JPH03122137A - Thermoplastic resin molded article - Google Patents

Abstract

PURPOSE:To obtain the titled molded article remarkably excellent in adhesion of coating film while retaining transparency of these components useful for car, etc., by applying a specific composition onto the surface of molded article consisting essentially of a monomer composed of a norbornene derivative having a specific structure. CONSTITUTION:The aimed composition obtained by applying (B) a mixed composition consisting of (i) 100 pts. wt. organoalkoxysilane expressed by the formula Rsi(OR')3 (R is 1-8C organic group; R' is 1-5C alkyl, etc.) or hydrolyzate thereof or partially condensed product thereof, (ii) colloidal silica dispersed into hydrophilic solvent, of 0-50 pts. wt. expressed in terms of solid content, (iii) 0.1-50 pts. wt. water and (iv) 100-1,000 pts.wt. solvent to the surface of (A) resin molded article consisting essentially of a hydrogenated polymer obtained by further hydrogenating a ring-opened polymer obtained by subjecting a monomer consisting of at least one norbornene derivative expressed by the formula (A and B are H or 1-10C hydrocarbon; X and Y are H, 1-10C hydrocarbon, halogen, etc.) or the monomer and copolymerizable monomer copolymerizable with the monomer to ring opening polymerization.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a molded product having excellent heat resistance, weather resistance, chemical resistance, and scratch resistance by forming a highly hard film on the surface of a heat-resistant resin molded product. Regarding products.

[Prior Art] Hydrogenated polymers obtained by hydrogenating ring-opening polymers or ring-opening copolymers of norbornene derivatives have good optical properties, low hygroscopicity, and excellent heat resistance, so they are particularly used in various fields. It is expected that it will be applied in optical applications.

However, since the surface of the molded product does not have sufficient scratch resistance, it is easily scratched and is easily noticeable. In order to improve this, painting and surface coatings have been applied, but transparency is lost with painting. Furthermore, existing coating materials have poor adhesion to molded products, making them impractical at present.

[Problem to be solved by the invention] Creating a coated molded product that can take advantage of the optical properties such as transparency that hydrogenated polymer molded products have, and that forms a film with good adhesion and excellent scratch resistance. It is to be.

[Means for Solving the Problems] As a result of extensive research into the above-mentioned problems, the present invention has been completed by discovering that the coating material shown in the present invention achieves the object of the present invention.

That is, the present invention discloses (1) (A) a monomer consisting of at least one norbornene derivative represented by the following general formula (I), or a polymer thereof and a copolymerizable polymer copolymerizable therewith. The ring-opened polymer obtained by ring polymerization is
Furthermore, the following (B-1) or (B
The present invention provides a thermoplastic resin molded article coated with the composition of -2).

General formula (I) [wherein A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and X and Y are hydrogen atoms and 1 to 10 carbon atoms]
10 hydrocarbon groups, halogen atoms, hydrocarbon groups having 1 to 10 carbon atoms substituted with halogen atoms, SakiCH2) C
0OR', (CH2) n0COR', (CH2),
OR'Saki CH2) CN, -(-CH2) C0N
R2n R3, (CH2) C00ZS (CH2) n0n COZ, (CH2) 0ZS-GCH2). At least one of X and Y composed of W or X and Y is a group other than a hydrogen atom and a hydrocarbon group (here, R', R2, R3
and R4 is a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group substituted with a halogen atom, and W is 5iR5D
(R5 is a carbon 3-p hydrocarbon group having 1 to 10 prime numbers, D is a halogen atom, -〇〇OR6 or 10R6 (R6 is a hydrocarbon group having 1 to 10 carbon atoms), p is a hydrocarbon group having 0 to 3 carbon atoms, (represents an integer), n is 0 to 1
Indicates an integer of 0. ), and m is 0 or 1. ] (B-1) (a) General formula R3i (OR' ) 3 [
In the formula, R is an organic group having 1 to 8 carbon atoms, and R' is an organic group having 1 to 5 carbon atoms.
represents an alkyl group or an acyl group having 1 to 4 carbon atoms. ]
For 100 parts by weight of organoalkoxysilane, its hydrolyzate, or its partial condensate represented by (
b) 0 to 50 parts by weight of colloidal silica dispersed in a hydrophilic organic solvent, (c) 0.1 to 50 parts by weight of water, and (d) a hydrophilic organic solvent (however, (b) (including hydrophilic organic solvents present in the ingredients) 100-1°00
A composition obtained by mixing 0 parts by weight.

(B-2) (a) General 2〇H3SiX3 In formula C, X
is a halogen atom or a group represented by OR+, where R1 is an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 4 carbon atoms.
represents an acyl group. ] Methylsilane or its hydrolyzate or its partial condensate and/or the above-mentioned methylsilane, general formula R25i (OR')
In formula C, a 4-C H2 represents an organic group having 2 to 8 carbon atoms, a represents an integer of 0 to 2, and OR+ is the same as above. ] or a partial cocondensate with an organoalkoxysilane or its hydrolyzate, and (b) the general formula R3(CH3) bS i (OR'
)3-b In the formula, R3 is an organic group of 0 or 10, b is an integer of 0 or 1, and OR1 is the same as above. A composition prepared by mixing an alkoxysilane represented by the following formula, a hydrolyzate thereof, or a partial condensate thereof.

