JPH0489217A - Hydrogenated norbornane family resin molded body - Google Patents

Abstract

PURPOSE:To modify the surface of a resin molded body and upgrade surface appearance, resistance to weather, resistance to scars and the like by applying a coating material containing a compound having two or more of ethylene double bonds in its molecule to a specified hydrogenated norbornane family resin molded body and curing. CONSTITUTION:A coating material containing a compound (herein-after referred to as 'curing compound') having two or more of ethylene double bonds in its molecule is applical to a hydrogenated norbornane family resin molded body formed by metathesis polymerizing at least one kind of norbornane derivative represented by the formula I or an unsaturated cyclic compound polymerizable with said derivative and hydrogenating, and cured. In the formula, (m) represents 0 or 1 C hydrocarbon, A and B represent H or 1-10 C hydrocarbon, X and Y represent H, 1-10 C hydrocarbon, -(CH2)nCOOR', -(CH2)nOCOR', -(CH2)nCN, -(CH2)nCONR<2>R<3> and the like. R<1>, R<2>, R<3> and R<4> represent 1-20 C hydrocarbon, and (n) represents 0-10 integer. As a crosslinking inorganic polymerized film is formed on the surface of the molded body, its surface appearance is good and also such characteristics as resistance to weather, resistance to scars and the like are upgraded to a large extent.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hydrogenated norbornene resin molded article, and more particularly to a hydrogenated norbornene resin molded article that has excellent surface appearance, weather resistance, and scratch resistance. .

[Conventional technology]

Ring-opening polymerization of norbornene derivatives using a metathesis catalyst (
A resin with excellent thermal stability (hydrogenated norbornene resin) obtained by hydrogenating (hereinafter referred to as "hydrogenation") a polymer subjected to metathesis polymerization is disclosed in, for example, JP-A-1-240517.
It has been proposed in publications such as No.

This hydrogenated norbornene resin has much higher heat resistance than conventional methacrylic resin, has low water absorption, and is lightweight, making it suitable for optical applications such as lenses and optical discs, as well as for general molded products. It has very good properties.

However, these resins have the disadvantage that their weather resistance is slightly inferior compared to conventional (meth)acrylic resins, and their surface hardness is low, making resin molded products manufactured using these resins easily damaged. have.

[Problem to be solved by the invention]

The present invention was made against the background of the above-mentioned problems of the prior art, and consists of hydrogenated norbornene that modifies the surface of a resin molded product, thereby significantly improving the surface appearance, weather resistance, scratch resistance, etc. of the resin molded product. The purpose of the present invention is to provide a resin molded article based on the above-mentioned resin.

[Means to solve the problem]

The present invention is produced by hydrogenating a polymer obtained by metathesis polymerizing at least one norbornene derivative represented by the following general formula (I) or an unsaturated cyclic compound copolymerizable with the norbornene derivative. Hydrogenated norbornene is obtained by applying a paint containing a compound having two or more ethylenic double bonds in the molecule (hereinafter referred to as a "curable compound") to a molded product of hydrogenated norbornene-based resin, and then curing it. The object of the present invention is to provide a resin molded article based on the above-mentioned resin.

[In the formula, m is 0 or 1, A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, X and Y are hydrogen atoms,
Hydrocarbon group having 1 to 10 carbon atoms, (CH,), C0OR+ CCHt) 11OCOR' (CHz)-
CN, (CHz) 1lCONR” R” (c) (z) llCOOZ.

(CH,)n　ocoz, -(cH,), loz.

(CH2), , W, or composed of X and Y.

In addition, R1, RZ, R3 and R4 have 1 to 20 carbon atoms.
hydrocarbon group, Z is a hydrocarbon group, W is S 1R5pD3
-p (R5 is a hydrocarbon group having 1 to 10 carbon atoms, D is 10
COR5 or -○R5, P is an integer from 0 to 3),
n represents an integer of 0 to 10. ] In the compound represented by the general formula (1), the substituent X and At least one of Y is preferably a group other than a hydrogen atom and a hydrocarbon group.

