate and the like are preferable.

(Acrylic monomer having epoxy group)
Examples of the acrylic monomer having an epoxy group used for the production of the copolymer that is the film forming component of the coating agent of the present invention include glycidyl acrylate and glycidyl methacrylate, but glycidyl methacrylate is particularly skin irritating. Is preferred because of its low toxicity.

(Copolymer) The copolymer, which is the film-forming component of the coating agent of the present invention, has 5 repeating structural units derived from an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms.
0% by weight or more and 99% by weight or less, preferably 80% by weight or more and 98% by weight or less, and 1% by weight or more and 50% by weight or less, preferably 2% by weight or less of repeating structural units derived from an acrylic monomer having an epoxy group. It is above 20% by weight. This polymer becomes brittle when the amount of the acrylic monomer is too small, and when it is too large, the effect of reducing the friction on the surface of the molded article of the present invention is small and the polymer is easily scratched.

In order to obtain a copolymer which is a film-forming component of the coating agent of the present invention, 50% by weight or more and 99% by weight or less, preferably 80% by weight, of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms. % To 98% by weight and an epoxy group-containing acrylic monomer 1% to 50% by weight, preferably 2% to 20% by weight in a solvent, preferably in a nitrogen atmosphere. Then, polymerization is carried out using a radical polymerization initiator.

The solvent used is not particularly limited as long as it can dissolve the monomer and the copolymer, and hydrocarbons such as cyclohexane, benzene, xylene and toluene;
Examples thereof include esters such as ethyl acetate and butyl acetate; ketones such as methyl isobutyl ketone and methyl ethyl ketone. 0.5 to 10 parts by weight of solvent, preferably 1 to 7 parts by weight, relative to 1 part by weight of the monomer mixture,
More preferably, 2 to 5 parts by weight is used. If the amount of the solvent used is too small, the molecular weight becomes large, and if it is too large, the molecular weight becomes small.

As the radical polymerization initiator to be used, acetyl peroxide, cumyl peroxide, tert-butyl peroxide,
Peroxides such as propionyl peroxide and benzoyl peroxide; 2,2′-azobisisobutyronitrile, 2,2 ′
-Azo compounds such as azobis-2-methylbutyronitrile; and the like. The radical polymerization initiator is 0.002 to 0.05 parts by weight with respect to 1 part by weight of the monomer mixture,
The amount is preferably 0.005 to 0.04 parts by weight, more preferably 0.01 to 0.03 parts by weight. If the amount of radical polymerization initiator used is too small, the molecular weight becomes large, and if it is too large, the molecular weight becomes small.

The polymerization temperature depends on the radical polymerization initiator used,
Depending on the boiling point of the solvent used, it is preferable to carry out refluxing at or above the decomposition temperature of the radical polymerization initiator, near the boiling point of the solvent.For example, azobisisobutyronitrile was used as the radical polymerization initiator, and ethyl acetate was used as the solvent. In this case, 70 to 77 ° C is preferable. Usually, it is carried out at 0.8 to 1.2 atm, preferably under normal pressure. If the reaction temperature is too low, the polymerization cannot be started and the production efficiency is poor. If the reaction temperature is too high, the reaction cannot be controlled and bumping may occur.

The reaction stops when all the monomers have been consumed. Under the above conditions, it stops within 7 hours, but depending on the formulation, it may stop within 3 hours.

When recovering the copolymer, the solvent is removed. The method of removing the solvent is not particularly limited, and, for example, the reaction solution is heated under reduced pressure to volatilize. In addition, if the solvent used in the reaction does not dissolve the resin constituting the base material, the solvent obtained by volatilizing a part of the solvent of the reaction solution, the solvent added to the reaction solution, or the reaction solution itself is used. You may use it as a coating agent of the invention. Further, in the case of carrying out polyamine addition modification described later, similarly, polyamine may be further added to obtain the coating agent of the present invention.

The resulting copolymer of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms and an acrylic monomer having an epoxy group is a number average in terms of polystyrene by gel permeation chromatography. Molecular weight 5,
000 or more, preferably 7,000 or more, 100,00
It is 0 or less, preferably 20,000 or less. If the molecular weight is too large, the surface of the coating layer of the molded article of the present invention becomes sticky, and if it is too small, the coating layer easily separates from the surface of the base material of the molded article of the present invention by steam sterilization. Further, the glass transition temperature of the copolymer is preferably 0 ° C. or lower in order to reduce the friction on the surface of the coating layer of the molded article of the present invention and prevent scratches.

(Polyamine) Further, the film forming component of the coating layer of the present invention may contain polyamine as the second component. By adding a polyamine to the copolymer, which is the first component, and modifying it, the coat layer becomes more difficult to peel from the base material of the molded article of the present invention. For example, even if steam sterilization is repeated, peeling is difficult and the effect is unlikely to decrease.

