JPH05271620A - Covered molding - Google Patents

Abstract

PURPOSE:To obtain a covered molding having a cured covering film which is pliable and tough and has good adhesion by coating a molding with a composition containing a specific amount of a polymerizable compound which has an acyl-urethane structure represented by a specific formula and curing the composition. CONSTITUTION:A coating composition comprising as an essential ingredient at least 0.5wt.% polymerizable compound (a) having an acyl-urethane structure represented by formula I (wherein R is H or a lower alkyl) is used to cover a molding and the coating is cured. Thus, a covered molding is obtained in which the cured covering film is pliable and tough and has good adhesion. The compound (a) is produced by, for example, reacting a compound having an active hydrogen, e.g. a compound having OH, with an acyl isocyanate represented by formula II (wherein R is as defined above). This reaction proceeds readily in the presence or absence of an inert solvent in a temp. range from temps. with ice-cooling to room temp.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated molded body, and more particularly to a coated molded body formed with a cured coating which is flexible and tough and has good adhesion. In this specification, “coating” is used in the broadest sense and means that a coating film is provided on a substrate so as to cover at least a part thereof.

[0002]

2. Description of the Related Art Various coating compositions for coating a substrate have been heretofore known. However, it is necessary to always form a coating having sufficient flexibility, toughness and adhesion in a wide temperature range. There are few such coating compositions. This will be explained by taking an optical fiber used for optical transmission as an example.
The glass fiber, which is the main body of the transmitter, is brittle, is easily scratched, and lacks flexibility, so that it is easily broken even by a slight external force. Therefore, a resin coating is provided on the outer circumference of the optical transmission fiber made of glass to protect it. Epoxy resins, urethane resins, etc. have been conventionally used as such coating resin materials, but they have sufficient flexibility and toughness in the normal operating temperature range of optical fibers, -40 to 80 ° C. In addition, the workability is poor because the curing takes a relatively long time. Therefore, there is a demand for the appearance of a resin material capable of providing a coating excellent in flexibility and toughness in a relatively short curing time, and some proposals have actually been made. For example, JP-A-57-925
No. 53, it is proposed to use a diacrylate of polyether polyol having a molecular weight of 2000 or more. JP-A No. 58-223638 discloses a polymerizable oligomer having an amide urethane structure and a polyalkylene polyether structure. It has been proposed to use a composition containing, as an essential component, a polymerizable monomer giving a low glass transition point polymer and a polymerizable monomer capable of forming a strong hydrogen bond.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The inventors of the present invention have long been engaged in various studies to provide a coating composition excellent in flexibility, toughness and adhesion. In particular, in the case of a composition for coating an optical fiber, as is clear from the above, it is in the normal operating temperature range of -40 to 80.
It is necessary for the resin material to be capable of forming a coating that always exhibits good flexibility and toughness at 0 ° C within a short curing time.

[0004]

As a result of research, the present inventors have found that the use of a polymerizable compound having an acylurethane structure serves the above purpose, and based on this finding, the present invention is completed. Came to.

No polymerizable compound having an acylurethane structure has been produced so far. Therefore, it can be said what kind of characteristics such a polymerizable compound has and also a polymer of such a polymerizable compound. It was not known what kind of characteristics it had.

[0006] According to the research conducted by the present inventors, a polymerizable compound having an acylurethane structure has an extremely high vinyl bond present therein, and it is easy to irradiate with a high energy ray or a radical polymerization catalyst. It was clarified that the polymerization and curing were efficient and efficient. Further, it has been clarified that the polymer obtained by such polymerization and curing is rich in flexibility and at the same time has high toughness and good adhesion. Such characteristics of the polymerizable compound having an acylurethane structure and the polymer thereof indicate that they are suitable as the main component of the coating composition and as the coating material of the coated molded body.

The gist of the present invention resides in a coated molded product obtained by coating a molded product with a coating composition containing at least 0.5% by weight of a polymerizable compound having an acylurethane structure as an essential component and curing it.

Since the above-mentioned polymerizable compound having an acyl urethane structure has an extremely high polymerization activity, the polymerization reaction is rapidly advanced and cured by irradiation of high energy rays and blending of a catalyst. Further, the coating film obtained by curing has excellent flexibility, toughness and adhesion.

[0009]

As described above, the coating composition used in the present invention is characterized in that it contains a polymerizable compound having an acyl urethane structure as an essential component. A typical example of the acyl urethane structure is It can be shown by the following formula: Formula (A) (In the formula, R represents hydrogen or lower alkyl). Specific examples of the acyl urethane structure include an acryloyl urethane structure, a methacryloyl urethane structure, and an ethacryloyl urethane structure.