Further, it is preferable that one of the substituents X and Y is a carboxylic acid ester represented by the formula -(cH,)ゎC0OR' in that it does not change during the hydrogenation step during resin production, and the other one is hydrogen. An atom or a hydrocarbon group is preferable in that the water absorption of the resin does not become high.

Furthermore, among the carboxylic acid ester groups represented by -(CH,)n COOR', those with smaller n are preferable because the heat resistance of the hydrogenated norbornene-based resin increases, and in particular, those with the formula -
In (CH2), COOR', it is preferable that n is 0 from the viewpoint of synthesizing the compound and the stability of the hydrogenated norbornene resin. R1 is carbon number 1
-20 aliphatic, alicyclic, or aromatic hydrocarbon groups, and the larger the number of carbon atoms, the lower the water absorption of the resulting resin, which is preferable, but the thermal decomposition is generally lower as the number of carbon atoms becomes larger. Therefore, in order to make the most of the characteristics of the resin of the present invention, it is necessary to use a chain hydrocarbon group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 5 or more carbon atoms, a phenyl group, or a substituted phenyl group. Preferably, 8-methyl-8-methoxycarbonyltetracyclo(4,4,0,1'',
1"")-3-dodecene is preferred.

The polymer can also be made into a copolymer by using two or more kinds of compounds represented by the general formula (I).

For example, 8-methyl-8-methoxycarbonyltetracy'70(4,4,0,1"°5.17°to)-3-dodecene and 5-methyl-5-methoxycarbonylbicyclo(2,2,1 )-2-heptene can also be copolymerized. In this combination, 5-methyl-5-methoxycarbonylbicyclo[2°2.1)-2-heptene is copolymerized with 8-methyl-8-methoxycarbonyltetracyclo(4, 4,
It is particularly preferred because it can be obtained as an intermediate in the production of 0°12.5.17.I0]-3-dodecene.

In addition, other monomers that can be copolymerized with the compound represented by general formula (1) include cyclopentene, cyclohexene,
Cycloheptene, cyclooctene, pentacyclo(6,
Examples include cycloalkanes such as 5,1,13=', O'·70"")-11-pentadecene, and alkyl substituted products thereof.

When using a copolymerizable monomer to obtain a copolymer with a compound represented by general formula (1), if the amount of this compound is small, the final resin obtained will not have high heat resistance. Therefore, the proportion of the compound represented by general formula (I) is 50 mol% or more, preferably 70 mol% or more, and more preferably 80 mol% or more.

In addition, the polymerization of the compound represented by the general formula (1) can be carried out using polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene-nonconjugated diene copolymer,
It can also be carried out in the presence of an unsaturated hydrocarbon polymer containing a carbon-carbon double bond in its main chain, such as polynorbornene; in this case, the resulting hydrogenated norbornene resin has particularly high impact resistance. . Among these unsaturated hydrocarbon polymers, styrene-butadiene copolymer and styrene-isoprene copolymer are preferred because transparent molded products can be easily obtained. In this case, the styrene and diene copolymer may be a random copolymer or a block copolymer. When polymerizing in the presence of an unsaturated hydrocarbon polymer, the amount of the polymer is 1 to 50% by weight, preferably 3 to 40% by weight, more preferably 5% by weight, based on the compound represented by general formula (1).
~30% by weight is used.

Metathesis polymerization to obtain a polymer consists of (a) W, T
At least one selected from the compounds of i, Mo and Re
(6) periodic table IA, IIA, DB, I
I An additive (C) may be added to the components (a) to (b) that increase the .

Representative examples of W, Ti, Mo or Re compounds suitable as the component (a) include WCZ, , T i CIl
a , Mo CII s , Re OCl 3 and the like.

(b) Specific examples of components include n-BuLi, CCt
Hs)! Af, (C! H5)t AlCII, L
Examples include iH.