The polyamine as the second component is not particularly limited, and includes diethylenetetramine, triethylenetetramine,
Chain-like aliphatic polyamines such as diethylenetriamine, tetraethylenepentamine, dipropylenediamine and diethyleneaminopropyneamine; cyclic aliphatic polyamines such as N-aminoethylpiperazine, mensendiamine and isophoronediamine; m-xylenediamine and the like Aromatic polyamines are exemplified. Further, commercially available heterocyclic polyamines (for example, Epomate manufactured by Yuka Shell Epoxy Co., Ltd.) and modified polyamines (for example, Adeka Hardener manufactured by Asahi Denka Co., Ltd.) can also be used.

The modification reaction itself is usually carried out by applying a coating agent to a molded article which is a base material and then heating it to remove the solvent.

(Coating agent) The coating agent of the present invention contains the above-mentioned copolymer as a film-forming component, and is usually a film-forming component diluted with a solvent.

The solvent used as the diluting component of the coating agent is
A resin that does not dissolve the resin constituting the molded article that is the base material and is highly volatile in terms of easy removal of the solvent is preferable, for example, a halogenated hydrocarbon such as dichloromethane or chloroform; diethyl ether, THF, etc. Ethers; ketones such as methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone; ethyl acetate,
Esters such as butyl acetate; and the like.

The amount of the copolymer in the coating agent is 0.1% by weight or more, preferably 0.2% by weight or more, more preferably 1% by weight or more, particularly preferably 2% by weight or more, and 10% by weight or more.
It is not more than 6% by weight, preferably not more than 6% by weight. If the concentration is too high, the tackiness increases and the work efficiency of coating decreases. If the concentration is too low, it will be difficult to apply a sufficient thickness.

When polyamine is added, the amount of active hydrogen of the amine is 2. with respect to 1 equivalent of the epoxy group contained in the copolymer, usually 1 equivalent of the epoxy group contained in the monomer mixture used for the copolymerization. The polyamine is added so as to be 0 equivalent or less, preferably 0.5 equivalent or more and 1.5 equivalent or less. When the amount is too small, the effect of addition modification is small, and when the amount is too large, unreacted polyamine is likely to remain after modification, which may become an impurity in the coat layer.

(Resin) The resin constituting the molded article as the base material of the present invention is not particularly limited, but a thermoplastic resin is preferable from the viewpoint of easy molding, and transparency, heat resistance, low elution of organic substances, etc. From the viewpoint, a thermoplastic norbornene-based resin is preferable.

The thermoplastic norbornene resin used in the present invention is disclosed in JP-A-51-80400 and JP-A-60-2.
6024, JP 1-168725, JP 1-190726, JP 3-14882, JP 3-122137, JP 4-638.
No. 07, etc., specifically, ring-opening polymers of norbornene-based monomers, hydrogenated products thereof, addition-type polymers of norbornene-based monomers, norbornene-based monomers and olefins. And addition type copolymers thereof.

The norbornene-based monomer is also a monomer known in the above-mentioned publications, JP-A-2-227424 and JP-A-2-276842, and examples thereof include norbornene, its alkyl, alkylidene, and aromatic. Substituted derivatives and halogens of these substituted or unsubstituted olefins,
Polar group substituents such as hydroxyl group, 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, 5-hexyl-2-norboernene, 5-octyl-2-norbornene, 5-
Octadecyl-2-norbornene, etc .; Monomers in which one or more cyclopentadiene is added to norbornene, derivatives or substitution products similar to the above, for example, 1,4: 5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-
2,3-cyclopentadienooctahydronaphthalene,
6-methyl-1,4: 5,8-dimethano-1,4,4
a, 5,6,7,8,8a-octahydronaphthalene,
1,4: 5,10: 6,9-trimethano-1,2,3,3
4,4a, 5,5a, 6,9,9a, 10,10a-dodecahydro-2,3-cyclopentadienoanthracene, etc .; a polycyclic monomer which is polymerized by a Diels-Alder reaction of cyclopentadiene; Derivatives and substituents similar to the above, for example, dicyclopentadiene, 2,
3-dihydrodicyclopentadiene and the like; adducts of cyclopentadiene and tetrahydroindene and the like, derivatives and substitution products similar to the above, for example, 1,4-methano-
1,4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4
a, 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 a 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. In addition, in order to obtain a resin excellent in moisture resistance and chemical resistance, a thermoplastic norbornene-based resin containing no polar group is preferable.

In the present invention, the number average molecular weight of the thermoplastic norbornene-based resin is the GPC with a toluene solvent.
The polystyrene conversion value measured by the (gel permeation chromatography) method is 10,000 to 200,
000, preferably 15,000 to 100,000, more preferably 20,000 to 50,000. Further, when the thermoplastic norbornene-based resin has an unsaturated bond in the main chain structure, it can be made into a thermoplastic saturated norbornene-based resin by hydrogenation. In the case of hydrogenation, the hydrogenation rate is 90% or more, preferably 95%, from the viewpoint of heat deterioration resistance and light deterioration resistance.
Or more, more preferably 99% or more.