In order to produce a polymerizable compound having the above-mentioned acyl urethane structure (A), for example, an active hydrogen-containing compound such as a hydroxy group and a compound of the formula (B): (In the formula, R has the same meaning as described above.) The acyl isocyanate represented by the formula may be reacted. This reaction easily proceeds in the presence or absence of an inert solvent, at −40 to 100 ° C., preferably under ice cooling to room temperature (0 to 30 ° C.). If necessary, an appropriate polymerization inhibitor may be present in order to prevent the progress of side reactions relating to the vinyl bond.

The active hydrogen-containing compound is not particularly limited as long as it has at least one active hydrogen atom, and various compounds such as monomers, oligomers and polymers can be selected and used, and specific examples thereof are given. For example:

Low molecular weight hydroxy compounds such as alkanols (eg methanol, ethanol, n-propanol, isopropanol, stearyl alcohol),
Alkenols (e.g. allyl alcohol, crotyl alcohol), alalkanols (e.g. benzyl alcohol, phenethyl alcohol), alalkenols (e.g. cinnamyl alcohol), phenols, di (lower) alkylamino (lower) alkanols (e.g. dimethylamino). Methanol, dimethylaminoethanol, dimethylaminopropanol, diethylaminoethanol, diethylaminopropanol, N-methyl-N-ethylaminopropanol), di (lower) alkylaminophenol Le
(For example, o-dimethylaminophenol, m-dimethylaminophenol, p-dimethylaminophenol, m-
Diethylaminophenol), lower alkyl-phenylamino (lower) alkanol (eg N-methyl-N-
Phenylaminoethanol, N-methyl-N-phenylaminopropanol), lower alkyl-phenyl (lower)
Alkylamino (lower) alkanols (eg N-methyl-N-benzylaminoethanol, N-ethyl-N-
Benzylaminoethanol, N-ethyl-N-phenethylaminopropanol), N-hydroxypyrrolidine,
N-hydroxypiperidine, N-hydroxymorpholine, pyrrolidino (lower) alkanol (eg pyrrolidinoethanol, pyrrolidinopropanol), piperidino
(Lower) alkanol (e.g. piperidinoethanol,
Piperidino propanol), morpholino (lower) alkanol (e.g. morpholino ethanol, morpholino propanol), di (lower) alkylamino (lower) alkoxy
(Lower) alkanol (e.g., dimethylaminoethoxyethanol, dimethylaminoethoxypropanol, diethylaminoethoxypropanol), atropine, etc .;

Polyether polyol compounds such as polyalkylene glycols (eg polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol) or alkylene oxides (eg ethylene oxide, propylene oxide, tetrahydrane) are polyols (eg ethylene glycol). , Diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,2,6-hexanetriol, pentaerythritol, sorbitol , Sorbitan, sucrose), and other polyether polyols obtained by the addition thereof;

Polyester polyol compounds such as polybasic acids (eg phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid,
Tetrabromphthalic acid, hexahydrophthalic acid, hymic acid, het acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, dodecenyl succinic acid, trimellitic acid, pyromellitic acid) or their anhydrides and polyhydric alcohols (For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane,
1,3-butanediol, 1,4-butanediol, 1,
6-hexanediol, neopentyl glycol, 1,
2,6-hexanetriol, pentaerythritol,
Polyester polyol obtained by condensation reaction with sorbitol, bisphenol A), polyester obtained by reaction of the above polyhydric alcohol and epoxy compound (for example, Curdula E, n-butyl glycidyl ether, allyl glycidyl ether) and the above polybasic acid Polyol, polyester polyol obtained by reaction of the epoxy compound and the polybasic acid, higher fatty acid (for example, soybean oil, linseed oil, safflower oil, coconut oil, dehydrated castor oil, tung oil, rosin) and the polybasic acid And an alkyd polyol obtained by the reaction of the above polyhydric alcohol, a polymerized polyester polyol obtained by ring-opening polymerization of ε-caprolactam and the above polyhydric alcohol, and the like;

Acrylic polyol compounds, such as ethylenically unsaturated monomers having hydroxyl groups (eg 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate) as an essential monomer, and if necessary, other monomers (for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl) Acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile. , Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate) And the like;

