JPS6334881B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photopolymerizable resin composition. Unsaturated polyester resin has excellent physical and chemical properties such as mechanical, electrical properties and chemical resistance, is easy to handle, and is inexpensive, so it is widely used in electrical insulation materials, FRP, etc. However, these industrially used unsaturated polyester resins have drawbacks such as lack of flexibility, high volume shrinkage, and poor photopolymerizability. To solve this problem, soft resins are often mixed. This uses a glycol such as diethylene glycol and adipic acid as part or all of a saturated carboxylic acid. However, the flexibility and volume shrinkage of the polyester resin obtained by this method are not necessarily satisfactory. In addition, in order to improve photopolymerizability, a method of adding double bonds such as allyl acid to the side chains of unsaturated polyesters, for example, trimethylolpropane diallyl ether, pentaerythritol diallyl ether, etc., is added to the alcohol component of unsaturated polyesters. However, the flexibility deteriorates and the volumetric shrinkage rate increases, making it impractical. On the other hand, if an acrylic or methacrylic polymerizable monomer is used as a polymerizable monomer for unsaturated polyester resin, the copolymerizability with unsaturated polyester will decrease, and flexibility and volumetric shrinkage may not be satisfied. It's not a kimono. Furthermore, conventionally,
Vinyl ester resin is made by reacting bisphenol A epoxy resin with methacrylic acid or acrylic acid and dissolving it in styrene, acrylic, or methacrylic polymerizable monomers, but this is photopolymerized. Although it has excellent properties, it has disadvantages such as the use of expensive epoxy resin, and the limited availability of epoxy resin, which makes it difficult to obtain satisfactory flexibility and volume shrinkage. The present invention has been made in view of these points, and has been made for the purpose of providing a resin composition that has low shrinkage, extremely improved flexibility, and excellent photopolymerizability. That is, the present invention provides (a) 20 to 80 parts by weight of an unsaturated polyester obtained by reacting an acid component containing an α,β-unsaturated dibasic acid and diisobutenylsuccinic acid or its anhydride with an alcohol component; b) A photopolymerizable resin composition containing 80 to 20 parts by weight of an acrylic or methacrylic polymerizable compound. In the present invention, α,β- contained in the acid component
Examples of unsaturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid,
α,β-unsaturated dibasic acids such as muconic acid, and optionally phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, adipic acid,
Saturated acids such as sebacic acid, dodecanedioic acid, succinic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, and benzoic acid are used.
α,β-unsaturated dibasic acid is 70 mol% of the acid component
The following is preferable from the viewpoint of properties such as reactivity and flexibility. Diisobutenylsuccinic anhydride has isomers, and the typical structural formula is It is indicated by. Alcohol components include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, hydrogenated bisphenol A, etc. of polyhydric alcohols are used. Cyclohexanol is part of the alcohol component,
A monohydric alcohol such as benzyl alcohol may be used, and the amount thereof is preferably 20 mol % or less of the alcohol component in view of the properties of the cured product. In addition to the above acid components and alcohol components,
One or more of the compounds represented by the structural formula [], the compounds represented by the structural formula [], or dicyclopentadiene may be used in combination. Structural formula〔〕 In the above formula, R ₁ is an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an aromatic ring, or an aliphatic ring residue. Structural formula〔〕 In the above formula, _R2 is an alkylene group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an aliphatic ring, or a _-R3 -O- _R4- group. However, R ₃ and
R ₄ is an alkylene group having 1 to 5 carbon atoms, and R ₃ and
R ₄ may be the same or different. In the present invention, the acid component and the alcohol component are defined as the total number of carboxyl groups/total number of hydroxy groups.
It is preferable that the ratio is in the range of 1.0/1.0 to 1.5 and that the reaction is carried out in an inert gas atmosphere. The reaction water is distilled off by heating to 150-250°C. Hydroquinone, as a polymerization inhibitor during the reaction.