As representative examples of the component (C), alcohols, aldehydes, ketones, amines, etc. can be suitably used.

The usage ratio of component (a) and component (b) is a metal atomic ratio of (a):(b) of 131 to 1:50, preferably 1
:2 to 1:30.

The usage ratio of component (C) and component (a) is the molar ratio of (C)
):(a) is 0.005=1 to 10:1, preferably 0
．． It is used in a range of 0.05:1 to 2:1.

The molecular weight of the polymer can also be adjusted by the polymerization temperature, type of catalyst, and type of solvent, but more preferably ethylene,
It is preferable to make α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene coexist in the reaction system and adjust the amount by changing the amount.

The polymer used in the present invention has a molecular weight of [η] 11 and 0.
．． 2 to 5.0 is preferred.

The hydrogenation reaction of the polymer obtained by the above metathesis polymerization is carried out by a conventional method.

As the catalyst used in this hydrogenation reaction, those used in ordinary hydrogenation reactions of olefinic compounds can be used.

For example, examples of the heterogeneous catalyst include solid catalysts in which a catalyst material such as palladium, platinum, ruthenium, rhodium, or nickel is supported on a carrier such as carbon, silica, alumina, or titania. In particular, a catalyst in which palladium is supported on a silica/magnesia carrier is preferred from the viewpoint of activity and life.

In addition, homogeneous catalysts include nickel, cobalt, titanium, and vanadium compounds soluble in organic solvents such as nickel naphthenate, titanocene dichloride, and cobalt acetylacetonate, and organic aluminum compounds such as triethylaluminum, triisobutylaluminum, and diethylaluminum monochloride. , or a catalyst in combination with organolithium such as butyllithium can be used.

In addition, noble metal complex catalysts such as dichlorotris(triphenylphosphine)rhodium can also be used.

The hydrogenation reaction is carried out at normal pressure to 300 atmospheres, preferably 3 to 150 atmospheres.
It can be carried out under a hydrogen gas atmosphere at atmospheric pressure at a temperature of 0 to 200°C, preferably 20 to 180'C. The hydrogenation rate was measured by 60MHz NMR, and δ = 4.5 to 6.
It needs to be 90% or more, preferably 90% or more, calculated from the reduction of the peak in the 0 ppm range due to the hydrogenation reaction.
It is 5% or more, more preferably 98% or more.

If the hydrogenation rate is less than 90%, problems may arise in the stability of the hydrogenated norbornene resin, which is not preferable.

The gel content of the hydrogenated norbornene resin used in the present invention is 1% by weight or less, preferably 0.1% by weight or less, and the water content is 300ppm or less, preferably 1oop.
pm or less, and the halogen content is 50 ppm or less, preferably 20 ppm or less.

In addition, in the present invention, the hydrogenated norbornene resin includes:
Other thermoplastic resins may be added as necessary. Other thermoplastic resins have a glass transition temperature of 2.
It is a polymer with a temperature of 5°C or higher, and includes amorphous polymers, crystalline polymers, liquid crystal polymers, etc. Examples of specific thermoplastic resins include styrene resin, vinyl chloride resin, acrylic resin, polyphenylene ether resin, polyarylene sulfide resin, polycarbonate resin, polyester resin, polyamide resin, polyether sulfone resin, polysulfone resin, Examples include polyimide resin. The ratio of hydrogenated norbornene resin to other thermoplastic resin is 10 to 95:90 to 5, preferably 15 by weight.
~90: 85-10, more preferably 20-80
: The ratio is 80 to 20.

Furthermore, a resin composition that is a blend of a hydrogenated norbornene resin and another thermoplastic resin may contain a rubbery polymer and a rubber-reinforced thermoplastic resin, either alone or in combination. good.

Here, the glass transition temperature of the rubbery polymer is 0°C.
The following polymers include conventional rubbery polymers and thermoplastic elastomers.