The hydrogenated polymer (A) for the molded article according to the present invention is:
By ring-opening polymerization of the monomer consisting of the norbornene derivative represented by the above general formula (I) (hereinafter referred to as "specific monomer") alone, or by copolymerizing the specific monomer with this monomer. It is a hydrogenated polymer obtained by further hydrogenating a ring-opening polymer obtained by ring-opening copolymerization with a copolymerizable monomer. The molecular weight of this hydrogenated polymer (A) is from 20,000 to 700.000 in terms of a polymerization average molecular weight in terms of polystyrene, especially from 30,000 to 700,000.
Preferably, it is between 000 and 500,000.

Among the specific monomers, the polar substituent X or Y in the above general formula (I) is of the formula (CH2) Co.

The specific monomer represented by R1, which is a carboxylic acid ester group, is preferable because the resulting polymer has a high glass transition temperature and low hygroscopicity.

In particular, the polar substituent consisting of this carboxylic acid ester group is
It is preferable to contain one per molecule of the specific monomer because the resulting polymer has low hygroscopicity.

Among the carboxylic acid ester groups represented by the formula (CH2) C0oR1, those with a smaller value of n are preferable because the glass transition temperature of the obtained polymer becomes higher. , is preferred because its synthesis is easy and the resulting polymer has good properties.

In the above formula, R1 is a hydrocarbon group having 1 to 2 carbon atoms, which is preferable because the greater the number of carbon atoms, the lower the hygroscopicity of the obtained polymer. However, from the viewpoint of balance with the glass transition temperature of the obtained polymer, the number of carbon atoms is 1 to 1.
It is preferably a chain hydrocarbon group of 4 or a (poly)cyclic hydrocarbon group having 5 or more carbon atoms.

Furthermore, to the carbon atom to which the carboxylic acid ester group is bonded,
At the same time, a specific monomer to which a hydrocarbon group having 1 to 10 carbon atoms is bonded as a substituent is preferable because it lowers the hygroscopicity without lowering the glass transition temperature of the resulting polymer.

In particular, a specific monomer in which the substituent is a methyl group is preferable because it is easy to synthesize.

The ring-opening polymer according to the hydrogenated polymer (A) in the present invention may be one obtained by ring-opening polymerization of a specific monomer alone, but the specific monomer and a copolymerizable monomer may be used. It may be ring-opening copolymerized with. When a copolymerizable monomer is used in this way, the proportion of the specific monomer in the ring-opening polymer is 5 mol% or more, preferably 20 mol% or more. Examples of the copolymerizable monomers used include monomers that can be ring-opening polymerized by a metathesis polymerization catalyst and partially polymerized low polymers having a carbon-carbon double bond in the main chain of the polymer. be able to.

Further, as a specific monomer, a tetracyclododecene derivative in which m is 1 in the above general formula (I) is preferable to one in which m is 0 in that a polymer with a high glass transition point can be obtained, and also a tetracyclododecene derivative in which m is 1 When using a specific monomer, it is also possible to obtain a ring-opening polymer by carrying out ring-opening copolymerization with a cyclic olefin compound.

Specific examples of such cyclic olefin compounds include cycloolefins such as cyclopentene, cyclooctene, 1,5-cyclooctadiene, and 1.5.9-cyclododecatriene; bicyclo[2°2.1]-2-heptene; , tricyclo[5,2°1.02"] -]8-decentric tricyclo[5,2°1.02'6-3-decene,
Tricyclo[6,2゜1, ()1-8-9-undecene, tricyclo[6゜2.1. O"8]-4-undecene, tetrashif2.5 7.10 [4,4,0,1,1]-]3-dodecenepentacyclo[6,5,1,1"" 2°709° 13]
4-pentadecene, pentacyclo[6°3.6
2,7 9.146.1,1 ,O,O]-
4-hexadecene, pentacyclo[6,5,1,1”°
62.7 9.13 0. 0]-]11-pentadecene dicyclopentadiene, pentacyclo[6,5,1°3.6 2
．． 7 9.13 1. 0, O] -] Pentadecar 4.11-
Dienes include polycycloalkenes such as compounds in the above general formula (I) where m is 0.

The polycycloalkenes described above are useful in reducing the hygroscopicity of the ring-opened polymer and controlling the glass transition temperature of the ring-opened polymer. For example, if tetracyclodecene alone or a copolymer with bicycloheptene has a glass transition temperature that is too high and causes undesirable silver streaks or molecular total deterioration during molding, copolymerization with cycloolefin may cause glass transition temperature. The transition temperature can be lowered to a point where molding can actually be easily achieved. Also. The resulting ring-opened polymer has a low glass transition temperature (
When the temperature is 100° C. or lower, by copolymerizing polycycloalkene, it is possible to raise the glass transition temperature of the ring-opening polymer and to lower the hygroscopicity.

In addition, examples of copolymerizable monomers include polybutadiene, polyisoprene, styrene-butadiene copolymer, and ethylene-butadiene copolymer.
Unsaturated hydrocarbon polymers containing a carbon-carbon double bond in the main chain of the polymer may also be mentioned, such as propylene non-conjugated diene copolymer rubber, polynorbornene, and polypentenamer.