It is preferable to use p-tertiarybutylcatechol or the like. Examples of the acrylic or methacrylic polymerizable compounds of the present invention include methyl methacrylate, ethyl methacrylate, butyl methacrylate,
Ethyl acrylate, butyl acrylate, (R is H or CH ₃ ) and other acrylates, methacrylate polymerizable monomers, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, Polyfunctional polymerizable monomers such as propylene glycol diacrylate, diethylene glycol diacrylate, and trimethylolpropane triacrylate are used. It is also possible to use a mono- or polyfunctional epoxy compound reacted with acrylic acid or methacrylic acid. For example, Cardiula E acrylic acid adduct, Cardiula E methacrylic acid adduct, acrylic acid or methacrylic acid adduct of bisphenol A-based epoxy compounds (e.g. Epicote 828, 1001, 1004, trade name of Ciel Petrochemical Co., Ltd.) There is. The proportion of the unsaturated polyester obtained using the acid component containing the α,β-unsaturated dibasic acid and diisobutenylsuccinic acid or its anhydride of the present invention and the acrylic or methacrylic polymerizable compound is the unsaturated polyester. 80 to 80 parts by weight of acrylic or methacrylic polymerizable compound
~20 parts by weight. If the amount of unsaturated polyester is less than 20 parts by weight, flexibility will be reduced, and if it exceeds 80 parts by weight, photocurability will be reduced. When photocuring the photopolymerizable resin composition of the present invention, a photosensitizer such as benzoin alkyl ether is added and mixed. For photocuring of the photopolymerizable resin composition of the present invention, usual conditions are applied and there are no particular limitations. The photocurable resin composition of the present invention may contain styrene, vinyl acetate, vinyl toluene,
Polymerizable monomers such as diallyl phthalate and chlorostyrene, curing accelerators such as cobalt octylate, cobalt naphthenate and dimethylaniline, organic peroxides such as methyl ethyl ketone peroxide and benzoyl peroxide, pigments, mold release agents,
A filler, glass fiber, carbon fiber, etc. may be used in combination. Examples of the present invention will be described below. Parts are by weight. Example 1 Maleic anhydride 196 was added to 2 four-necked flasks.
parts, 148 parts of phthalic anhydride, 420 parts of diisobutenylsuccinic anhydride, 155 parts of ethylene glycol, 228 parts of propylene glycol, and 0.17 parts of hydroquinone.
After 2 hours of reaction at 150°C in a nitrogen stream, the mixture was heated to 200°C and reacted until the acid value reached 110.
After cooling, an unsaturated polyester was obtained. Fifty parts of this unsaturated polyester were dissolved in 50 parts of neopentyl glycol diacrylate containing 3 parts of benzophenone and 0.01 part of hydroquinone. This composition was applied to an iron plate, and a 80W/cm high-pressure mercury lamp (Toshiba Electric Materials Co., Ltd.
A cured coating film was obtained by irradiating the coating film with a high-pressure mercury lamp (H2000L/6 lamp manufactured by Co., Ltd.) for 1 minute at a distance of 30 cm. As shown in Table 1, this coating film had excellent flexibility (Dupont impact, Erichsen extrusion) and acetone resistance. Comparative Example 1 196 parts of maleic anhydride, 444 parts of phthalic anhydride, 155 parts of ethylene glycol, propylene glycol
228 parts of hydroquinone and 0.16 parts of hydroquinone were reacted in the same synthesis process as in Example 1 until the acid value reached 110 to obtain an unsaturated polyester. 50 parts of this unsaturated polyester was mixed with 3 parts of benzophenone and 0.01 part of hydroquinone.
Neopentyl glycol diacrylate containing
Dissolved in 50 parts. Apply this composition to the iron plate,
80W/cm high-pressure mercury lamp (H2000L/manufactured by Toshiba Electric Materials Corporation)
6 lamps) and the distance between the paint film and the high pressure mercury lamp is 30cm.