The hydrogenated norbornene resin used in the present invention is formed into a molded article by applying various known molding methods, such as injection molding, compression molding, and extrusion molding. Here, the form of the hydrogenated norbornene resin molded article may be any form.

For example, it may be in the form of an intermediate molded product before the hydrogenated norbornene resin is made into a final molded product or a final molded product.

In the present invention, a coating material containing a curable compound is applied to a molded article of hydrogenated norbornene resin as described above, and then the coating film is cured.

Examples of the curable compound used in the present invention include crosslinkable monomers having two or more acrylic or methacrylic double bonds in the molecule, and crosslinking monomers having two or more allyl groups in the molecule. Examples include crosslinkable monomers, crosslinkable monomers having two or more aromatic vinyl double bonds in the molecule, and oligomers or polymers thereof.

Among these curable compounds, examples of crosslinkable monomers having two or more acrylic or methacrylic double bonds in the molecule include 2.2-bis(methacryloxyphenyl)propane and 2.2-bis(methacryloxyphenyl)propane. [4-(3-methacryloxy)-
2-Hydroxypropoxyphenyl]propane, 2,2
-bis(4-methacryloxyethoxyphenyl)propane, 2.2-bis(4-methacryloxyjethoxyphenyl)propane, 2.2-bis(4-methacryloxytetraethoxyphenyl)propane, 2゜2-bis( 4-
methacryloxypentaethoxyphenyl)propane, 2
．． 2-bis(4-methacryloxydipropoxyphenyl)propane, 2(4-methacryloxyethoxyphenyl)-2(4methacryloxydiethoxyphenyl)propane, 2(4-methacryloxyjethoxyphenyl)2(
4-methacryloxytriethoxyphenyl)propane,
2(4-methacryloxydipropoxyphenyl)-2-
(4-methacryloxytriethoxyphenyl)propane, 2.2-bis(4-methacryloxypropoxyphenyl)propane, 2.2-bis(4-methacryloxyisopropoxyphenyl)propane; 2-hydroxyethyl methacrylate, 2- -O such as hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate or these acrylates
A combination of a vinyl monomer having an H group and a diisocyanate compound such as diisocyanate methylbenzene, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate), etc. Sheaducts obtained from adducts; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1. 4-butanediol dimethacrylate, 1.6-hexanethiol dimethacrylate; acrylic anhydride, methacrylic anhydride, 1.2-
Difunctional monomers such as bis(3-methacryloxy-2-hydroxypropoxy)ethyl, di(2-methacryloxyethyl) phosphate, di(3-methacryloxypropyl) phosphate; trimethylolpropane trimethacrylate, trimethylolethane Trifunctional monomers such as trimethacrylate, pentaerythritol trimethacrylate, and trimethylolmethane trimethacrylate; pentaerythritol tetramethacrylate; sheaduct obtained from the adduct of the same diisocyanate compound and glycidol dimethacrylate; tricyclode Candimetatool dimethacrylate, dicyclopentadiene dimethacrylate, tricyclodecane (5,
2°10! Examples include tetrafunctional monomers such as "')-3,8-diyldimethylene dimethacrylate, and compounds in which the methacryloyl group of the above compound is replaced with an acryloyl group. Commercially available products include Visco-700
(manufactured by Osaka Organic Chemical Industry ■), KAYARAD R-5
51 (manufactured by Nippon Kayaku ■), Aronix M-315 (manufactured by Toagosei ■), Aronix M-210 (manufactured by Toagosei ■), BP-4PA (manufactured by Kyoeisha Yushi ■), BP-4EA (same), Yupi 7-UV5A
-1002 (manufactured by Mitsubishi Yuka), 5A-2006 (manufactured by Mitsubishi Yuka)
etc. can be mentioned.

Further, examples of crosslinkable monomers having two or more allyl groups in the molecule include diallyl phthalate, diallyl terephthalate, diallyl isophthalate, triallyl isocyanurate, triallyl cyanurate, diethylene glycol bisallyl carbonate, etc. I can do it.