The ring-opened polymer obtained as described above preferably has a saturated water absorption of 1.8% or less and a glass transition temperature of 100° C. or higher. The saturated water absorption rate is more preferably 1.2% or less, most preferably 0.8% or less. The glass transition temperature is more preferably 120°C or higher.

The metathesis polymerization catalyst used in the production of ring-opening polymers is usually a catalyst consisting of a combination of the following components (a) and (b). Agents may be added.

(a) Component: At least one selected from compounds of W, Mo, and Re. (b) Component: IA and IIA of Deming's periodic table.

At least one compound selected from IrB, HA, TVA, or a group IVB element having at least one element-carbon bond or element-hydrogen bond, the above (a) component and (b) component; The metal atomic ratio (a):(b) is in the range of 1:1 to 1:20, preferably 1:2 to 1:10.

The metathesis polymerization catalyst prepared from the above components (a) and (b) usually has high catalytic activity in the metathesis ring-opening polymerization reaction of a specific monomer, but it also has the following component (C). By adding an activator, it can be used as a catalyst with even higher activity.

Various compounds can be used as the component (c), and particularly preferably used compounds include the following.

■ Elemental boron, BF3, BCl3, B (0-n-C4H
s) 3・BF30 (CH3) 2・BF30 (C2
H5)2, BF30 (n-C4Hs)2, BF3 φ
2C6H50H, BF3 φ2CH3C00HSBF3
Urea, BF3 ・Triethanolamine, BF3
・Piperidine, BF3 ・C2H5NH2, B2 o3
, boron compounds such as H3B03, Si (OC2H5
) Silicon compounds such as 4.5iC14, ■Alcohols, hydroperoxides and peroxides, ■Water,
■Oxygen, ■Carbonyl compounds and their oligomers or polymers such as aldehydes and ketones, ■Cyclic ethers such as ethylene oxide, shrimp chlorohydrin, and oxetane, ■N,N-diethylformamide, N,N-
Amides such as dimethylacetamide, amines such as aniline, morpholine, and piperidine, and azo compounds such as azobenzene, ■N-nitrosodimethylamine, N
- N-nitroso compounds such as nitrosodiphenylamine, ■ trichloromelamine, N-talolosuccinoimide,
Compounds containing S-C1 or N-CI groups such as phenylsulfenyl chloride.

In addition, the quantitative relationship between component (a) and component (C) cannot be uniformly defined because it varies extremely depending on the type of component (C) added, but in many cases, (c)
/ (a) (molar ratio) is used in a range of 0.005 to 10, preferably 0.05 to 1.0.

In the metathesis ring-opening polymerization reaction, the molecular weight of the resulting polymer can be adjusted by changing reaction conditions such as the type and concentration of the metathesis polymerization catalyst, the polymerization temperature, the type and amount of the solvent, and the overall concentration of the monomers. It is usually preferable to adjust the molecular weight of the ring-opened polymer by adding an appropriate amount of a suitable molecular Tll adjuster to the polymerization reaction system.

Such molecular weight regulators include α-olefins, α,
Examples include compounds having at least one carbon-carbon double bond or carbon-carbon triple bond in the molecule, such as ω-diolefins or acetylenes, or polar allyl compounds such as allyl chloride, allyl acetate, and trimethylallyloxysilane. can.

Examples of solvents used in the polymerization reaction include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as dichlorohexane, cyclohebutane, cyclooctane, decalin, and norbornane; benzene, toluene, xylene, Aromatic compounds such as ethylbenzene and cumene; chlorobutane,
Compounds such as halogenated alkanes and halogenated aryls such as bromhexane, dichloroethane, hexamethylene dipromide, and chlorobenzene; and saturated carboxylic acid esters such as ethyl acetate and methyl propionate.

The hydrogenation reaction of the ring-opened polymer obtained as described above can be carried out in the usual manner, that is, by adding a hydrogenation catalyst to a solution of the ring-opening polymer, and adding the hydrogenation catalyst to the solution at normal pressure to 300 atm, preferably 3 to 300 atm.
Hydrogen gas at 150 atm is heated at 0 to 180°C, preferably at 20°C.
It is carried out by operating at ~150°C.

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

As this hydrogenation catalyst, heterogeneous catalysts and homogeneous catalysts are known.

Heterogeneous catalysts include palladium, platinum, nickel,
Examples include solid catalysts in which a catalyst material such as rhodium or ruthenium is supported on a carrier such as carbon, silica, alumina, or titania.

In addition, examples of homogeneous catalysts include nickel triethylaluminum naphthenate and nickel acetylacetonate.
Examples include triethylaluminum, cobalt-n-butyllithium octenoate, titanocene dichloride-diethylaluminum monochloride, rhodium acetate, and chlorotris(triphenylphosphine)rhodium.

Hydrogenated polymer (A) obtained in hydrogenation reaction
The hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 80% or more. When the hydrogenation rate is less than 50%, weather resistance decreases.

The hydrogenated polymer (A) of the present invention is defined in claims (1) and (2).
It has good compatibility with the coating composition which is component (B), and as a result, it has excellent adhesion to the coating film after application.

