JP2790413B2 - Polydicyclopentadiene-coated article and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polydicyclopentadiene-coated article having improved durability and a method for producing the same, and more particularly, to coating a polydicyclopentadiene article with a specific organic solvent when coating the article surface. The present invention relates to a method for coating a polydicyclopentadiene article characterized by improving adhesion and durability by applying a solvent-soluble fluororesin paint after contact.

[0002]

2. Description of the Related Art Polydicyclopentadiene is obtained by converting C in petroleum.
The cyclopentadiene present in the five fractions is heated to 2
It is a resin obtained by polymerizing dicyclopentadiene obtained by quantification. Although this resin is a relatively new resin launched in 1985, it can be used for reaction injection molding, and the resulting molded product has excellent impact resistance at low temperatures. It is increasingly used for exterior parts. In addition, compared to other reaction injection molding resins, it has the features of being able to produce large molded products, high yield, and low molding temperature and pressure, so that relatively inexpensive molding machines and molds can be used. It is expected to expand to other applications in the future.

However, since the polydicyclopentadiene molded product taken out of the molding machine has a light brown color, the appearance is poor as it is, and it is usually supplied to each user after being colored with various paints. .

[0004]

Urethane resin-based paints and acrylic resin-based paints have conventionally been used for coating polydicyclopentadiene molded products. However, over time, peeling, reduction in gloss, and change in color have occurred. Phenomenon occurs,
In many cases, the appearance was impressive.

On the other hand, polydicyclopentadiene molded articles have the above-mentioned excellent properties, but have the disadvantage that dicyclopentadiene, an unreacted monomer, always remains in a small amount. Therefore, it has a peculiar odor, and it is known that this odor continues to be emitted for a considerably long period of time. Therefore, painting on the surface is considered to be a kind of measure against this odor in addition to meaning of coloring. On the other hand, from the viewpoint of painting, the fact that unreacted monomers volatilize constantly from the surface means that not only is adhesion not easy during painting, but the coating film is also affected by unreacted monomers over a long period of time. It is clear that it works as a negative factor from the viewpoint of durability.

Accordingly, an object of the present invention is to provide an article made of polydicyclopentadiene which has no change in appearance even after long-term use and has little volatilization of unreacted monomers.

[0007]

Means for Solving the Problems From the above-mentioned viewpoints, the present inventors have conducted intensive studies on a method for improving the adhesion of a coating film to the surface of a polydicyclopentadiene article and a method for improving durability. After contacting the surface of the substrate with a specific organic solvent, a solvent-soluble fluororesin paint is applied to the surface, so that the polydicyclo has good adhesion to the substrate and has long-term durability. The inventors have found that a pentadiene-coated article can be obtained, and have completed the present invention.

[0008] That is, the present invention is to contact a solvent containing an aromatic organic solvent with the surface of a polydicyclopentadiene article to reduce the influence of a releasing agent, an additive or the like adhering to the article surface during molding. The purpose is to eliminate and eliminate the effect of modifying the surface of the resin, whereby the adhesion to the solvent-soluble fluororesin paint to be applied later is enhanced. Although it is not clear what the modification is, it is considered that the modification is caused by swelling due to penetration of a solvent into the resin surface. Furthermore, since the solvent-soluble fluororesin paint is known to have better weather resistance and chemical resistance than non-fluorine paints,
It has been found that a coated article having good adhesion and excellent durability can be obtained even when exposed to the monomer for a long period of time or exposed to the outdoors.

The aromatic organic solvent to be brought into contact with the surface of the polydicyclopentadiene article used in the present invention includes benzene, toluene, xylene, ethylbenzene, 1-methyl-3-ethylbenzene, cumene, mesitylene, monochlorobenzene, o-dichlorobenzene. , Trichlorobenzene, bromobenzene, benzyl alcohol, cresol, etc., which are commonly used as paint solvents, can be used alone or in combination, and these solvents can be used in combination with non-aromatic organic solvents. If
It is important that the content of the aromatic solvent is 30% or more by weight.