Furthermore, examples of crosslinkable monomers having two or more aromatic vinyl double bonds in the molecule include divinylbenzene, diisopropenylbenzene, divinyltoluene, trivinylbenzene, diisopropenyltoluene, and divinylnaphthalene. , diisopropenylnaphthalene, 4.4'-
Examples include divinylbiphenyl, 4,4'-diisopropenylbiphenyl, and the like.

Further, among the curable compounds, examples of oligomers include oligomers of the above-mentioned crosslinkable monomers, and the degree of polymerization thereof is usually about 2 to 1,000, preferably about 2 to 100.

Further, among the curable compounds, examples of the polymer include polyether polyurethane, polyester polyurethane, and polycaprolactone polyurethane, which have an ethylenically unsaturated group resulting from an acrylic or methacrylic double bond at the molecular end.

In addition, when the curable compound is used as a thermosetting compound, other monomers, oligomers, or polymers having thermal polymerizability may be added.

In this case, if the proportion of the thermosetting compound decreases, a strong coating cannot be obtained, so the proportion thereof should be at least 20% by weight or more, preferably 30% by weight or more, and more preferably 50% by weight or more. It is necessary to be present.

Furthermore, when used as a thermosetting compound, a radical polymerization initiator may be added.

Examples of the radical polymerization initiator include peroxides and azo compounds, and more specifically, benzoyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, etc. . These radical polymerization initiators can be used alone or in combination of two or more.

The amount of the radical polymerization initiator added is 1 to 1 of the thermosetting compound.
0 to 2 parts by weight, preferably 0.0 parts by weight
01 to 1 part by weight is used.

On the other hand, when the curable compound is used as a photocurable compound such as ultraviolet rays, other photopolymerizable monomers,
Oligomers or polymers may also be added. In this case, if the proportion of the photocurable compound decreases, a strong film cannot be obtained, so the proportion thereof is at least 20% by weight, preferably 30% by weight or more, and more preferably 50% by weight or more. It is necessary.

Furthermore, when used as a photocurable compound, a photopolymerization initiator may be added.

Examples of the photopolymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-
Phenyl acetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde,
Fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone,
4.4'-diaminobenzophenone, Michler's ketone,
Benzoinpropyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-
1-one, 2-hydroxy-2-methyl-phenylpropan-1-one, thioxanthone compound, 2-methyl-1-[4(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4. Examples include 6-trimethylbenzoyldiphenylphosphine oxide. These photopolymerization initiators can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is 0 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the photocurable compound.
More preferably, it is 0.2 to 3 parts by weight. Moreover, a photosensitizer (polymerization accelerator) such as an amine compound can be used in combination with the photopolymerization initiator, if necessary.

The curable compound used in the present invention may contain a reactive diluent, an anti-aging agent, a polymerization inhibitor, a leveling agent, a surfactant, and the like, in addition to a solvent added as necessary.

Examples of means for applying the curable compound to the hydrogenated norbornene resin molding include known coating methods such as a spinner method, a spray method, a roll coater method, and a dipping method.

In addition, at this time, the thermosetting compound usually has a molecular weight of 40 to 300
°C1 preferably 0.1 to 10 at a temperature of 50 to 150 °C
0 hours, preferably 0. It can be cured over a period of 5 to 20 hours.

Further, at this time, as the conditions for curing the photocurable compound, it is preferable to irradiate the photocurable compound with ultraviolet rays having a wavelength within the range of 200 to 550 nm for 0.1 seconds or more, preferably 0.5 to 60 seconds.

Note that the cumulative amount of irradiation light here is usually 30 to 5.0
00 mj/cdl, and as a light source, a low pressure mercury lamp, a high pressure mercury lamp, a carbon arc, a metal halide lamp, a mercury discharge tube, a tungsten lamp, a halogen lamp, a sodium discharge tube, a neon discharge tube, etc. can be used.