In the case of a resin other than the hydrogenated polymer (A), the compatibility with the coating composition is insufficient, and the hydrogenated polymer (A) is not compatible with the coating composition.
Excellent adhesion like A) cannot be obtained.

Next, the resin and other materials to be mixed with the hydrogenated polymer (A) are not particularly limited, and any material may be used as long as they can be mixed. However, when mixed, the content of the hydrogenated polymer (A) in the mixture is preferably 50% by weight or more, more preferably 60% by weight or more. Content is 50% by weight
If it is less than 20%, the compatibility with the coating composition will be poor, and as a result, the adhesion to the coated film will be poor. PMMA
, PC1 amorphous, transparent resins such as nylon, and opaque engineering plastic resins such as nylon, PBT, and PET.

The coating composition of component (B) in claim (1) of the present invention will be explained.

(a) Organopolysiloxane (a) Organopolysiloxane has the general formula R3i (O
It is obtained by hydrolyzing and polycondensing organoalkoxysilane represented by R')3, and functions as a binder in the coating composition of the present invention.

R in this organoalkoxysilane has 1 to 1 carbon atoms.
8 organic groups, such as alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, and other γ
-talolopropyl group, vinyl group, 3,3.3-)lifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group,
Examples include phenyl group, 3,4-epoxycyclohexylethyl group, and γ-aminopropyl group.

Furthermore, R' in the organoalkoxysilane has 1 carbon number.
-5 alkyl group or C1-4 acyl group, such as methyl group, ethyl group, n-propyl group, i-
propyl group, n-butyl group, 5ec-butyl group, ter
Examples include t-butyl group and acetyl group.

Specific examples of these organoalkoxysilanes include:
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane,
i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-talolopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3.3-trifluoropropyltrimethoxysilane, 3,3 .3-Trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ
-methacryloxypropyltrimethoxysilane, γ-
Methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexyl Examples include ethyltriethoxysilane, but methyltrimethoxysilane and methyltriethoxysilane are preferred.

These organoalkoxysilanes can be used alone or in combination of two or more.

Furthermore, in the organoalkoxysilane represented by the general formula R8i (OR')3, 80 mol% or more is CH
3S i (OR')3 is preferred.

In addition, such organoalkoxysilane releases alcohol by hydrolysis in an acidic aqueous medium, and
Polycondensation occurs to produce organopolysiloxane.

The average molecular weight of such organopolysiloxane in terms of polystyrene is 500 to 5,000, preferably 700.
~3,000, and if it is less than 500, the resulting coating film is likely to crack, and weather resistance, water resistance, stain resistance, etc. will deteriorate, while if it exceeds 5,000, the coating film will not be sufficiently cured. Therefore, the hardness of the resulting coating film decreases, and the scratch resistance deteriorates.

(b) Colloidal silica Cb') Colloidal silica is used to increase the solid content while maintaining the transparency of the coating composition of the present invention, and the thickness of the coating film obtained depending on the amount of this component. It depends on the situation.

Here, colloidal silica is a dispersion of highly purified silicic acid anhydride dispersed in a hydrophilic organic solvent as described below, and usually has an average particle size of 5 to 30 mμ, preferably 10 to 20 mμ.
, the solid content concentration is about 10 to 40% by weight.

The water content in this colloidal silica is preferably 4% by weight or less, particularly preferably 2% by weight or less. That is, when the water content in the colloidal silica exceeds 4% by weight, the amount of water, which is component (c), becomes relatively large, and precipitates may easily form in the coating composition.

As such, colloidal silica is commercially available, for example, isopropatol silica sol and methanol sol, manufactured by Nissan Chemical Industries, Ltd.; Oscar, manufactured by Catalysts and Chemicals Industries, Ltd., are commercially available.

The proportion of colloidal silica (b) as described above in the coating composition is 0 to 50 parts by weight, preferably 5 to 40 parts by weight in terms of solid content, based on 100 parts by weight of component (a).
By using component (b), it is easy to achieve a thick coating film obtained by coating, and a coating film with high hardness can be obtained. On the other hand, if the amount exceeds 50 parts by weight, a thick film can be easily obtained, but the coating film is likely to crack, resulting in poor weather resistance and water resistance.

(c) Water (C) Water is an essential component for the hydrolysis of organoalkoxysilane, and also serves as a dispersion medium for the component (b). As such water, general tap water, distilled water, ion exchange water, etc. can be used. In particular, when the coating composition of the present invention is to be highly purified, distilled water or ion-exchanged water is preferred.

(c) The proportion of water in the coating composition is (a
) is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the component.If it is less than 0.1 part by weight, hydrolysis will be insufficient, and the resulting coating composition may not be used for coating. However, if the amount exceeds 50 seedlings, the storage stability of the coating composition decreases, which is not preferable.

(d) Hydrophilic organic solvent (d) Hydrophilic organic solvent includes the hydrophilic organic solvent present in the component (b), and mainly mixes components (a) to (b) uniformly, and (a) ~(b) Adjusts the concentration of the component and adjusts the solid content of the coating composition of the present invention, and at the same time can be applied to various coating methods and improves the dispersion stability and storage stability of the coating composition. .

As such a hydrophilic organic solvent, alcohols or low-boiling hydrophilic organic solvents having a boiling point of 120°C or less are suitable.