The organic solvents other than the aromatic solvents include alcohols, esters, ethers, ketones and the like, singly or in combination. Specifically, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isoamyl alcohol, methyl isobutyl carbinol, n-hexyl alcohol, 2-ethylbutanol, n-octanol, 2-ethylhexanol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl Alcohol, methyl formate, ethyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate,
Amyl acetate, isoamyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, ethyl propionate, butyl propionate, amyl propionate, butyl butyrate, diethyl carbonate, diethyl oxalate, methyl lactate, ethyl lactate, triethyl phosphate, γ-butyrolactone, Ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, isopropyl ether, n-butyl ether, dichloroethyl ether, anisole,
Dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone,
Examples include dimethyl oxide, diacetone alcohol, cyclohexanone, methylcyclohexanone, isophorone or mixtures thereof.

If the content of the aromatic solvent is 30% or less, the adhesion of the solvent-soluble fluororesin paint to the polydicyclopentadiene article becomes poor, and the intended purpose cannot be achieved. Mixed solvents containing aromatic organic solvents are also commercially available, for example, Solvesso 100, 150
(Manufactured by Esso Chemical), Swazole 100, 200, 31
Examples thereof include 0, 1000, 1500, and 1800 (manufactured by Maruzen Petrochemical), Shellsol A, and AB (manufactured by Shell Chemical), and these can also be used.

In addition, if the time until the coating is too long after the surface is brought into contact with the aromatic organic solvent, the modified surface may return to its original state or its effect may be diminished. Usually, it is preferable to apply the coating within 2 hours at room temperature, more preferably within 1 hour, but this time varies considerably depending on the coating environment.

The fluorinated copolymer which is a main component of the solvent-soluble fluororesin paint used in the present invention is a fluorinated copolymer having a hydroxyl group and / or a carboxyl group in a molecule.

The fluorinated copolymer is a polymer containing at least one fluorinated monomer selected from fluoroolefins such as chlorotrifluoroethylene, tetrafluoroethylene, and vinylidene fluoride as a copolymer component. is there.

The vinyl compound which can be used as another copolymer component of the fluorine-containing copolymer is represented by the general formula CH ₂ = CHOC
Vinyl ester represented by (= O) R ₁ , for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate (versatic pentanate), vinyl caproate, vinyl isocaproate, vinyl caprylate,
Vinyl ethers represented by the general formula CH ₂ = CHOR ₂ , such as vinyl caprylic acid, vinyl caproic acid, vinyl versatate 9, vinyl versatate 10, and vinyl benzoate, for example, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether Allyl ethers represented by the general formula CH ₂ = CHCH ₂ OR ₃ , such as ethyl allyl ale, butyl allyl ether, benzyl allyl ether, allyl glycidyl ether, cyclohexyl allyl ether, etc.
₂ = (meth) acrylate represented by CR ₄ COOR ₅ , for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, vinyl silane represented by the general formula CH ₂ = CHOSi (OR ₆ ) ₃ ,
For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (methoxyethoxy) silane,
Examples include vinylmethyldiethoxysilane and vinylphenyldimethoxysilane. In each of the above general formulas
R ₁ , R ₂ , R ₃ , and R ₅ are a linear, branched or alicyclic alkyl group having 1 to 22 carbon atoms, an aromatic group, a group containing an ester bond or an ether bond, or a combination thereof. R ₄ is hydrogen or a methyl group, and R ₆ is hydrogen or an alkyl group. However, 3 bonded to Si
Number of R ₆ is not necessarily the same.

Examples of the polymerizable compound containing a hydroxy group that can be used in the fluorine-containing copolymer include the above-mentioned vinyl esters, vinyl ethers, allyl ethers, (meth)
An acrylate compound having one terminal or side chain
Compounds containing one or many hydroxy groups, crotonic acid-modified compounds such as hydroxyethyl crotonate,
Vinyl lactate, allyl alcohol and the like are preferably used. Specifically, as the hydroxyalkyl allyl ether, 2-allyloxy-1-ethanol (ethylene glycol monoallyl ether), 3-allyloxy-1-
Propanol, 4-allyloxy-1-butanol, 5-
Allyloxy-1-heptanol, 6-allyloxy-1-
Hexanol, 3-allyloxypropane-1,2-diol, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, cyclohexane dimethanol allyl ether, glycerin monoallyl ether, ethylene glycol monoallyl ether
-A monomer modified with caprolactam.

Examples of the hydroxyalkyl vinyl ether include hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether and the like. As hydroxyalkyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, N-
Methylol acrylamide, cyclohexane dimethanol (meth) acrylate and the like can be mentioned.