When used for medical purposes, it is preferable that the transition metal derived from the polymerization catalyst does not remain in the resin and is not eluted. Pore volume 0.5 cm ³ /
g or more, preferably 0.7 cm ³ / g or more, preferably a specific surface area of 250 cm ² / g or more, a heterogeneous catalyst in which a hydrogenation catalyst metal such as nickel is supported on an adsorbent such as alumina. Hydrogenate the polymer using
The residual amount of each transition metal atom derived from the polymerization catalyst in the resin is treated by treating the resin solution with such an adsorbent to adsorb metal atoms or repeatedly washing the resin solution with acidic water and pure water. Can be 1 ppm or less.

Further, the higher the glass transition temperature of the thermoplastic norbornene resin used in the present invention is, the more preferable it is. When it is used for medical purposes, it is preferably 105 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. belongs to. Some sterilization methods do not require heating such as γ-ray irradiation, but the simplest sterilization methods include methods that require heating, particularly boiling methods and steam sterilization methods. Glass sterilization temperature is 105 ℃ in sterilization by boiling
If the above conditions are satisfied, steam sterilization requires different heat resistance depending on the temperature setting during sterilization. The most common steam sterilization is a method performed at 121 ° C using an autoclave. In this case, a glass transition temperature of 130 ° C. or higher is preferable. Generally, the more the number of monomers having a large number of rings, the higher the glass transition temperature of the resin becomes.
The hydrogenated product of a ring-opening polymer containing only monomers having 4 or more rings is
It usually has a glass transition temperature of 130 ° C. or higher. Further, in the case of the addition type polymer, the glass transition temperature is 300 ° C. or higher even for the addition type polymer of norbornene. However, if the glass transition temperature is too high, there are adverse effects such as difficulty in injection molding. Therefore, select a monomer, comonomer, polymerization method, etc. to produce a thermoplastic norbornene resin with a glass transition temperature according to the purpose. do it.

Further, the thermoplastic norbornene-based resin includes
Various additives may be added as long as the object of the present invention is not impaired. For example, in the case of thermoplastic norbornene-based resin, phenol-based or phosphorus-based antioxidants; phenol-based thermal deterioration inhibitors; benzophenone-based UV stabilizers; amine-based antistatic agents; aliphatic alcohols Lubricants such as esters, partial esters of polyhydric alcohols and partial ethers; and the like may be added, and other resins, rubbery polymers and the like may be mixed and used. In particular, a rubbery polymer having a glass transition temperature of 40 ° C. or lower is 0.01 to 10% by weight, preferably 0.02 to 5% by weight, more preferably 0.05 to 1% by weight, and particularly preferably 0.1 to 0. One having 5% by weight dispersed in a thermoplastic norbornene-based resin as a microdomain having a particle size of 0.3 μm or less, preferably 0.2 μm or less is excellent as a medical resin. If too much is added, transparency,
The glass transition temperature, heat resistance, etc. are reduced. If the amount added is too small, it may become cloudy due to steam sterilization and the transparency may be lost. In addition, by forming the microdomains, light rays having a wavelength equal to or larger than the particle diameter are less likely to be scattered and excellent in transparency. A rubbery polymer having a glass transition temperature of 40 ° C. or lower is difficult to elute and is difficult to modify the drug. In addition, although there are cases where the glass transition temperature of the block copolymer or the like is two or more, the lowest glass transition temperature may be 40 ° C. or lower. As such a rubbery polymer, a copolymer of an aromatic vinyl monomer and a conjugated diene monomer,
A norbornene-based rubbery polymer that is incompatible with the hydrogenated product and the used thermoplastic norbornene-based resin is preferable.

(Substrate) The substrate used in the present invention is a resin molded product. The molding method is not particularly limited. When a thermoplastic norbornene-based resin is used, it is possible to use injection molding, melt extrusion, hot pressing, solvent casting, stretching and the like, which are general molding methods for thermoplastic resins.

The shape of the molded article is not particularly limited, and may be a desired shape depending on the application, and a preferable application is, for example, a chemical container required to have a low impurity elution property, particularly a medicine bottle.

(Formation of Hard Coat) In the production of the molded article of the present invention, a hard coat layer may be formed on the surface to be formed prior to forming the friction reducing layer.

Before forming the hard coat layer, the surface to be formed may be subjected to a surface modification treatment. The surface tension of the untreated thermoplastic norbornene-based resin is usually about 25 to 40 dyne / cm. In one of the methods for producing a molded article of the present invention, the surface tension of the surface of the molded article made of a thermoplastic norbornene-based resin is 50 dyne / cm or more, preferably 60 dyne / cm or more, and more preferably Is 70 dy
You may modify so that it may become ne / cm or more. The surface modification treatment is not particularly limited, and specific examples thereof include energy ray irradiation treatment and chemical treatment. These treatments are preferably not performed from the viewpoint of production efficiency, but are preferably performed from the viewpoint of adhesion to the hard coat layer, so that the necessity of the treatment is determined according to the purpose.