Examples of alcohols include monohydric alcohols, dihydric alcohols, and glycol derivatives, and among these, saturated aliphatic alcohols having 1 to 8 carbon atoms are preferred as monohydric alcohols.

Specific examples of these alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, 5eC-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, and acetic acid. Examples include ethylene glycol monoethyl ether.

Examples of the low-boiling hydrophilic organic solvent having a boiling point of 120° C. or lower include acetone, methyl ethyl ketone, and tetrahydrofuran.

Among these hydrophilic organic solvents, alcohols and glycol derivatives such as i-propyl alcohol, 5eC-butyl alcohol, n-propyl alcohol, n-butyl alcohol, diethylene glycol, and acetic acid ethylene glycol monoethyl ether are preferred, especially Preferred are i-propyl alcohol and acetic acid ethylene glycol monoethyl ether.

These hydrophilic organic solvents can be used alone or in combination of two or more.

(d) The proportion of the hydrophilic organic solvent in the composition is 100 to 1,000 parts by weight, preferably 150 to 1,000 parts by weight, and less than 100 parts by weight, based on 100 parts by weight of component (a). (a) The dispersibility of the organopolysiloxane and the filler used as necessary deteriorates, storage stability deteriorates, and the viscosity of the resulting composition becomes too high, making it impossible to obtain a homogeneous coating film. On the other hand, if it exceeds 1,000 parts by weight, the amount of other components will be relatively small, and the coating film formed by coating the resulting coating composition will be too thin, making it difficult to obtain the desired coating film. I won't be able to do that.

It is also possible to add other fillers to the composition of the present invention, if necessary.

Such fillers are water-insoluble and can include, for example, pigments such as organic or inorganic pigments. In addition, particulate or fibrous metals and alloys other than pigments, and their oxides, hydroxides, carbides, nitrides, sulfides, etc. Specific examples include particulate or fibrous iron, copper, aluminum, nickel, Silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide,
Titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconium oxide, cobalt oxide, synthetic mullite, zircon (zirconia silicate), aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, molybdenum disulfide Examples include, but are not limited to, the following.

The coating composition of component (B) in claim (2) of the present invention will be explained.

Component (B) is (a) General 2CH35iX3 [wherein,
is a halogen atom or a group represented by OR+, where R1 is an alkyl group having 1 to 5 carbon atoms; l: is an alkyl group having 1 to 5 carbon atoms;
4 shows the acyl group. ] Methylsilane or its hydrolyzate or its partial condensate and/or the methylsilane represented by the general formula R25i (OR')
(In the formula a4-a, R2 is an organic group having 2 to 8 carbon atoms, a is an integer of 0 to 2, and OR1 is the same as above.) (b) general formula R3(CH3) Si (OR'
) (wherein, R3 is carbon b
3-b An organic group of 3 to 10, b is an integer of 0 or 1, and OR1 is the same as above. This is a coating composition prepared by mixing an alkoxysilane represented by the following formula, a hydrolyzate thereof, or a partial condensate thereof.

(a) of the above coating composition will be explained.

The methylsilane condensate used in (a) has the general formula CH
It is obtained by hydrolyzing and partially polycondensing methylsilane represented by 35iX3.

In this methylsilane, X is a halogen atom such as a chlorine atom, a fluorine atom, a bromine atom, or a group represented by -OR+.

Here, R1 is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, S -butyl group, t-butyl group, acetyl group, etc.

Specific examples of these methylsilanes include methyltrichlorosilane, methyltrimethoxysilane, and methyltrichlorosilane.
-propoxysilane, methyltrimypropoxysilane, methyltri-n-butoxysilane, methyltri-S-butoxysilane, methyltri-t-butoxysilane, methyltriacetoxysilane and the like.

On the other hand, the partial cocondensate of methylsilane and organoalkoxysilane used in the other (a) is a cocondensate obtained by cocondensing the methylsilane and organoalkoxysilane represented by the general formula R2aSi (OR'). It is a thing.

In the general formula of the organoalkoxysilane, when a is 0, the organoalkoxysilane is a tetraalkoxysilane represented by the general formula 5i(OR')4, in which all four bonding points of the silicon atom are Since it is subjected to siloxane bonding, it can act as a densifying component in component (a).

Specific examples of this tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetran-propoxysilane, tetramypropoxysilane, tetran-butoxysilane, tetramybutoxysilane, tetrat-butoxysilane, and tetraacetoxysilane. Among them, tetramethoxysilane, tetraethoxysilane, and tetramypropoxysilane are preferred.

Further, in the general formula of the organoalkoxysilane, when a is 1, the organoalkoxysilane is an organotrialkoxysilane represented by the general formula R2Si (OR')3, and R2 shown in the formula
When the resulting methylsilane cocondensate is used as a coating material, coating film performance such as hardness, adhesion, and water repellency can be improved.

R2 in the organotrialkoxysilane represented by the general formula R2S i (OR' )3 has 2 to 2 carbon atoms.
8 organic groups, such as ethyl group, n-propyl group,
Alkyl groups such as i-propyl group, γ-chloropropyl group, vinyl group, 3゜3.3-)lifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group group, phenyl group, 3,4-epoxycyclohexylethyl group, etc.