Polyurethane polyol compounds such as isocyanate compounds (eg ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1
-Methyl-2,4-diisocyanate cyclohexane,
1-methyl-2,6-diisocyanate cyclohexane, ω, ω′-diisocyanate diethylbenzene, ω,
ω'-diisocyanate dimethylaminotoluene, ω,
ω'-diisocyanate dimethyl xylene, ω, ω'-diisocyanate diethyl xylene, lysine diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 4,4'-ethylene bis (cyclohexyl isocyanate), ω, ω'-diisocyanate-1 , 3-Dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, isophorone diisocyanate, 2,4-
Tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 4,
4'-methylenebis (phenylisocyanate), triphenylmethanetriisocyanate) or a multimer thereof and an excess amount of a low molecular weight polyol (for example, ethylene glycol, propylene glycol, 1,3-butyl glycol, neopentyl glycol, 2) , 2,4-
Polyurethane polyol obtained by addition reaction with trimethyl-1,3-pentanediol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, sorbitol, sorbitan, sucrose, pentaerythritol, etc., as described above. Polyether polyols, polyester polyols, polymerizable polyester polyols and polyurethane polyols obtained by addition reaction of a relatively low molecular weight polyol compound among acrylic polyols with isocyanate compounds such as monoisocyanate, diisocyanate and triisocyanate;

Epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Polycarboxylic acid ester type epoxy resin, epoxidized type resin of aliphatic unsaturated compound, etc .;

Polybutadiene compounds such as hydrogenated or non-added 1,4-polybutadiene diol having a hydroxyl group at the terminal;

Polychloroprene compounds such as chloroprene compounds having a hydroxyl group at the terminal and / or side chain;

An amino resin compound, for example, melamine, guanamine, urea, etc., which is obtained by polymerizing an addition reaction product of formaldehyde and modified with an alcohol such as methanol, butanol, isobutanol, etc., has a high degree of methylolation and is alkoxyetherified. Low, especially butylated melamine resin having two or more methylol groups per triazine nucleus;

Star polymer compounds, such as a star polymer having an active hydrogen at the terminal obtained by cationic polymerization of pentol and ethylene oxide;

Phenolic resin compounds, such as novolac type or resol type phenolic resins obtained by the reaction of phenol and formaldehyde, rosin-modified phenolic resins, alkylphenol resins, butylated or allyl etherified resole resins, etc .;

A xylene resin compound;

Silicon compounds such as dimethyl (poly) siloxane, methylphenyl (poly) siloxane, methylvinyl (poly) siloxane, cyanoalkylmethyl
(Poly) siloxane, fluorinated alkylmethyl (poly) siloxane, and block copolymers or graft copolymers of any combination thereof, wherein the hydroxyl group is at the terminal or in the molecule;

Vinyl compounds such as polyvinyl alcohol and polyvinyl acetal;

Cellulosic compounds such as cellulose, nitrocellulose and the like;

Oligosaccharide compounds such as maltose, amylose and other oligosaccharides and their derivatives.

The inert solvent is not particularly limited as long as it does not adversely affect the reaction, and various ones can be used, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, benzene, toluene, xylene, etc. Aromatic hydrocarbons, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as decalin, hydrocarbon solvents such as petroleum ether, petroleum benzine, carbon tetrachloride, chloroform, halogenated carbonization such as 1,2-dichloroethane Hydrogen-based solvents, ethyl ether, isopyrether, anisole, dioxane, tetrahydrofuran, etc.
Tellurium solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone,
It may be appropriately selected from ketones such as isophorone, esters such as ethyl acetate and butyl acetate, acetonitrile, dimethylformamide, dimethylsulfoxide and the like. These may be used alone or as a mixture.

In order to collect the reaction product from the reaction mixture, a conventional separation means such as a solvent extraction method or a distillation method may be adopted.

In the above reaction and separation operation, a polymerization inhibitor may be added in order to avoid unnecessary polymerization of the vinyl bond of the acyl isocyanate (B). Specific examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 4-t-butylcatechol, bisdihydroxybenzylbenzene and 2,2′-methylenebis (6 -T-butyl-
3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), p-nitrosophenol, diisopropylxanthogen sulfide, N-nitrosophenylhydroxylamine ammonium salt,
1,1-diphenyl-2-picrylhydrazyl, 1,3,
5-Triphenylferdazyl, 2,6-di-t-butyl-α- (3,5-di-t-butyl-4′-oxo-2,5-
Cyclohexadiene-1-ylidene) -p-trioxy,
2,2,6,6-tetramethyl-4-piperidone-1-oxyl, dithiobenzoyl sulfide, p, p'-ditolyl trisulfide, p, p'-ditolyl tetrasulfide, dibenzyl tetrasulfide, tetraethyl thiuram disulfide And so on.