Examples of the energy ray irradiation treatment include corona discharge treatment, plasma treatment, electron beam irradiation treatment and ultraviolet ray irradiation treatment. From the viewpoint of treatment efficiency, corona discharge treatment and plasma treatment, particularly corona discharge treatment are preferable. The energy beam irradiation treatment conditions are not particularly limited as long as the desired surface modification is performed, and a known method may be used. For example, in the case of corona discharge treatment, the conditions known in JP-B-58-5314 and JP-A-60-146078 may be used.
Also, in the case of plasma treatment, the conditions known in Japanese Patent Publication No. 53-794 and Japanese Patent Laid-Open No. 57-177032 may be used.

The chemical treatment may be carried out by immersing in a potassium dichromate solution, an aqueous oxidizer solution such as concentrated sulfuric acid, and thoroughly washing with water. Although it is efficient to shake in a state of being immersed, there is a problem that the surface is dissolved and the transparency decreases when treated for a long period of time, and particularly in a thermoplastic norbornene-based resin having a polar group,
It is necessary to adjust the treatment time depending on the reactivity and concentration of the chemicals used.

Further, a primer treatment may be carried out before the formation of the hard coat layer. The primer is not particularly limited. When the hard coat layer is formed of a UV-curable polyfunctional acrylic hard coat agent, for example, the molecular weight is 5,000 to 200,000, preferably 10,000.
˜150,000, more preferably 20,000 to 10
A halogenated hydrocarbon polymer having a halogen content of 10,000 and a halogen content of 15 to 55% by weight, preferably 20 to 45% by weight, more preferably 25 to 35% by weight can be used as a primer. When the hard coat layer is formed with a silicone hard coat agent, the one used as a primer for a silicone hard coat agent on a substrate made of polycarbonate or polymethylmethacrylate can be used, and examples thereof include a thermoplastic acrylic resin. . In addition, before forming the primer layer of the silicone-based hard coat agent primer, a modified product obtained by introducing a polar group into a copolymer of a vinyl aromatic compound and a conjugated diene or a hydrogenated product thereof, or a propylene / ethylene copolymer Although it is possible to form a primary primer layer composed of a modified product in which a polar group is introduced into the united body to make it difficult to peel off the hard coat layer,
A colorant may be added to these modified products to uniformly disperse the colorant in the primary primer layer.

As the hard coating agent used for forming the hard coating layer, a silicone type or organic type hard coating agent is usually used. Of these, the silicone-based hard coating agent tends to leave monomer, and if it remains,
Since it is highly toxic to the human body, it is usually not used for medical purposes, especially for chemical containers. On the other hand, organic hard coating agents are preferable because they are relatively safe and can be easily applied, and they can be widely used in medical applications. As the organic hard coat agent, a UV-curable polyfunctional acrylic hard coat agent having excellent hardness and weather resistance is preferable. Further, a hard coat agent is selected according to the application. For example, in a chemical container or the like, a hard coat agent capable of forming a hard coat layer having a low impurity elution property is selected.

Curing of the hard coat agent is carried out by a method suitable for each hard coat agent. To cure the silicone-based hard coat agent, generally 80 to 140 ° C,
It is preferably heated at 100 to 120 ° C. for 1 to 2 hours.
Further, in the case of an ultraviolet curable hard coat agent, ultraviolet rays are radiated and cured using a high pressure mercury lamp or the like. The amount of energy to be applied varies depending on the composition, thickness, etc. of the coating agent, but is usually 5 to 3 using a high pressure mercury lamp of 80 mW.
In a time of about 0 seconds, the integrated light amount is 700 to 1500 mJ / c
Irradiate about m ² .

(Formation of Coat Layer) The coating agent of the present invention is applied to a base material which is a resin molded product and dried to form a coating layer on the outer surface of the molded product by a film forming component. By forming this coat layer, surface friction can be reduced.

The coating method is not particularly limited, and a usual coating method such as brush coating, dipping, spraying, spin coating or roll coater may be used. The drying method is also not particularly limited as long as it is a method capable of removing the solvent without deteriorating the resin or the coating layer or scratching, and may be a heating drying method, a reduced pressure drying method, a heating reduced pressure drying method, an air drying method, or the like. Good.
For example, in the case of the solvent for the coating agent exemplified above, 110
By performing the treatment at 5 ° C. for 5 minutes or more, the solvent can be removed to the extent that there is substantially no problem.