The coating was irradiated for 1 minute to obtain a cured coating film. The properties of this coating film are shown in Table 1, and it was found to be poor in flexibility and acetone resistance. Example 2 420 parts of diisobutenylsuccinic anhydride, 296 parts of phthalic anhydride, 588 parts of maleic anhydride, 836 parts of propylene glycol, and 0.20 part of hydroquinone were placed in the four-necked flask of Example 2, and the mixture was heated at 150°C in a nitrogen stream.
After reacting for 2 hours, the mixture was heated to 200°C and reacted until the acid value reached 30 to obtain an unsaturated polyester. 60 parts of this unsaturated polyester were dissolved in 3 parts of benzoin methyl ether and 10 parts of methyl methacrylate and 30 parts of trimethylolpropane triacrylate containing 0.01 part of hydroquinone. This composition was applied to an iron plate, and irradiated for 1 minute with an 80 W/cm high-pressure mercury lamp (using a H2000L/6 lamp manufactured by Toshiba Electric Materials Co., Ltd.) with a distance of 30 cm between the coating film and the high-pressure mercury lamp.
A cured coating film was obtained. As shown in Table 1, this coating film had excellent flexibility and acetone resistance. Example 3 380 parts of bisphenol A-based epoxy resin AER331 (trade name of Asahi Kasei Industries, epoxy equivalent: 190), 144 parts of acrylic acid, and cation M ₂ 100 (trade name of Nippon Oil & Fats Co., Ltd.) as a catalyst were placed in a four-necked flask. , dimethylbenzyldodecyl ammonium chloride)
1.5 parts were charged and reacted at 120°C until the acid value reached 5 to obtain an acrylic polymerizable compound. 35 parts of this acrylic polymerizable compound and 35 parts of the unsaturated polyester obtained in Example 2 were dissolved in 30 parts of 1,6-hexanediol diacrylate containing 3 parts of benzoin methyl ether, 2 parts of dimethylaminoethanol, and 0.01 part of hydroquinone. did. This composition was applied to an iron plate and a 80W/cm high-pressure mercury lamp (manufactured by Toshiba Electric Materials Corporation) was used.
A cured coating film was obtained by irradiating the coating film with a high-pressure mercury lamp (using a H2000L/6 lamp) for 1 minute at a distance of 30 cm between the coating film and a high-pressure mercury lamp. As shown in Table 1, this coating film had excellent flexibility and acetone resistance. Example 4 55 parts of the unsaturated polyester obtained in Example 1 and 10 parts of the acrylic polymerizable compound obtained in Example 3 were mixed with 35 parts of diethylene glycol diacrylate containing 3 parts of benzoin methyl ether, 2 parts of dimethylaminoethanol, and 0.01 part of hydroquinone. It was dissolved in parts. This composition was applied to an iron plate, and a high-pressure mercury lamp of 80W/cm (using H2000L/6 lamp manufactured by Toshiba Electric Materials Co., Ltd.) was used.
The distance between the coating film and the high-pressure mercury lamp was set at 30 cm, and irradiation was performed for 1 minute to obtain a cured coating film. As shown in Table 1, this coating film had excellent flexibility and acetone resistance.

[Table] The photopolymerizable resin composition of the present invention has excellent photocurability and flexibility, and has a low curing shrinkage rate, so it is suitable for painting iron plates, etc., and its application range is paints, electrical insulation materials, etc. etc. is extremely wide.

Claims (1)

[Scope of Claims] 1 (a) 20 to 80 parts by weight of an unsaturated polyester obtained by reacting an acid component containing an α,β-unsaturated dibasic acid and diisobutenylsuccinic acid or its anhydride with an alcohol component. and (b) a photopolymerizable resin composition containing 80 to 20 parts by weight of an acrylic or methacrylic polymerizable compound. 2. The photopolymerizable resin composition according to claim 1, wherein the acrylic or methacrylic polymerizable compound is an acrylic acid or methacrylic acid adduct of a bisphenol A-based epoxy resin.