Examples of the carboxyl group-containing monomer that can be used in the fluorine-containing copolymer include vinyl acetic acid, lactic acid, undecylenic acid, allyloxyacetic acid, acrylic acid, methacrylic acid, crotonic acid, and itaconic acid.

As an example of the fluorine-containing copolymer used in the present invention, the content of units based on a fluorine-containing monomer, vinyl carboxylate, hydroxyl group-containing allyl ether and other comonomer is 25 to 75, respectively. Mol%, 10-40 mol%, 3-40 mol% and 0-20 mol%.

In the polymerization method of the above-mentioned multicomponent fluorine-containing copolymer, a usual radical polymerization method can be adopted, and the polymerization form can be solution polymerization, suspension polymerization, emulsion polymerization, or bulk polymerization. . The temperature of such a polymerization step is
Usually 0 to 130 ° C., depending on the radical polymerization initiator used
It is. Examples of the solvent include water, alcohols such as t-butanol and ethyl alcohol, n-hexane and n-hexane.
-Saturated hydrocarbons such as heptane, aromatic hydrocarbons such as toluene and xylene, fluorines such as trichlorotrifluoroethane and dichlorotetrafluoroethane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate and acetic acid Esters such as butyl can be used. As the radical initiator,
For example, diisopropyl peroxydicarbonate, di-
Dicarbonates such as n-propylperoxydicarbonate and di-2-ethylhexylperoxydicarbonate; or diacyls such as n-heptafluorobutylic peroxide, lauroylperoxypivalate and t-butyloxyneodecanate Peroxides,
Conventional radical initiators such as alkyl peroxides such as di-t-butyl peroxide and t-butyl cumyl peroxide can be used.

The molecular weight of the fluorine-based copolymer polymerized as described above can be used in the range of 1,000 to 30,000 depending on the required strength and flexibility of the coating film.
In this case, if it is less than 1,000, the weather resistance and flexibility of the coating film are reduced, and if it is more than 30,000, it becomes unfavorable because it has a high viscosity in the preparation of a coating and it is difficult to handle.

The fluorocopolymers thus produced vary depending on the production method, but all are used in the form of being dissolved in an organic solvent and, if necessary, used in paints other than the solvent-soluble fluororesin paint described below. And additives such as a resin, a pigment, a leveling agent, an ultraviolet absorber, a light stabilizer, and an anti-settling agent, to obtain a solvent-soluble fluororesin paint. Since the coating has a hydroxyl group and / or a carboxyl group as a curing site, a curing reaction can be caused by combining with a curing agent. As the curing agent, polyisocyanurate which is a two-pack type paint, blocked isocyanate or melamine which is a one-pack type paint can be used, and polyisocyanurate is more preferable in consideration of the heat resistance of the polydicyclopentadiene article. The amount of the curing agent added is preferably in the range of 0.5 to 1.5 for the NCO / OH ratio.
If it is larger, it is not preferable in terms of weather resistance.

The solvent for the paint containing these fluorinated copolymers is an aromatic, ester, ether, ketone or other single or mixed solvent. Specifically, for example, toluene, xylene, ethylbenzene, cumene,
Mesitylene, monochlorobenzene, o-dichlorobenzene, trichlorobenzene, bromobenzene, methyl formate, ethyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, acetic acid 2-ethylhexyl, cyclohexyl acetate, ethyl propionate, butyl propionate, amyl propionate, butyl butyrate, diethyl carbonate, diethyl oxalate, methyl lactate,
Ethyl lactate, triethyl phosphate, γ-butyrolactone,
Ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, isopropyl ether, n-butyl ether, dichloroethyl ether, anisole, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dimethyl oxide, diacetone alcohol,
Examples include cyclohexanone, methylcyclohexanone, isophorone or mixtures thereof.

In the present invention, the polydicyclopentadiene article may be prepared even if the polydicyclopentadiene is accompanied by a filler such as glass, glass fiber, metal, metal fiber, wollastonite, mica, carbon black, talc or calcium carbonate. As a polymer modifier, various polymers, for example, natural rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene copolymer, styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene It can be used in combination with a triblock rubber, an ethylene-propylene-diene copolymer or the like. In addition, the polydicyclopentadiene article is not limited to an article composed of only polydicyclopentadiene, and may be an article combined with another base material, such as metal, plastics, or glass. Examples of the article include molded articles having various shapes, but the shape is not particularly limited, and examples thereof include articles for uses such as automobiles, electric appliances, sporting goods, and construction machines.