When the polyamine is added, that is, when the polyamine is added to the copolymer to modify the copolymer, it is always 80
The treatment is carried out at a temperature not lower than 0 ° C. and lower than the glass transition temperature of the used thermoplastic norbornene-based resin for not less than 5 minutes, preferably not less than 10 minutes, more preferably not less than 1 hour and not more than 2 hours to remove the solvent and carry out polyamine addition modification. If the time is too short, the modification is insufficient and the polyamine may remain and become an impurity. If the time is too long, the efficiency will be poor.

(Molded Article Having Coat Layer) The molded article of the present invention is formed by the film forming component of the coating agent of the present invention on at least a part of the surface of a base material made of a resin, that is, the above-mentioned copolymer It is a molded article having a coat layer composed of a united product or a polyamine addition modified product thereof. This molded article shows good results in the eluate test and the hemolytic test based on the Japanese Pharmacopoeia 12th revised general test method “Plastic test method for infusion”. Therefore, drug containers, syringes,
It can be used as a medical device such as an infusion tube.

The coat layer formed of the above-mentioned copolymer or its polyamine addition modified product is not a hard coat layer but a very soft layer and is not adhered to the surface of the resin molded article as the base material. Absent. However, the coating layer of the coating agent of the present invention is a coating layer, or a coating layer composed of a modified product obtained by adding a polyamine to the copolymer,
Difficult to peel off from the substrate surface. For example, the coating layer formed on the surface of the thermoplastic norbornene-based resin molded product and comprising the copolymer or the modified product has a normal condition, that is, 110.
It does not peel off from the surface of the molded product by steam sterilization at 130 ° C for 1 hour or less. Further, this coat layer reduces friction after steam sterilization as before the sterilization, thereby preventing the surface of the molded article from being damaged.

When the coating layer of the molded article of the present invention is composed of the above-mentioned copolymer, it may be peeled off by repeated steam sterilization, but when it is composed of a copolymer polyamine addition modified product, peeling is difficult. , Usually steam sterilization 3
Does not peel off after repeated use.

The thickness of the coat layer is 0.1 μm after removing the solvent.
m or more, preferably 0.2 μm or more, particularly preferably 0.5 μm or more and 10 μm or less, preferably 5 μm or less. If it is too thin, the friction cannot be sufficiently reduced, and if it is too thick, the transparency of the molded product may be lost.
Further, if the residual solvent amount is high, it may cause foaming during steam sterilization and may fail the dissolution test. Therefore, the residual solvent amount in the formed coat layer is 5
It is preferably 0 ppm or less.

[0048]

INDUSTRIAL APPLICABILITY The molded article of the present invention whose surface is coated with the copolymer of the present invention or the modified product of the present invention has a small friction coefficient on the surface of the formed copolymer layer or modified product layer. Therefore, there is no problem of scratching even if strongly rubbed, peeling off by steam sterilization, transparency loss due to cloudiness of the coating layer, etc. It is safe when used in containers.

Further, as the present invention and its embodiment,
(1) A coating agent containing a copolymer of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms and an acrylic monomer having an epoxy group as a film forming component, (2) a system of thermoplastic norbornene The resin is a rubbery polymer having a glass transition temperature of 40 ° C. or lower, 0.01 to 10% by weight, and having a particle size of 0.3 μm.
The coating agent according to (1), which is dispersed as m or less microdomains, and (3) the repeating structural unit derived from an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms, 50 to 99% by weight, and 50 to 1% by weight of a repeating structural unit derived from an acrylic monomer having an epoxy group (1) to
(2) The coating agent, (4) The number average molecular weight of the copolymer is 5,000 to 100,000 in terms of polystyrene by gel permeation chromatography, and the coating agent according to (1) to (3). (5) The coating agent according to (1) to (4), wherein the glass transition temperature of the copolymer is 0 ° C. or lower, and (6) the acrylic monomer having a hydrocarbon group having 4 or more carbon atoms is butyl. Acrylate, butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate,
Lauryl acrylate, lauryl methacrylate, stearyl acrylate, or stearyl methacrylate, the coating agent according to (1) to (5), (7) the acrylic monomer having a hydrocarbon group having 4 or more carbon atoms has 6 or more carbon atoms. The coating agent according to (1) to (6), which is an acrylic monomer having a linear hydrocarbon group, and (8) the acrylic monomer having an epoxy group is glycidyl acrylate or glycidyl methacrylate (1 ) ~
(7) The coating agent, (9) The coating agent according to (1) to (8), which further contains a polyamine as a film-forming component, (10) The polyamine is a linear aliphatic polyamine, a cycloaliphatic polyamine, or an aroma. (9) The coating agent according to (9), which is a group polyamine, (11) The polyamine is diethylenetetramine, triethylenetetramine, diethylenetriamine, tetraethylenepentamine, dipropylenediamine, diethyleneaminopropyneamine, N-aminoethylpiperazine, mensendiamine. , Isophoronediamine, or m-xylenediamine (9) to
(10) The coating agent according to the above item (12), wherein the modified polyamine is a product obtained by adding and heating a polyamine having an active hydrogen amount of the amine of 2.0 equivalents or less per 1 equivalent of the epoxy group of the copolymer. (9) to (11) the coating agent, (13) a coating layer formed by the film forming component of the coating agent of (1) to (12) on at least a part of the surface of the substrate made of resin. Articles having (14)
The molded article according to (13), wherein the coat layer comprises a copolymer of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms and an acrylic monomer having an epoxy group.
5) The coating layer comprises a modified product obtained by adding polyamine to a copolymer of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms and an acrylic monomer having an epoxy group (14). (16) The molded product of (16), wherein the resin forming the base material is a thermoplastic norbornene-based resin (13) to (1)
The molded product according to 5). (17) The residual amount of each transition metal atom derived from the polymerization catalyst of the thermoplastic norbornene resin is 1 ppm.
(16) A molded article according to (16), wherein the coating layer has a thickness of 0.1 to 10 μm (13) to (1).
(7) Molded product, (19) The amount of residual solvent in the coating layer is 50 ppm or less (13) to (18), (20) A container having a coating layer on the outer surface (13). To (19), (21) medical devices, (13) to (20), and the like.