Specific examples of this organotrialkoxysilane include:
Ethyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i
-Propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3,3.3-trifluoropropyltrimethoxysilane, 3,3.3 -Trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-
methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-aminopropyltrimethoxysilane, Examples include 3,4-epoxycyclohexylethylmethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, and the like.
Preferably ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ- It is chloropropyltriethoxysilane.

Furthermore, in the general formula of the organoalkoxysilane, when a is 2, the organoalkoxysilane is a diorganodialkoxysilane represented by the general formula R22Si(OR1)2, in which 2 atoms per silicon atom are Since the methylsilane cocondensate can generate siloxane bonds, a highly flexible component having a linear siloxane bond can be included in the methylsilane cocondensate.

Specific examples of such diorganodialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-propoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-i
-propoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, dimethyldiacetoxysilane, di-n-propyldiacetoxysilane, and the like.

The co-condensation ratio of the above methylsilane and organoalkoxysilane is 85 to 0 parts by weight, preferably 70 to 0 parts by weight of organoalkoxysilane to 100 parts by weight of methylsilane.
If the resulting composition is used as a coating material, the curability of the material decreases.

The weight average molecular weight of the above component (a) in terms of polystyrene is usually 500 to 300,000, preferably 800.
~100,000, more preferably 1.000-50
．． 000, and if it is less than 500 or exceeds 300.000, when the resulting composition is used as a coating material, the adhesion of the coating film tends to decrease.

Next, component (b) will be explained.

By adding component (b) to component (a), (a
) A substance that reacts with and condenses with the silanol groups remaining in the component to reduce the amount of remaining silanol groups and improves the storage stability of the resulting composition due to the high price of the organic group represented by R3. It is.

The general formula of this (b) component is R3(CH3) b S t
R3 in (OR+)3-5 is an organic group of 0 or 1o, such as an alkyl group such as n-probyl group, i-propyl group, butyl group, γ-chloropropyl group, 3
, 3.3-trifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-methylcaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group, etc. It will be done.

When the number of carbon atoms in R3 is less than 3, the effect of improving the storage stability of the resulting composition is small, while when the number of carbon atoms exceeds 10, the condensation reactivity of component (b) is significantly reduced, Moreover, the compatibility with component (a) also decreases.

In addition, if the value of b in component (b) is 2 or more, (a)
The condensation reaction with the components consumes all the silanol groups and alkoxy groups in the reaction system, and the curability of the resulting composition is significantly reduced.

Specific examples of these component (b) include n-propyltrimethoxysilane, n-propyltriethoxysilane,
i-Propyltrimethoxysilane, i-Propyltriethoxysilane, γ-Clopropyltrimethoxysilane, γ-Clopropyltriethoxysilane, 3.3.3
-}-lifluoropropyltrimethoxysilane, 3.3.
3-Trifluoropropyltriethoxysilane, γ-glycidoxypyltrimethoxysilane, γ-glycidoxypyltriethoxysilane, γ-methacryloxypyltrimethoxysilane, γ-methacrylicoxypyltriethoxysilane, γ Preferred examples include -mercaptopyrtrimethoxysilane, γ-mercaptopyrutriethoxysilane, 3,4-epoxyhexylethyltrimethoxysilane, 3,4-epoxyhexylethyltriethoxysilane, and the like. n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ- glycidoxypyltrimethoxysilane, γ-glycidoxypyltriethoxysilane,
γ-Mercaptopropyltriethoxysilane, γ-mercaptopropyltriethoxysilane, 3,4-epoxyhexylethyltrimethoxysilane, 3,4-epoxyhexylethyltriethoxysilane, etc., more preferably These include γ-glycytoxysilane, γ-glycidoxysilane, 3,4-epoxyhexylethyltrimethoxysilane, 3,4-epoxyhexyltriethoxysilane, and the like.

In the present invention, the specific reaction product is (a) component 100
Component (b) is generally added in an amount of 1 to 25 parts by weight, preferably 2 to 15 parts by weight, and reacted preferably at 50°C or higher, more preferably at 60 to 80°C.

The proportion of the specific reaction product in the composition of the present invention is usually 10 to 100% by weight, preferably 20 to 100% by weight.

Further, the composition of the present invention may generally contain 0 to 50% by weight of component (a) and 0 to 50% by weight of component (b).

The composition of the present invention may contain a metal oxide, if necessary.

Examples of this metal oxide include silica, silica sol,
Alumina, alumina sol, titania, zirconia, antimony pentoxide, kaolin, slaked lime, M n O2, F
e 203, F e 304.5n02, Sn○, N
i20, CuO1Cu20, Zn○, Co2O3, etc.

The particle size of this metal oxide is usually 0.1 to 100 μm, preferably 1 to 70 μm, and may be dispersed in water or an organic solvent. Here, the concentration of the metal oxide when dispersed in a solvent is usually 10 to 80% by weight.

Further, the proportion of the metal oxide in the composition is usually 0 to 70% by weight.

Next, when the composition of the present invention is used as a coating material, an organic solvent is added for the purpose of improving workability during coating film formation or for mixing the composition of the present invention with other paint pigments or fillers. can be used.

Examples of the organic solvent include methanol, ethanol, n-propyl alcohol, i-propyl alcohol,
S-butyl alcohol, t-butyl alcohol, n-pentyl alcohol, ne.