The thickness of the curable compound coating formed on the surface of the hydrogenated norbornene resin molding is usually 0.01 to 1.
000 μm, preferably 0.00 μm. It is about 1 to 300 μm.

The surface of the hydrogenated norbornene resin molded product coated with a curable compound and cured in this way has a crosslinked organic polymer film formed on its surface, so it not only has a good surface appearance but also has good weather resistance. Properties such as durability and scratch resistance are significantly improved.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

In the examples, parts and percentages are based on weight unless otherwise specified.

Further, various measurements in the examples are as follows.

In accordance with JIS K5400, the molded plate was irradiated for 1,000 hours with a sunshine weather meter, and the degree of coloring of the molded plate was measured. Those with no coloring and those with O1 coloring were expressed as x.

Δ and; The presence or absence of defective phenomena such as rough skin and cloudiness was visually determined. Those with no defective phenomena were expressed as ○, and those with defective phenomena were expressed as ×.

Hold the test piece in a cycle of - 30°C (1 hour) > room temperature (15 minutes) > 80°C (1 hour).
After the test, a base grain test and tape peeling test were performed according to JIS K5400.

Out of 100 items, the number of peeling occurrences is 1 or less as 012
~5 pieces were expressed as Δ, and 6 or more pieces were expressed as ×.

Rainbow scratch resistance: Pencil hardness (JIS K5400), load 1
Measured at 00g.

Reference example 1 Nitrogen-substituted content 150f in a nitrogen atmosphere
In the reaction vessel of i, 8-methyl-8-methoxycarbonyltetracyclo(4,4,0°12・5.17,103
5 kg of 3-dodecene, 201 g of toluene, 650 g of 1-hexene as a molecular weight regulator, 86 M1 of a chlorobenzene solution of tungsten hexachloride as a catalyst with a concentration of 0.05 mol/l, and toluene with a concentration of paraaldehyde of 0.1 mol/l. Solution 34d and a toluene solution 2051d of diethylaluminium monochloride having a concentration of 0.5 mol/l were added and reacted at 80°C for 4 hours.

Add 1.0 kg of triethanolamine and 16 kg of methanol to this polymer solution. After stirring well, unreacted monomers and catalyst were removed by discarding the upper layer.

In the obtained lower layer, pentaerythrityl-tetrakis (3
-(3,5-di-t-butyl-4-hydroxyphenyl)
After adding 0.05% of [propionate] to the polymer, the polymer was recovered by steam stripping and drying.

This polymer was dissolved in tetrahydrofuran, charged into a high-pressure reactor, 1 kg of 5% palladium/alumina catalyst was added as a hydrogenation catalyst, and the temperature was 150°C, hydrogen pressure was 100 kg/
Hydrogenation reaction was carried out in c1il for 5 hours.

This was filtered to remove the catalyst, followed by steam stripping and drying to recover the hydrogenated norbornene resin (A).

Intrinsic viscosity of the obtained resin ([η)t-t, 30°C,
In chloroform, the same applies hereafter)) is 0.75 d1/g,
No olefin peak was substantially observed on the NMR chart, and the hydrogenation rate was 99% or more.

Reference Example 2 In Reference Example 1, the monomer was 8-methyl-8methoxycarbonyltetracyclo(4,4,O.

4.5 kg of 1t・5.17・”)-3-dodecene,
5-Methyl-5-methoxycarbonylbicyclo(2,2
, 1) Polymerization, hydrogenation, etc. were carried out in the same manner as in Reference Example 1, except that -2-heptene was changed to 0.5 kg, to obtain a hydrogenated norbornene resin (B). The intrinsic viscosity ([η]i,) of the obtained resin was 0.9 d1/g, substantially no olefin peak was observed on the NMR chart, and the hydrogenation rate was 99% or more.