[0050]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Comparative Examples. The steam sterilization treatment, friction coefficient measurement, shaking test, eluate test and hemolytic test were carried out as follows.

(Steam sterilization treatment) 1 in autoclave
The treatment was performed at 21 ° C. for 30 minutes.

(Measurement of Friction Coefficient) Thickness of 120 μm as a sample
Using a sheet of m, a friction coefficient measuring device (HEIDON-14SANL manufactured by Shinto Kagaku Co., Ltd.) was used to measure the friction coefficient between a 10 mmφ SUS ball under a load of 200 g and a pulling speed of 1000 mm / min. did.

(Shaking test) Inner dimensions of 155 mm in length and 2 in width
In a container made of Styrofoam with 55 mm and height of 40 mm,
The container B obtained in Reference Example 1 below was provided with a friction-reducing layer as described in Example 1 on the outer surface of the container B.
A total of 60 pieces are arranged side by side, with an amplitude of 5 cm in the horizontal direction.
It was shaken once per second for 24 hours.

(Eluate Test and Hemolytic Test) Based on the Japanese Pharmacopoeia 12th revised general test method “Plastic test method for infusion solution”, an eluate test and a hemolytic test were carried out. The cut pieces used in any of the tests had a friction-reducing layer formed on the outer surface of the container B obtained in Reference Example 1 as described in Example 1, and the side surface had a length of 5 cm and a width of 0.5 cm. The cut one was used. In the eluate test, 240 cut pieces were used. The test liquid A and the blank test liquid A ′ used for the hemolytic test were prepared according to the acute toxicity test of “Plastic test method for infusion”, and the test liquid A was prepared by using 180 cut pieces. Furthermore, 7 to 8 ml of the supernatant of the liquid subjected to the visual hemolysis test was sampled, and the visible light absorption spectrum of this liquid was measured under the following conditions. When the supernatant was 2.0% or less, it was evaluated that there was no hemolytic property. Measuring device: JASCO Corporation spectrophotometer U-best30 type cell: 10 mm quartz cell Control solution: Test solution A, physiological saline used for hemolytic test Sample solution: A'supernatant, A'supernatant

Reference Example 1 60 parts by weight of ethyl tetracyclododecene, 600 parts by weight of cyclohexane and 6.0 parts of 1-hexene under nitrogen substitution.
Parts by weight, 45 parts by weight of triethylaluminum 15% by weight toluene solution and 15.0 parts by weight of triethylamine are added, and the mixture is kept at 20 ° C. while stirring, and 240 parts by weight of ethyl tetracyclododecene and 20% by weight titanium tetrachloride in toluene solution 27 0.0 weightless was continuously added over 60 minutes. Then, after reacting for 1 hour, ethyl alcohol 1
The reaction was stopped by adding 5.0 parts by weight and 6.0 parts by weight of water. After the reaction solution was heated to 40 ° C. to hydrolyze the catalyst, 9 parts by weight of calcium sulfate and 180 parts of cyclohexane were added.
Parts by weight were added to remove excess water. The precipitated metal-containing precipitate was removed by filtration to obtain 1113 parts by weight of a transparent polymer solution containing an ethyltetracyclododecene ring-opening polymer.

To 750 parts by weight of this polymer solution, Ni-
Add 15 parts by weight of diatomaceous earth catalyst (N113, manufactured by JGC Chemical Co., Ltd.), put in a pressure resistant reactor, introduce hydrogen, and pressurize at a pressure of 50.
A hydrogenation reaction was carried out at a temperature of 200 ° C. for 3 hours at kg / cm ³ . After completion of the reaction, 700 parts by weight of cyclohexane was added for dilution, and the catalyst was removed by filtration to obtain 1350 parts by weight of hydrogenated solution of ethyltetracyclododecene ring-opening polymer.