-pentyl alcohol, n-hexyl alcohol, n-
Heptyl alcohol, methyl cellosolve, ethyl cellosolve, propyl cellosolve, ethylene glycol, propylene glycol, methyl diglyme, ethyl diglyme, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, methyl propyl ketone, methyl n-butyl ketone, methyl isobutyl ketone , acetophenone, benzophenone, benzene, toluene, xylene, ethyl acetate, propyl acetate, butyl acetate, dichloromethane, chloroform, carbon tetrachloride, and various fluorocarbon solvents.

The amount of this organic solvent to be added may be determined as necessary, and it may be a mixed solvent system of two or more types or more.

In addition to using the organic solvent, water can be mixed in the composition of the present invention. In this case, a hydrophilic organic solvent is usually selected.

The coating composition of the present invention is a target object (A)
Apply to the surface of the component using a coating method such as brushing, spraying, or dipping using a conventional method such as sinking, spraying, or dipping, and apply at a temperature of about 20 to 100°C for 5 to 2 minutes.
By drying for about 4 hours, a dry film thickness of 1 coat can be achieved with one coat.
It is possible to form a coating film of ~100 μm, preferably 3 to 50 μm, and if it contains a filler,
It is possible to form a coating film of about 300 μm, preferably about 10 to 100 μm.

Note that the technology of the present invention can also be applied to resins other than the norbornene resins described above as the component (A).

Examples of resins that can be used as the component (A) include aromatic vinyl-based resins such as methacrylic acid ester (co)polymers, polystyrene, styrene-acrylonitrile copolymers, ABS resins, AAS resins, MBS resins, and HIPS. (co)polymer, aromatic vinyl-conjugated diene block copolymer or hydrogenated product thereof, grafted with aromatic vinyl and/or methacrylic acid ester, hydrogenated product of polystyrene, (di)acrylate of norbornene derivative, or Examples include (co)polymers of (di)arylates and addition (co)polymers of the compound of general formula (I).

Although resins with low transparency can be used as component (A), resins with excellent transparency are preferred in that they can effectively obtain the effects of the present invention.

[Example] The present invention will be described in detail below, but the present invention is not limited thereto. In addition, below, "
"Parts" and "%" indicate parts by weight and % by weight, respectively.

Molded article A-1 (molded article within the scope of the present invention) A hydrogenated polymer produced by the following method was
The sample was pelletized at 280°C using a mm extruder, and then a test piece was prepared at 280°C using an injection molding machine (Toshiba 1s-80A).

In a reaction vessel purged with nitrogen gas, 500 g of a specific monomer 8-carboxymethyltetracyclo[4,4,0,1,1''0]-32,5-dodecene represented by the following structural formula (1) was added. , 1,2-dichloroethane 200
0ml, 3.8g of 1-hexene as a molecular weight regulator, and a concentration of 0.05M/A of tungsten hexachloride as a catalyst.
91.6 ml of a chlorobenzene solution and a concentration of balaldehyde of 0. 68.7 ml of 1M/fl 1°2-dichloroethane solution and triisobutylaluminum with a concentration of 0.
．． 5M/I! Add 37 ml of toluene solution of , 6
By reacting at 0°C for 10 hours, the intrinsic viscosity (ηi
nh) 0. 78 tan/g (in chloroform, 306
C1 concentration 0. 450 g of a ring-opened polymer (5 g/wash) was obtained.

This ring-opening polymer was dissolved in 9000 ml of tetrahydrofuran, 45 g of palladium-alumina catalyst with a palladium concentration of 5% was added, and hydrogen gas was introduced at a pressure of 100 kg/cr.
It was charged so that it became I, and hydrogenation reaction was carried out at 150°C for 5 hours.

After the hydrogenation reaction, the catalyst was separated and the P solution was poured into a large excess of methanol acidified with hydrochloric acid to produce a hydrogenated polymer.

The hydrogenation rate of this polymer A-1 was substantially (60 MHz
(measured by NMR) was 100%.

Structural formula (A-1) 0OCH3 Molded article A-2 (molded article within the scope of the present invention) 80% of Kraton G1650, which is obtained by hydrogenating a block copolymer of aromatic vinyl and butadiene, is added to the composition of molded article A-1. This is a test piece obtained by molding a composition blended with a ratio of /20.

Molded products A-3 to 6 (molded products outside the scope of the present invention) Molded product A
-3: AS resin (AN content 32%) molded product Molded product A-4: Polycarbonate (Idemitsu A2200) molded product A-5: MMA molded product A-6: Nylon 6 (East CMI 017) molded product Reflux In a reactor equipped with a cooler and a stirrer, (a) 9225 parts of methyltrimethoxine, (b) methanol-dispersed colloidal silica (solid content concentration 30%, manufactured by Nichiwa Kagaku Kogyo ■),
Mix 10 parts of methanol sol) and 6 parts of tap water (C), heat to 70°C and react for 2 hours,
- 38 parts of propyl alcohol was added to obtain coating composition (2).

By the same operation as above, (a) the type and amount of organoalkoxysilane, (b) the amount of colloidal silica,
Coating compositions (1) to (2) were obtained by changing (C) the amount of tap water, (d) the type and amount of the hydrophilic organic solvent, and the reaction temperature and reaction time as shown in Table 1.