As a result of the above reaction, the active hydrogen atom of the active hydrogen-containing compound is added to the isocyanate group of the acyl isocyanate (B), and the polymerizable compound having the acyl urethane structure (A) is produced. The reaction proceeds extremely smoothly in a short time, and the polymerizable compound is obtained in good yield and purity.

The coating composition used in the present invention contains a polymerizable compound having an acyl urethane structure as an essential component in an amount of at least 0.5% by weight based on the weight of the composition.

As the other components, if necessary, a polymerizable monomer as a crosslinking agent or a diluent, a polymerization initiator as a curing accelerator, etc. may be added. The polymerizable monomer used here is not particularly limited as a cross-linking agent as long as at least one polymerizable double bond is present. Specific examples thereof include acrylic acid esters (eg, methyl acrylate, acrylic acid). Ethyl, butyl acrylate, todecyl acrylate, 2-ethylhexyl acrylate, ethyldiethylene glycol acrylate), methacrylic acid esters (for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, todecyl methacrylate, 2-ethylhexyl methacrylate, ethyl diethylene glycol) (Methacrylate), allyl ester, crotonic acid ester, maleic acid ester, vinylpyrrolidone, diacetone acrylamide, isobutoxymethyl acrylamide, acrylamide, N, N-dimethyl acrylamide, acetic acid Le acid, itaconic acid, dimethylaminoethyl acrylate Le - DOO and the like. As the polymerization initiator, benzoyl peroxide, t-butyl peroxybenzoate, acetophenone, benzophenone, etc. may be used. The usual amount used is 5 for the polymerizable monomer.
0% by weight or less, 10% by weight of the composition with respect to the polymerization initiator
It is below.

In addition to the above, a modifying resin and various additives may be blended as other optional components. Examples of the modifying resin include epoxy resin, polyamide, polyurethane, polyether, polyamideimide, silicone resin, and phenol resin. Other various additives include cobalt naphthenate, zinc naphthenate, curing accelerators such as dimethylaniline, organic silicon compounds, and surfactants.

The coating composition used in the present invention is cured by irradiation with various types of high energy rays. High-energy rays include ultraviolet rays, electron rays, x-rays, and radiation (eg, alpha rays, beta rays, gamma rays, hard x-rays), and any of these may be used, but the use of ultraviolet rays is common.

In order to coat the glass fiber with the above coating composition, a conventional method such as a die ironing method, a spray method or a fluidized dipping method may be employed. 2,459,320, JP-A-5
It may be performed by the method disclosed in the specification of 3-139545 or the like. When the glass fiber is coated by these methods and cured by irradiation with ultraviolet rays, the drawing speed of the glass fiber may be 3 to 5 m / sec or more. Also, one layer of coating is sufficient for coating on the glass fiber, but a two-layer coating may be applied. The performance of the obtained optical fiber is very excellent and has a sufficient practical value.

Originally, a resin which is polymerized and hardened by irradiation with a high energy ray can be hardened in seconds, so that productivity can be improved. In addition, since electric energy can be used for curing and there is almost no evaporation of the solvent, low pollution can be achieved. Furthermore, again
Since it does not require high temperature for curing, there is no thermal deformation of the coated object,
Since the curing device can be made compact, it is possible to save space. Furthermore, since the wavelength of the energy ray is short, the image reproducibility is good. Since the coating composition used in the present invention also has such advantages, in addition to the use as the above-mentioned coating agent for an optical fiber, an ultraviolet curable coating material, an electron beam curing coating material, a photoresist, an electron beam resist, an X-ray. Paint as resist, plate making material, etc.
It has a wide range of uses in the printing industry, electronic industry, and the like.

The resin composition which is cured with high energy rays generally has (1) a photocrosslinkable (or non-crosslinkable) polymer or oligomer, (2) a photopolymerizable monomer or a low molecular weight oligomer, and (3) a light A polymerization initiator (or a sensitizer) and (4) a thermal polymerization inhibitor (or a stabilizer) are contained, and if necessary, additives such as a sensitization aid and a colorant are contained.