[0057] poured while stirring the hydrogenated product solution 550 parts by weight of the isoprene <br/> b Pi alcohol 1500 parts by weight and allowed to coagulate the ring-opening polymer hydrogenation product. The solidified ring-opening polymer hydrogenated product was collected by filtration, washed twice with 300 parts by weight of isopropyl alcohol, and then dried in a rotary vacuum dryer at 5 torr and 120 ° C. for 48 hours to obtain ethyl tetracyclododecene. 52 parts by weight of a hydrogenated product of a ring-opening polymer was obtained.

100 parts by weight of the hydrogenated product of this ring-opening polymer was retained in a column having an inner diameter of 10 cm and a length of 100 cm filled with 900 parts by weight of a cyclohexane solution and 4,5 parts by weight of activated alumina (Neobead D manufactured by Mizusawa Chemical Co., Ltd.). It was passed for 100 seconds and circulated for 24 hours. Pour into 2500 parts by weight of isopropyl alcohol while stirring,
The ring-opened polymer hydrogenated product was solidified. The solidified ring-opening polymer hydrogenated product was collected by filtration, washed twice with 430 parts by weight of isopropyl alcohol, and then dried at 5 torr and 120 ° C. for 48 hours in a rotary vacuum drier to open ethyl tetracyclododecene. 78 parts by weight of hydrogenated ring polymer was obtained.

The molecular weight of the hydrogenated product of this ring-opening polymer was calculated by gel permeation chromatography as a polystyrene equivalent number average molecular weight of 28,000, weight average molecular weight of 58,000, hydrogenation rate of 99.8 or more, and differential scanning. Glass transition temperature 142 ° C, molecular weight 2,0 by calorimetric analysis
Less than 0.1% of resin component less than 00, titanium atomic weight 1 pp
m (detection limit) or less, nickel atomic weight 0.1 ppm (detection limit) or less, aluminum atomic weight 0.21 ppm,
The chlorine atom weight was 0.37 ppm.

0.2 parts by weight of a rubbery polymer (Tuftec H1052, glass transition temperature 0 ° C. or lower, manufactured by Asahi Kasei), 99.8 parts by weight of this ring-opening polymer hydrogenated product, an antioxidant (Irganox 1010, Ciba Geigy). (Manufactured by Mitsui Chemicals Co., Ltd.) 0.05 part by weight, and a twin-screw kneader (TEM-35B, screw diameter 37 mm, L / D = 32, screw rotation speed 250 r
pm, resin temperature 265 ° C., feed rate 10 kg / hour) and kneaded to obtain extruded pellets.

This pellet was blown into a container B (diameter 25 mm, height 50 mm, thickness 2 mm) having a cylindrical side surface and one bottom surface at a mold temperature of 100 ° C., a resin temperature of 290 ° C., and an air pressure of 5 kg / cm ^2. Molded.

Also, 5 g of this pellet was added to 30 cm × 30
cm, 100 μm thick, made of SUS, chrome-plated on the surface, and scissors on two mirror-finished metal plates, 12
A 0 μm spacer was inserted and pressed in a press molding machine heated to 220 ° C. for about 2 minutes, and the edge of the obtained sheet was cut to produce a sheet C having a size of 15 cm × 20 cm and a thickness of 120 μm.

Example 1 95 parts by weight of lauryl acrylate (Kyoeisha Chemical, light acrylate LA), 5 parts by weight of glycidyl methacrylate (Kyoeisha Chemical, light ester G), and azobisisobutyronitrile 2 as a polymerization initiator Add parts by weight to 400 parts by weight of ethyl acetate, and in a nitrogen atmosphere at 70 ° C.
The resulting mixture was stirred for 3 hours, and an ethyl acetate solution of a copolymer having a number average molecular weight of 12,000 in terms of polystyrene by gel permeation chromatography and a glass transition temperature of -9.2 ° C was obtained. This copolymer is a film forming component of the coating agent of the present invention. When this solution was analyzed, both lauryl acrylate and glycidyl methacrylate were below the detection limit. 1 part by weight of this solution was added to 99 parts by weight of ethyl acetate to obtain a diluent. This solution and diluent are the coating agent of the present invention.

Example 2 To the diluent obtained in Example 1, the container B obtained in Reference Example 1 was applied by dipping so that the diluent did not enter the inside and applied to the entire outer surface. The thickness of the coat layer obtained by drying at 90 ° C. for 1 hour was about 0.5 μm, and the container B having the coat layer was transparent. The container B having this coat layer is the molded product of the present invention.

As a result of the shaking test, no scratch was found on the surface. As a result of the eluate test, foaming disappeared within 3 minutes, pH difference was 0.01, ultraviolet absorption was 0.002, and potassium permanganate reducing substance was 0.13 ml. In addition, the result of the hemolytic test showed that no hemolytic property was visually observed, and the blank physiological saline and the hemolytic test solution were 540 nm.
The difference in light transmittance was 0.4%.