In the production method of the present invention, the method of contacting the aromatic organic solvent with the polydicyclopentadiene is particularly limited. For example, a flexible substance (for example, cloth or paper) impregnated with the aromatic organic solvent is used. , A porous substance, etc.), immersion of an aromatic organic solvent in a bath, spray treatment, and the like. In performing such contact processing,
The polydicyclopentadiene article may be preliminarily subjected to removal of foreign substances such as a release agent which adheres to the article surface as it is usually molded by using a solvent other than the aromatic organic solvent or containing only 30% or less of the aromatic organic solvent. Although possible, such pre-processing is not necessary. The temperature of the treatment with the aromatic organic solvent of the present invention does not need to be particularly limited, but is preferably performed at a temperature at which the vapor pressure of the solvent does not become too high from the viewpoint of working environment and equipment. Therefore, it is usually about −20 to 60 ° C., preferably 0 to 50 ° C.
C., more preferably at room temperature.

The method of applying the solvent-soluble fluororesin paint used in the present invention is not particularly limited, and after the above-mentioned contact treatment, spray coating, dipping coating, and the like usually used in the field of the art. Methods such as roll coating and brush coating can be applied, and after coating, the coating can be cured in a temperature range from room temperature to several hundred degrees Celsius.

The polydicyclopentadiene-coated article of the present invention may further comprise a paint other than a solvent-soluble fluororesin paint on the outside thereof for imparting various purposes, for example, aesthetics, fire resistance, conductivity, etc. Phenolic resin, phthalic acid resin, maleic acid resin, urea resin, melamine resin, vinyl acetate resin, vinyl chloride-vinyl acetate resin, styrene resin, acrylic acid resin, acrylic-silicone resin, polyvinyl butyral, epoxy resin, silicone resin,
One or more layers of paint consisting of furan resin, polyester resin, nitrocellulose, alkyd resin, and a mixture of these resins, and a mixture of these resins with metal powder, glass, wollastonite, mica, carbon black, talc, or calcium carbonate You can also.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. Example,
In the comparative examples, "parts" means "parts by weight".

[0029]

【Example】

[Synthesis Example A of Resin and Production of Enamel Using It]
92.3 g of vinyl pivalate (VPv) in a 1.4 L stainless steel autoclave with magnetic stirrer
9 (V-9) 132.5 g, ethylene glycol monoallyl ether (EGMAE) 37.9 g, undecylenic acid (UA)
7.6 g, 3.8 g of perbutyl PV (trade name of Nippon Oil & Fat), 320 g of butyl acetate (BuAc) and 1.6 g of sodium carbonate were charged, and the autoclave was replaced with nitrogen gas and degassed three times. Thereafter, after introducing 263.8 g of chlorotrifluoroethylene (CTFE) into the autoclave, the temperature was gradually raised. 55 ℃
After 17 hours of polymerization, unreacted CTFE was removed and the autoclave was opened. Then, the polymerization solution was transferred to an eggplant-shaped flask and concentrated by an evaporator. At the same time, unreacted monomers other than CTFE were also removed, and then diluted with BuAc to a solid concentration of about 55% by weight, filtered and purified to obtain a varnish.
The yield was 82% based on the charged monomer based on the solid concentration at the time of opening the autoclave. The OH value of the obtained resin was 45 mgKOH / g (measured by an acetylation method using acetic anhydride), and the acid value was 6.9 mgKOH / g (JIS K 5400
), And the molecular weight (Mn) was 15,300 (polystyrene reduced number average molecular weight).

To 100 g of the obtained varnish, 27.5 g of titanium oxide and 0.06 g of a leveling agent were added as a pigment and kneaded for 1 hour in a batch-type sand mill. After filtering the beads, 110 g of enamel was obtained (obtained). The enamel was designated as A-1).

[Resin Synthesis Examples B and C and Production of Enamels Using the Same] In the same manner as in Resin Synthesis Example A, the copolymer charge composition shown in Table 1 (however, the charge amount of perbutyl PV is based on the monomer amount) 0.5% by weight)
The yield, OH value, acid value, and molecular weight were measured. The obtained varnish was enamelled by the same method as described in Synthesis Example A of the resin (the obtained enamels were designated as B-1 and C-1, respectively).