Reference Example 3 In Reference Example 1, the monomer was 8-methyl-8-methoxycarbonyltetracycloC4,4,0°12.5.17
・”)-3-Dodecene was changed to 4.5 kg and dicyclopentadiene was changed to 0.5 kg, but polymerization, hydrogenation, etc. were carried out in the same manner as in Reference Example 1, and hydrogenated norbornene-based resin (C ) was obtained.

The intrinsic viscosity ((η), , h) of the obtained resin is 0.85
d/g, the olefin peak on the NMR chart was substantially observable, and the hydrogenation rate was 99% or more.

Reference Example 4 Polymerization and hydrogenation were carried out in the same manner as in Reference Example 1, except that the hydrogenation catalyst amount and hydrogenation time were changed, and the hydrogenation rate was 9.
A hydrogenated norbornene resin (D) with a hydrogenation rate of 7% and a hydrogenated norbornene resin (E) with a hydrogenation rate of 95% were obtained.

Reference example 5 Internal volume 50f with nitrogen substitution in a nitrogen atmosphere
In a reaction vessel, 3.5 kg of tetracycloC4,4,0,12・517°")-3-dodecene, a norbornene ring-containing monomer, and pentacyclo[6,5,1,1"
・6.02・7.09++3”-4 Pentadecene 1.
5kg, toluene 20ffi, molecular weight regulator 1
- Hexene 75m, concentration of catalyst titanium tetrachloride 1.
150 d of a toluene solution with a concentration of 0 mol/l, 200 d of a toluene solution with a concentration of triethylamine of 0.1 mol/l, and a concentration of 1.0 mol/l of triethylaluminum. 800 ml of toluene solution was added and reacted at 25°C for 2.5 hours. From this polymer solution, a polymer was recovered and hydrogenated in the same manner as in Reference Example 1, and a hydrogenated norbornene resin (F) with an intrinsic viscosity ([η)i, h) of 0.47 dl/g was obtained. 2
．． I gained 5 kg.

Reference Example 6 In a reaction vessel equipped with a stirrer, 128 g of 2,4-1-lylene diisocyanate and 1 g of dibutyltin dilaurate were added.
and 1 g of 2,6-di-t-butyl-4-methylphenol were charged.

Next, 57 g of hydroxyethyl acrylate was added while controlling the temperature below 20°C.

After the addition, stirring was further maintained at 10 to 20°C for 1 hour, and then polyether diol, a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran (manufactured by Hodogaya Chemical Industry ■, PTGL-2000, number average molecular weight -2) was added. ，
000) and 737 g of polyoxypropylene glycol (manufactured by Asahi Glass Co., Ltd., EXENOL 3020, number average molecular weight = 3.000) at a temperature of 40 to 5.
The mixture was added while maintaining the temperature at 0°C.

Then, after maintaining stirring at 40-50°C for 3 hours,
The reaction was completed and an ultraviolet curable compound having a number average molecular weight of about 5.700 was obtained.

Example 1 Using the resin (A) obtained in Reference Example 1, a molding machine of 80 x 55 x 2.4 m was molded using an injection molding machine [■Niigata Iron Works, NN30B].
A resin molded plate of I++ was manufactured.

The obtained resin molded plate was converted into bis(methacroyloxy)pentacyclo(6,5,1,1′3=602・7.09・
13] Hexadecane and bis(methacroyloxy)pentacyclo[7,4,0°13°b, l'l+1
3. QZ・7] Mixture with hexadecane (composition ratio =
84 parts of 90/10), 15 parts of methyl methacrylate, bis(4-t-butylcyclohexyl) peroxydicarbonate (manufactured by Nippon Kayaku ■, Bariki Dox PX-16)
was immersed in a mixture of thermosetting compounds consisting of 1 part, immediately pulled up, and heated at 120°C for 3 hours to form a coating layer with an average thickness of 150 μm on the surface of the resin molded plate.

Regarding the obtained resin molded plate, weather resistance, appearance, adhesion,
The scratch resistance was evaluated.

The results are shown in Table 1.