After the steam sterilization treatment, the shaking test was conducted again, but no scratch was observed on the surface.

The sheet C obtained in Reference Example 1 was used in Example 1
It was dipped in the diluted solution obtained in 1. and dried at 90 ° C. for 1 hour. Sheet C having a coat layer was transparent.

When the friction coefficient of this coat layer was measured, the static friction coefficient was 0.11 and the dynamic friction coefficient was 0.05.

After the steam sterilization treatment, the friction coefficient was measured again, but no change was observed.

Example 3 A solution was prepared by adding 0.00008 parts by weight of diethylenetriamine to 100 parts by weight of the diluted solution obtained in Example 1. The prepared diluted solution is the coating agent of the present invention containing polyamine as the second component of the film-forming component. This prepared diluted solution was used in place of the diluted solution obtained in Example 1, and drying was performed at 90 ° C. for 1 hour at 120 ° C. for 10 hours.
A transparent thickness of about 0.5 is obtained as in Example 2 except that the time is set to 5 minutes.
A container B having a coat layer of μm was obtained. What constitutes this coat layer is a polyamine addition modified product, and the container B having the coat layer is the molded product of the present invention.

As a result of the shaking test, no scratch was found on the surface. As a result of the eluate test, foaming disappeared within 3 minutes, pH difference was 0.02, ultraviolet absorption was 0.001, and potassium permanganate reducing substance was 0.15 ml. In addition, the result of the hemolytic test showed that no hemolytic property was visually observed, and the blank physiological saline and the hemolytic test solution were 540 nm.
The difference in light transmittance was 0.2%.

After the steam sterilization treatment, the shaking test was conducted again, but no scratch was observed on the surface.

Furthermore, after performing a steam sterilization treatment twice, a shaking test was conducted, but no scratch was observed on the surface.

The sheet C obtained in Reference Example 1 was used as Reference Example 2
The diluted solution (100 parts by weight) obtained by adding 0.00008 parts by weight of diethylenetriamine was dipped and dried at 120 ° C. for 10 minutes. Sheet C having the friction reducing layer was transparent.

When the friction coefficient of this friction reducing layer was measured, the static friction coefficient was 0.10 and the dynamic friction coefficient was 0.03.

After two more steam sterilization treatments,
When the friction coefficient was measured again, the static friction coefficient was 0.10 and the dynamic friction coefficient was 0.03.

When the coefficient of friction of this friction-reducing layer was measured twice by steam sterilization, the static coefficient of friction was 0.1.
2. The dynamic friction coefficient was 0.05.

Comparative Example 1 A shaking test was conducted using the container B obtained in Reference Example 1, and as a result, 41 out of 60 samples were visually observed to have white stripe-like scratches. Further, when the friction coefficient was measured using the sheet C obtained in Reference Example 1, the static friction coefficient was 0.15 and the dynamic friction coefficient was 0.10.

Comparative Example 2 10 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of 1,6-hexanediol diacrylate, 3 parts by weight of a photopolymerization initiator (Irgacure 184, manufactured by Ciba-Geigy), a silicone-based surfactant (FC- 430,
Sumitomo 3M) 0.1 part by weight of isopropyl alcohol 8 parts
It was dissolved in 0 part by weight to obtain a hard coat agent.

To this hard coat agent, the container B obtained in Reference Example 1 was applied by dipping so that the hard coat agent would not come into contact with the inside. After leaving it at 50 ° C. for 1 minute to volatilize isopropyl alcohol, UV irradiation is performed at 10000 mJ / cm ² by a high pressure mercury lamp for 2 minutes to cure the hard coating agent, and the outer surface of the container B is approximately A hard coat layer having a thickness of 1 μm was formed.

The pencil hardness of the hard-coated outer surface of the container B was 3H, but as a result of the shaking test, 19 of 60 samples were scratched to the extent that they could be visually discerned.

Further, the sheet C obtained in Reference Example 1 was similarly dipped, dried and cured on this hard coat agent,
A hard coat layer was formed on the surface of the sheet C.

When the coefficient of friction was measured using the sheet C having this hard coat layer, the static coefficient of friction was 0.18 and the coefficient of dynamic friction was 0.10.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Sadaji Ohara 1-2-1 Yokou, Kawasaki-ku, Kawasaki-shi, Kanagawa Nihon ZEON CORPORATION

Claims (3)

[Claims] 1. A coating agent containing a copolymer of an acrylic monomer having a hydrocarbon group having 4 or more carbon atoms and an acrylic monomer having an epoxy group as a film forming component. 2. A coating agent which further contains a polyamine as a film forming component. 3. A molded article having a coat layer formed by the film-forming component of the coating agent according to claim 1 or 2 on at least a part of the surface of a base material made of a resin.