Further, 45 parts of zirconium silicate and 6 parts of titanium dioxide were added to 77 parts of coating composition (2) to obtain coating composition (2).

Coating compositions 1 to 2 having the compositions shown in Table 1 were obtained in the same manner as B-1.

Furthermore, methanol-dispersed colloidal silica was mixed with water-dispersed colloidal silica (solid content concentration 20%, manufactured by Nichiryo Kagaku Kogyo ■,
Coating compositions 0 to 2 having the compositions shown in Table 1 were obtained in the same manner as in Example 1, except that Snowtex-0) was used instead.

The following margin coating compositions B-20~■ (scope of the present invention) In a reactor equipped with a reflux condenser and a stirrer, methyltrimethoxysilane 20%), 15 parts of i-propyl alcohol were added, heated to 60°C and reacted for 4 hours, further added 5 parts of γ-glycidoxypropyltrimethoxysilane, heated to 60°C and reacted for 20%. Let react for 10 minutes, cool to room temperature and add another 10 minutes of i-propyl alcohol.
0 parts added, the weight average molecular weight in terms of polystyrene is 8,
A composition [stock] containing a specific reaction product of 0.000 was obtained.

In the same manner as above, component (a) and component (b) are listed.
Coating compositions ① to ② of the present invention were obtained by making the following changes.

Examples 1 to 1, Comparative Examples 1 to 18 The coating compositions shown in Tables 1 and 2 were applied to the surfaces of molded products A-1 to A-6 using an air spray gun to a dry film thickness of 10 μm. A cured coating film was formed by applying the coating as described above and heating it at 140° C. for 60 minutes.

Evaluation results of coated molded products are shown in Table-3 and Table-4.
Shown below.

The following is based on margin heat resistance + ASTMD (value at a load of 4.6 kg/cJ).

Scratch resistance: Pencil hardness (JIS K5400) under load 1
Value at 00g.

Adhesion: Test piece was heated to [-30°C (1 hour) - room temperature (15
After conducting a conocycle three times at -80°C (1 hour m1), a base rotist and tape peeling test according to JIS K5400 was conducted.

Weather resistance: The degree of coloration of the coating film is measured by irradiating with a sunshine weather meter for 1000 hours according to JIS K5400.

○: Good, △: Slightly yellow, X: Yellow Chemical resistant gasoline is applied and it is determined whether or not the test piece is eroded.

O: No change, Δ: Cracks, X: Melts [Effects of the Invention] Molded articles coated with the coating composition of the present invention have extremely excellent coating film adhesion, and have excellent heat resistance, scratch resistance, weather resistance, It has excellent chemical resistance and has improved physical properties while maintaining the transparency of component (A), and has high industrial value and can be used as automobiles, electrical/electronic equipment, and housing materials. It is something.

Claims (2)

[Claims] (1) (A) Ring-opening polymerization of a monomer consisting of at least one norbornene derivative represented by the following general formula (I), or this monomer and a copolymerizable monomer copolymerizable therewith. (B) (a) General formula RSi(OR')_3 [wherein, R represents an organic group having 1 to 8 carbon atoms, and R' represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. (b) 0 to 50 parts by weight of colloidal silica dispersed in a hydrophilic organic solvent in terms of solid content; c) A composition formed by mixing 0.1 to 50 parts by weight of water, and (d) 100 to 1,000 parts by weight of a hydrophilic organic solvent (including the hydrophilic organic solvent present in component (b)). Thermoplastic resin molded products made by coating materials. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and
10 hydrocarbon groups, halogen atoms, hydrocarbon groups having 1 to 10 carbon atoms substituted with halogen atoms, ▲ mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ R^3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ COZ, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ composed of X and Y, and at least one of X and Y is a hydrogen atom and Groups other than groups selected from hydrocarbon groups {where R^1, R^2, R^3 and R^4 are hydrocarbon groups having 1 to 20 carbon atoms, and Z is a hydrocarbon substituted with a halogen atom group, W is SiR^5_pD_3_-_p
(R^5 is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR^6 or -OR^6 (R^6 is a hydrocarbon group having 1 to 10 carbon atoms), p is 0 ~3), n represents an integer of 0 to 10. }, and m is 0
or 1. ] (2) Claim 1 (A) on the surface of the molded product, (B)
(a) General formula CH_3SiX_3 [wherein, X is a halogen atom or a group represented by OR^1, where R^1
represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. ] Methylsilane or its hydrolyzate or its partial condensate and/or the methylsilane represented by the general formula R^2_aSi(OR^1)_4
_-_a [In the formula, R^2 is an organic group having 2 to 8 carbon atoms, a represents an integer of 0 to 2, and OR^1 is the same as above. ] or a partial cocondensate with an organoalkoxysilane represented by
)_bSi(OR^1)_3_-_b [wherein, R^3 is an organic group having 3 to 10 carbon atoms, b is an integer of 0 or 1, OR
^1 is the same as above. A thermoplastic resin molded article coated with a composition prepared by mixing an alkoxysilane represented by the following formula, a hydrolyzate thereof, or a partial condensate thereof.