As the polymer or oligomer of (1), unsaturated polyester resins, urethane acrylate resins, epoxy acrylate resins, polyester acrylate resins, spirane acrylate resins, polyether acrylate resins and the like are well known. As the photopolymerizable monomer or low molecular weight oligomer of (2), in addition to the low molecular weight oligomer of the polymer of (1) above, styrene, vinyltoluene, divinylpentene, vinyl acetate, acrylonitrile, methacrylonitrile, acrylic ester ( For example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, ethylene glycol diacrylate, trimethylolpropane triacrylate), methacrylic acid ester (for example, methyl methacrylate, ethyl methacrylate, methacrylic acid) Butyl, 2-ethylhexyl methacrylate, glycidyl methacrylate,
Ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate), diethyl itaconate,
Dibutyl itaconate, diethyl fumarate, diethyl maleate and the like are known. As the sensitizer of (3),
Known are benzoin, benzoin methyl ether, benzoin propyl ether, benzoin butyl ether, bezophenone, diacetyl, benzyl, dibutyl sulfide, dibenzyl sulfide and the like. As the thermal polymerization inhibitor (4), hydroquinone, t-butylhydroquinone, p-methoxyphenol, catechol, benzoquinone and the like are known.

The polymerizable compound having an acyl urethane structure in the present invention has the above-mentioned (1) and / or (2).
It may be used as all or part of the components of, especially as part or all of the components of (2).

The photo-curable resin composition as described above is used as a plate material or cured printing ink for letterpress, planographic printing, intaglio and screen printing plates in the printing industry, and as a paint, packaging material or adhesive in the coloring material industry. In the electronics industry, shadow masks, printed wiring, ICs, LSIs
As a resist for electronic parts such as, a dry film or a sealant, as a photoresist for plates and parts in the metal surface treatment industry, ceramics industry, glass industry, precision machinery industry, building materials industry, automobile industry or shipbuilding industry, In the textile industry, it can be used as a surface-treating agent, and in the biomedical industry, it can be used as an enzyme immobilizing agent or a cavity filling agent.

[0042]

EXAMPLES The present invention will be described in more detail with reference to the following Reference Examples and Examples.

Reference Example 1 (Synthesis of methacryloyl isocyanate) Methacrylamido 17.9 (g) and hydroquinone 0.1
To a suspension of 8 (g) of chloroform in 100 (ml),
Oxalyl chloride 20 (ml) in a nitrogen stream under ice cooling
15 ml of chloroform solution was added dropwise. After dropping
It returned to room temperature and stirred for about 100 minutes. Hydroquinone 0.18 (g) was added, and the mixture was further heated with stirring at 60 ° C. for 4 hours. After cooling, the reaction solution was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure to obtain methacryloyl isocyanate as a colorless liquid boiling at 52 to 53 ° C / 39 mmHg.

Reference Example 2 (Synthesis of Acryloyl Isocyanate) A solution of oxalyl chloride 95.25 (g) in 1,2-dichloroethane 150 (ml) was added to acrylamide 35.5 (g) at -30 to 0 ° C. And hydroquinone 0.54 (g) in 1,2-dichloroethane 200 (ml) solution about 30
Dropped in minutes. After dropping, heat reflux for about 1 hour,
After allowing to cool, distillation under reduced pressure was carried out to give 44.7 (g) of β-chloropropionyl isocyanate at a boiling point of 74 to 75 ° C / 2.
Obtained as a colorless liquid of 5 mmHg. Toluene 2 of the above-mentioned β-chloropropionyl isocyanate 13.35 (g)
Molecular sieve 4A20 (g) was added to the 0 (ml) solution, and the mixture was heated under reflux for 13.5 hours in a nitrogen stream. After cooling, the molecular sieve was filtered off, and the filtrate was distilled under reduced pressure to obtain acryloyl isocyanate. Boiling point 82
~ 83 ° C.

Reference Example 3 Xylene 165 (g) was added to a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, and 50 parts of styrene and 1 part of methyl methacrylate were added while the temperature was raised and the nitrogen gas was purged.
25 parts, 2-hydroxyethyl acrylate 150 parts,
A mixture of 150 parts of ethylhexyl acrylate, 25 parts of methyl acrylate, 25 parts of lauryl mercaptan, and 10 parts of Kayaester O was added dropwise over 3 hours to give an acrylic oligomer (1) having a molecular weight of 5500 and a hydroxyl value of 144. Manufactured.