[0032]

[Table 1]

Example 1 A plate-like polydicyclopentadiene article having a smooth surface (150 mm × 70 mm × 5 m
m) Wipe the surface with a rag soaked with toluene,
After a lapse of 30 minutes, coronate HX as a curing agent was added to 110 g of the white enamel (A-1) prepared in Synthesis Example A of the resin.
(Manufactured by Nippon Polyurethane Industry Co., Ltd.) in a predetermined amount (NCO /
(OH = 1.0) 7.6 g was added, and the mixture was applied using a spray. In order to dilute the white enamel to a spray concentration, the white enamel was diluted with a mixed solvent (composition ratio: 3/4/3) containing toluene, xylene, and isopropyl acetate as main components. The obtained coated plate was allowed to stand at room temperature for 10 minutes, cured and dried at 80 ° C. for 45 minutes, cooled, and then subjected to a cross-cut cellophane tape peel test (primary adhesion). 40 ° C for coated plate with good primary adhesion
Was immersed in warm water for 64 hours, and the same adhesion evaluation test was performed (secondary adhesion). The appearance at this time was visually observed. At the same time, the coated plate prepared was placed in a sunshine carbon arc weather meter (SWM), which is an accelerated weather resistance tester, subjected to a test for 2,000 hours, and the gloss of the coated plate before the test was compared.

The evaluation of various physical properties was carried out according to the following methods.・ Cross-cell to cellotape test: Cuts at 1 mm intervals are made in the coating film based on the adhesion test method of JIS K 5400 to make 100 cells. Then, a cellophane tape is stuck on the surface of the cells, and the cell is peeled off instantaneously, and the number of remaining cells is indicated. However, in Table 2, 100/100 is indicated by “で”.

Gloss measurement: described in JIS K 5400
Measure 60 degree gloss. -Appearance: Visually, if there is no abnormality, it is indicated by "O". Examples 2 to 7 and Comparative Examples 1 to 3 As shown in Table 2, enamel (A-1) or enamel (B-
1) Using an enamel (C-1) or a polyester resin coating containing a white pigment, coating, testing and measurement were performed in the same manner as in Example 1 except that treatment with various solvents shown in Table 2 was performed. Table 2 shows the results. Since the secondary adhesion was poor in Comparative Examples 1 and 2, the SWM test was not performed. In each case, the results are shown in Table 2.

In Comparative Examples 1 and 2, the aromatic solvent was not used. Therefore, in the primary adhesion test, the adhesive strength of the paint was changed so that the aromatic solvent was used as shown in the examples so that the coating already partially peeled off. It is clear that it is significantly inferior. On the other hand, in Comparative Example 3, since the solvent-soluble fluororesin paint was not used as the paint, the adhesiveness was sufficient, but the gloss was reduced in a short time.

[0037]

[Table 2]

[0038]

The polydicyclopentadiene-coated article of the present invention has an effect that it can be used in applications requiring aesthetic appearance, because the coated film has good long-term adhesion and a small decrease in gloss.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-235940 (JP, A) JP-A-63-162071 (JP, A) JP-A-63-224915 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) C08J 7/04 B32B 27/00-27/00 104 C09D 127/12

Claims (4)

(57) [Claims] 1. A polydicyclopentadiene article having on its surface a coating formed from a solvent-soluble fluororesin paint containing a fluorine-containing copolymer having a hydroxyl group and / or a carboxyl group in the molecule. Polydicyclopentadiene coated articles 2. The polydicyclopentadiene coating according to claim 1, wherein the fluorine-containing copolymer having a hydroxyl group and / or a carboxyl group in a molecule contains at least a fluoroolefin and a vinyl ester as a copolymerization component. Goods 3. The surface of the polydicyclopentadiene article is brought into contact with a solvent containing an aromatic organic solvent,
3. A polydicyclopentadiene-coated article according to claim 1, which is obtained by coating a solvent-soluble fluororesin paint containing a fluorine-containing copolymer having a hydroxyl group and / or a carboxyl group in a molecule. Manufacturing method 4. The method for producing a polydicyclopentadiene-coated article according to claim 3, wherein a solvent having an aromatic solvent content of 30% or more is used.