Example 2 Using the composition containing the ultraviolet curable compound produced in Reference Example 6, a resin molded plate produced in the same manner as in Example 1 was coated with a thickness of 1
After coating to a thickness of 0.00 μm, ultraviolet rays were irradiated thereon using a metal halide lamp at an irradiation amount of 0.5J/c+11 to cure it.

The obtained resin molded plate was evaluated in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 1 Example 1 except without coating the mixture of thermosetting compounds
Weather resistance, appearance, adhesion, and scratch resistance were evaluated in the same manner as above. The results are shown in Table 1.

Examples 3 to 7 In Example 1, hydrogenated norbornene resin (B),
A resin molded plate coated with a thermosetting compound was produced in the same manner as in Example 1 except that (C), (D), (E), and (F) were used.

The results are shown in Table 1.

Table 1 *1) Bis(methacroyloxy)pentacyclo(6,
5,1,13・h, □z,t, Q9++3
) hexadecane and bis(methacroyloxy)pentacyclo(7,4,0,1'·b, 19++3.
□z・7] Thermoplastic compound consisting of a mixture with hexadecane *2) Ultraviolet curable compound according to Reference Example 6 [Effects of the invention] According to the present invention, in a molded article of hydrogenated norbornene resin,
By applying and curing a paint containing a curable compound, it is possible to modify the surface of a resin molded article, thereby significantly improving the surface appearance, weather resistance, scratch resistance, etc. of the resin molded article.

The hydrogenated norbornene resin molded article of the present invention can be used for optical parts such as optical lenses and optical discs; automobile windshields, ceiling materials, headlamp lenses, fog lamp lenses, stop lamp lenses, turn lamp lenses, rear combination lenses, and room Automotive parts such as lamp lenses, lamp flaps, rearview mirrors, room mirrors, fuse covers, panel meter covers, wheel caps, and general interior and exterior parts; Cameras such as lens barrels, lens frames, and other camera exterior parts. parts;
Lighting equipment parts such as fluorescent lamp covers and lamp shades; Display parts; Electrical parts such as microwave oven lids and washing machine laundry lids; Electronic parts such as light emitting diode encapsulants;
OA equipment parts; audio equipment parts such as cassette cases and cassette halves; ramen cups, search cups, crystal cups, folding boxes, bento boxes, steam containers, frozen food containers, dry food containers, microwave food containers, trays, etc. Containers; Building materials; Civil engineering materials; Shipbuilding materials; Agricultural materials; Logistics materials; Clothing equipment such as syringes and petri dishes; Various nameplates; Daily goods; Films; Sheets, pipes; Bottles; Ru.

Patent applicant: Japan Synthetic Rubber Co., Ltd. Agent: Patent Attorney Takashi Shirai

Claims (1)

[Claims] (1) Obtained by hydrogenating a polymer obtained by metathesis polymerization of at least one norbornene derivative represented by the following general formula (I) or an unsaturated cyclic compound copolymerizable with the norbornene derivative. A hydrogenated norbornene resin molded product obtained by applying a paint containing a compound having two or more ethylenic double bonds in the molecule to a hydrogenated norbornene resin molding, and curing the coating. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) [In the formula, m is 0 or 1, A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and X and Y are hydrogen atoms. ,
Hydrocarbon group having 1 to 10 carbon atoms, -(CH_2)_nCO
OR^1, -(CH_2)_nOCOR^1, -(CH_2)_n
CN, -(CH_2)_nCONR^2R^3, -(CH_2)_nCOOZ, -(CH_2)_nOCOZ, -(CH_2)_nOZ
, -(CH_2)_nW, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. In addition, R^1, R^2, R^3 and R^4 have a carbon number of 1
~20 hydrocarbon groups, Z is a hydrocarbon group, W is SiR^5
_pD_3_-_p (R^5 is a hydrocarbon group having 1 to 10 carbon atoms, D is -OCOR^5 or -OR^5, p is 0 to
3), n represents an integer of 0 to 10. ]