After the temperature of the reaction vessel was lowered to 30 ° C., the methacryloyl isocyanate 28.5 obtained in Reference Example 1 was substituted so that 2/10 of all the hydroxyl groups of the acrylic oligomer (1) were replaced. Parts and 1.0 parts of hydroquinone were added dropwise over 30 minutes. After completion of dropping, the reaction between methacryloyl isocyanate and hydroxyl group was checked by infrared absorption spectroscopy.
Disappearance of peak at 250 cm ^-1 , 33 due to -NH group
Appearance of a peak at 00 cm ^{-1 and} a shift of 1760 from the usual carbonyl group due to an acylcarbonyl group
The appearance of a peak of cm ^-1 was confirmed. Further, by the nuclear magnetic resonance spectroscopy (NMR method), the appearance of a signal due to the proton of the -NH group and the chemical shift of the signal due to the vinyl proton to a high magnetic field of about 0.3 ppm were confirmed. All of these results show that the -OH group is replaced by the acyl urethane group of formula (A). The reaction mixture obtained was distilled under reduced pressure to remove volatile matter, thereby obtaining a nonvolatile content of 98%, a molecular weight of 5900,
A reactive acrylic oligomer (2) having a viscosity of 200 poise was obtained.

Reference Example 4 In the same manner as in Reference Example 3, 200 parts of polytetramethylene glycol having a molecular weight of 2000 and 0.4 parts of hydroquinone were used.
While maintaining the mixture of 30 parts at 30 ° C., 22.2 parts of methacryloyl isocyanate was added dropwise over 30 minutes so that all the hydroxyl groups of the polytetramethylene glycol were replaced. After completion of dropping, disappearance of absorption peak of -NCO group and appearance of absorption peak due to -NH group by infrared absorption spectrum method, appearance of signal due to -NH group by NMR method and high magnetic field of vinyl proton. Was confirmed to give a reactive polyether acrylate oligomer (1) having a molecular weight of 2200.

Reference Example 5 Silicone oil having a primary alcoholic hydroxyl group at both ends of dimethylsiloxane in the same reaction vessel as in Reference Example 3.
(Product name "X-22-160AS"; manufactured by Shin-Etsu Chemical Co., Ltd .;
200 parts of an average molecular weight of 1000; a hydroxyl value of 112) was added, and acryloyl isocyanate 39 was added so that all the hydroxyl groups of the silicone oil were replaced while maintaining the temperature at 30 ° C.
Parts were added dropwise over 30 minutes. After completion of the dropping, the disappearance of the -NCO group was confirmed by infrared absorption spectroscopy and NMR.
By confirming the appearance of the NH group, a reactive silicon acrylate oligomer having a molecular weight of 1200 was obtained.

Reference Example 6 Using the same apparatus as in Reference Example 3, 37 parts of maleic anhydride,
Sebacic acid 101 parts, long-chain aliphatic dibasic acid having 20 carbon atoms
(Brand name "SB-20"; manufactured by Okamura Oil Co., Ltd.) 170 parts and ethylene glycol 93 parts were charged, and the temperature was 180 to 200 ° C.
After the reaction was carried out until the acid value became 10, the mixture was cooled to room temperature to obtain a polyester oligomer having a molecular weight of 2000 and a hydroxyl value of 52. After adding 0.8 parts of hydroquinone,
18 parts of the acryloyl isocyanate obtained in Reference Example 2 was added dropwise over 30 minutes while maintaining it at 30 ° C. so that 5/10 of all the hydroxyl groups of the polyester oligomer would be substituted. After completion of the dropping, disappearance of the absorption peak of -NCO group and appearance of absorption peak of -NH group were confirmed by infrared absorption spectroscopy to obtain a reactive polyester acrylate oligomer having a molecular weight of 2100.

Reference Example 7 In the same manner as in Reference Example 4, while keeping a mixture of 300 parts of polyethylene glycol having a molecular weight of 300 and 0.4 part of hydroquinone at 30 ° C., methacryloyl isocyanate 220 was added so that all the hydroxyl groups of polyethylene glycol were replaced. Parts were added dropwise over 30 minutes. After finishing the dropping
It was confirmed by infrared absorption spectroscopy and NMR to obtain a reactive polyether oligomer (2) having a molecular weight of 520.

Reference Example 8 Using the same apparatus as in Reference Example 3, a bisphenol A type epoxy resin ("YD-011" manufactured by Tohto Kasei Co., Ltd .; epoxy equivalent 450-500; hydroxyl group number 2 / molecule; molecular weight 900
~ 1000) 41.7 parts and xylene 12.5 parts were charged, the internal temperature was heated to 150 ° C, and xylene was refluxed for about 2 hours to dissolve the epoxy resin. After 29.2 parts of propylene glycol monomethyl ether acetate was added and the internal temperature was lowered to room temperature while diluting, 4.6 parts of methacryloyl isocyanate was added dropwise over 20 minutes.
After confirming the disappearance of the -NCO group, the reaction was terminated to obtain a reactive epoxy acrylate oligomer having a molecular weight of 2300.

Reference Example 9 In the same reaction vessel as in Reference Example 3, 200 parts of polyethylene glycol having a molecular weight of 200 and dibutyltin dilaurate of 0.1 were added.
Parts and 0.2 parts of hydroquinone are added and the temperature is adjusted to 50-
While maintaining the temperature at 60 ° C, 112 parts of hexamethylene diisocyanate was added dropwise over 2 hours, and the mixture was further stirred for 1 hour to obtain a polyurethane resin having a molecular weight of 950. In order to replace 9/10 of all hydroxyl groups of the polyurethane resin,
67 parts of methacryloyl isocyanate was added dropwise over 30 minutes to obtain a reactive polyurethane acrylate oligomer having a molecular weight of 1200.

Reference Example 10 Butyl acetate 342 was prepared using the same apparatus as in Reference Example 3.
Parts, molecular weight 2000 polytetramethylene glycol 1
After adding 028 parts and 222 parts of isophorone diisocyanate and stirring sufficiently, dibutyltin dilaurate 1.2
5 parts was added, the temperature was gradually raised to 80 ° C., and the temperature was maintained for 1 hour. Next, 1.4 parts of hydroquinone was added, 116 parts of 2-hydroxyethyl acrylate was added dropwise over 30 minutes, and the mixture was kept at 80 ° C. for 3 hours. Completion of the reaction was confirmed by confirming the disappearance of the peak at 2250 cm ⁻¹ due to the —NCO group by infrared absorption spectroscopy. After completion of the reaction, the solvent was removed by heating under reduced pressure to obtain a reactive polyether oligomer (3).

Example 1 To 100 parts of the reactive polyether acrylate oligomer (1) obtained in Reference Example 4 was added 1.
By adding 5 parts and stirring sufficiently, an ultraviolet-curable optical fiber coating composition was obtained. This composition was coated on a clean glass plate with a doctor blade so as to have a dry film thickness of 200 μm, left at room temperature for 2 hours, and then treated with ultraviolet rays under the conditions described below to obtain a cured film. This coating was transparent and good without tack. Next, the cured film was peeled off from the glass plate and a tensile test was conducted. As a result, the initial Young's modulus was 0.22 kg / mm ² and the elongation was 54%.
Met.

Ultraviolet treatment conditions High voltage mercury lamp HI-20N (80 W / cm) manufactured by Nippon Batteries Co., Ltd.
The lamp length direction (using a reflector and a concentrating device) is placed at a right angle to the conveyor traveling direction, and the conveyor speed is 5 m / min at a height of 80 mm from the conveyor surface.

Tensileon Tensile Test Conditions Tensilon Tensile Tester (HI, manufactured by Toyo Baldwin Co., Ltd.)
-100 type) at a pulling speed of 50 mm / min for a sample having a film length of 50 mm and a width of 10 mm.

Example 2 20 parts of the reactive polyether acrylate oligomer (1) obtained in Reference Example 4, 80 parts of the reactive polyether acrylate oligomer (3) obtained in Reference Example 10 and benzoylmethyl ether
A coating composition for an optical fiber was obtained by mixing 1.5 parts of tel. Using this composition, a cured film was obtained in the same manner as in Example 1, and the tensile test was conducted to find that it was 2
Initial Young's modulus of 0.40 kg / mm ² and elongation of 63 at 0 ° C
%, Breaking strength 0.25 kg / mm ² , at 60 ° C. initial Young's modulus 0.37 kg / mm ² , elongation 55%, breaking strength 0.2.
It was 20 kg / mm ² .

Comparative Example 1 Reactive Polyether Oligomer Obtained in Reference Example 10
(3) A coating composition for an optical fiber was obtained from 100 parts of benzoin methyl ether and 1.5 parts. Using this composition,
A cured film was obtained in the same manner as in Example 1 and subjected to a tensile test. At 20 ° C., the initial Young's modulus was 0.61 kg /
mm ² , elongation rate 45%, breaking strength 0.19 kg / mm ² ,
At 60 ° C, the initial Young's modulus is 0.58 kg / mm ² , the elongation is 3
The strength was 5% and the breaking strength was 0.16 kg / mm ² .

Example 3 100 parts of the reactive silicon acrylate oligomer obtained in Reference Example 5 was mixed with 3 parts of diacetophenone to obtain a coating composition for an optical fiber.

Coating test A glass fiber was spun to a diameter of 100 μm from a base material containing quartz glass as a main component, and immediately after spinning, the above composition was ironed with a die to a film thickness of 100 μm, and ultraviolet rays were applied. By performing the treatment, a primary coated glass fiber was obtained. The coating of the obtained coated fiber-does not break or peel off even when the fiber is bent,
It had sufficient strength.

Example 4 The reactive polyester acrylate oligomer obtained in Reference Example 6 was roll-coated on 200 μm art paper so as to have a film thickness of 2 μm. After setting for 10 minutes, an electron beam with an electron energy of −300 keV was irradiated under an electron current of 30 mA to give a dose of 3 Mrad to obtain a cured film having no surface tackiness. The hardness of the coating film was H when measured with a pencil hardness, and the adhesiveness of the coating film was good even when tape peeling was performed by the cross-cut method.

Example 5 Reactive epoxy acrylate oligomer obtained in Reference Example 8
Kayamek A as a radical curing catalyst in 100 parts of solution
5 parts (55% by weight solution of methyl ethyl ketone peroxide in dimethyl phthalate) manufactured by Kayaku Nuri Co., Ltd. and 2.5 parts of 6% cobalt naphthenate were mixed to obtain a curable composition. Apply this composition to a 200 mm x 25 mm tin plate.
It was painted so that it would be 00μ. After setting for 20 minutes, the same tin plates were overlapped and pressed with a force of 5 kg / cm ² , and baked at 100 ° C. for 30 minutes to bond the tin plates. When the T-peel test of this tin plate was carried out, the peel strength was 5 kg / 25 mm.

Example 6 Saponification degree of 80.7 mol% and average degree of polymerization of 500
Polyvinyl alcohol 500 parts, saponification degree 87.7 mol%, average degree of polymerization 500 polyvinyl alcohol 325
And 680 parts of deionized water at a temperature of 90 ° C. for 30
Allow to dissolve for minutes. After the completion of dissolution, the temperature in the tank was lowered to 60 ° C., and a mixed solution of 1.2 parts of hydroquinone and 1673 parts of 2-hydroxyethyl methacrylate was added dropwise over 30 minutes. After the dropping, a solution of 50 parts of benzoin methyl ether dissolved in 215 parts of dimethyl sulfoxide was added,
The resin composition was obtained by mixing at 15 ° C. for 15 minutes. To 135 parts of this resin composition, 15 parts of the polyether oligomer (2) obtained in Reference Example 7 was added and further mixed with a kneader. After the mixing was completed, defoaming was performed under reduced pressure to obtain a photocurable resin composition.

This composition was kept at 60 ° C., and a solution prepared from polyvinyl alcohol and a red iron oxide pigment was applied onto a tin plate and extruded through a slit onto a support, which was then covered with a hard vinyl sheet. -Put it on the press and press 20
It was pressed at a pressure of kg / cm ² for 5 minutes and further dried at 60 ° C. to obtain a photopolymer plate. This play
After the negative was brought into close contact with the container and exposed with a mercury lamp for 3 minutes, the plate was developed by spraying tap water to obtain an uneven plate. The image reproducibility of the obtained plate is good,
It had a good shoulder angle and a chevron shape in cross section.

Example 7 100 parts of the acrylic oligomer (2) obtained in Reference Example 3 and 1.2 parts of an acrylic leveling agent were added to a stainless beaker.
Then, the mixture was thoroughly stirred with a disperser, defoamed and desolvated to obtain an X-ray cured composition. This composition was applied to a plastic plate made of polymethylmethacrylate having a thickness of 5 mm so that the cured film thickness was 200 μm.
Painted. In addition to this, the dose of X-ray was 120 at an acceleration voltage of 50 kV and a current of 40 mA using tungsten as the anticathode.
A cured coating was obtained by irradiation with 10,000 roentgens. The coating was transparent and had a pencil hardness of 2H.

Example 8 100 parts of the reactive polyurethane acrylate oligomer obtained in Reference Example 9 was mixed with 2 parts of benzoin methyl ether to obtain a leather coating composition. This composition was coated on cowhide so as to have a film thickness of 10 μm, and the leather was covered by irradiating with ultraviolet rays. The resulting coating film had sufficient flexibility.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryuzo Mizuguchi 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd.

Claims (3)

[Claims] 1. The formula: (In the formula, R represents hydrogen or lower alkyl.) The molded product is coated with a coating composition containing at least 0.5% by weight or more of a polymerizable compound having an acyl urethane structure represented by the formula, A coated molded product that is cured. 2. The molded body is glass fiber.
The coated molded article described. 3. The coated molded body is an optical fiber.
The coated molded article described.