JPS6357451B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to polybutadiene-modified unsaturated polyester resin compositions. Generally, the cured product of polybutadiene-modified unsaturated polyester resin composition has water resistance, flexibility,
Although it has excellent physical properties such as flexibility, it has the disadvantage of slow curing and poor compatibility with other unsaturated polyester resin compositions. For this reason, when used as a paint film, drying is slow and it takes a long time to polish, making it difficult to use as a paint that cures at room temperature. In addition, the cured product of the polybutadiene-modified unsaturated polyester resin composition has excellent physical properties, such as poor compatibility with other unsaturated polyester resin compositions that are often used as modifiers for workability and physical properties, making them difficult to modify. is not being utilized effectively. In view of this current situation, the inventors of the present invention have made extensive studies and have developed a cured product of a polybutadiene-modified unsaturated polyester resin composition that has the same curability and drying properties as an air-drying unsaturated polyester resin composition even at room temperature. Polybutadiene-modified unmodified polyester resin has the characteristics of water resistance, flexibility, and flexibility, and has superior water resistance and abrasiveness than cured products of vinyl ester, bisphenol, and isophthalic acid-based unsaturated polyester resin compositions. A saturated polyester resin composition was obtained. The cured product of the polybutadiene-modified unsaturated polyester resin composition of the present invention has excellent adhesion to metals, and the drawbacks of general polybutadiene-modified unsaturated polybutadiene resin compositions are improved by the present invention. The present invention provides: (1) α,β-unsaturated dicarboxylic acid or its anhydride (2) (i) Air-drying allyl compound (ii) Animal or vegetable oil or its derivative (iii) Dicyclopentadiene or its derivative (3) α ,ω-polybutadiene glycol and/
or α,ω-hydrogenated polybutadiene glycol (4) polyhydric alcohol or polybasic acid at least one of (1) and (2) in the molar ratio of (1) and (2), (2)/( 1)
0.8 to 1.2 and then reacting (3) and optionally (4) to obtain a polybutadiene-modified unsaturated polyester and a polymerizable monomer having one or more polymerizable double bonds. and (1) α,β-unsaturated dicarboxylic acid or its anhydride (2) (i) Air-drying allyl compound (ii) Animal or vegetable oil or its derivative (iii) Dicyclopentadiene or derivatives thereof (3) α,ω-polybutadiene glycol and/or
or α,ω-hydrogenated polybutadiene glycol (4) polyhydric alcohol or polybasic acid at least one of (1) and (2) in the molar ratio of (1) and (2), (2)/( 1)
Polybutadiene-modified unsaturated polyesters, dicyclopentadiene-modified unsaturated polyesters, and polymers having one or more polymerizable double bonds obtained by reacting 0.8 to 1.2 and then reacting (3) and optionally (4). The present invention relates to a polybutadiene-modified unsaturated polyester resin composition obtained by mixing polybutadiene monomers. Examples of α,β-unsaturated dicarboxylic acids or anhydrides thereof used in the present invention include maleic acid, maleic anhydride, itaconic acid, and citraconic acid. Examples of air-drying allyl compounds include ethylene glycol monoallyl ether, glycerin diallyl ether, trimethylolpropane diallyl ether, and pentaerythritol triallyl ether. Examples of animal and vegetable oils or their derivatives include castor oil, soybean oil fatty acids, linseed oil fatty acids, cottonseed oil fatty acids, rice sugar fatty acids, and oils such as soybean oil, linseed oil, and tung oil, as well as ethylene glycol, glycerin, trimethylolethane, and trimethylol. There are transesterified oils that are transesterified with propane, etc. Examples of dicyclopentadiene or its derivatives include dicyclopentadiene (tricyclo[5.2.1.0 ^2,6 ]decadiene-4,8), hydroxylated dicyclopentadiene (tricyclo[5.2.1.0 ^2,6 ]decadiene-4,8), -8 (or 9)-all). Examples of α,ω-polybutadiene glycol include Polybd R-45, CS manufactured by ARCO CHEMICAL.
-15, CN-15, manufactured by Nippon Soda represented by formula ()
Nisso PBG grade and so on. As an example of α,ω-hydrogenated polybutadiene glycol,
There are HPBG grades, etc. Examples of polyhydric alcohols that may be used as necessary include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-
Hexanediol, 1 mole of bisphenol A and 2 mols of ethylene oxide or propylene oxide
There are also adducts with moles. Examples of polybasic acids that may be used as necessary include phthalic anhydride, isophthalic acid, terephthalic acid, hymic anhydride (3,6-endomethylenetetrohydrophthalic anhydride, Hitachi Chemical trademark),
Examples include tetrahydrophthalic anhydride, sebacic acid, and adipic acid. α,β-unsaturated dicarboxylic acid or its anhydride (first component) and at least one of air-drying allyl compounds, animal and vegetable oils or derivatives thereof, dicyclopentadiene or derivatives thereof (second component); The reaction with α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol (third component) is carried out at a second component/first component molar ratio in the range of 0.8 to 1.2. At this molar ratio, the reaction is carried out at, for example, 100 to 220°C, and the reaction is terminated when the acid value reaches 120 to 240. If this molar ratio is less than 0.8, the acid will be excessive, making it difficult to react, and the stability of the polybutadiene-modified unsaturated polyester resin composition obtained by mixing it with a polymerizable monomer will be impaired. Furthermore, if the molar ratio exceeds 1.2, the curing properties of the resulting resin will deteriorate. This molar ratio is preferably in the range of 0.95 to 1.1. The third component, α,ω-polybutadiene glycol and α,ω-hydrogenated polybutadiene glycol, which are reacted with the compounds obtained from the first and second components, may be used in combination. The reaction of the compound obtained from the first and second components with the third component and optionally added fourth component can be carried out by the usual method used in the production of unsaturated polyester. There is no limit to the percentage. This reaction can be carried out, for example, by heating at 150 to 220°C in a solvent such as toluene or xylene or in the absence of a solvent while removing condensation water, and adding hydroquinone, p-benzoquinone, tert-butylcatechol, di-tert-butylcatechol, etc. as necessary. Add mono-ter-butylhydroquinone etc. to 40~
The reaction is terminated at an acid value of 60. Examples of polymerizable monomers having one or more polymerizable double bonds to be mixed in the polybutadiene-modified unsaturated polyester include styrene, chlorostyrene, vinyltoluene, methyl (meth)acrylate (meaning methyl acrylate, methyl methacrylate), (same below), ethyl (meth)acrylate,
Ethylene glycol di(meth)acrylate, vinyl acetate, ter-butylstyrene, etc. are used. Dicyclopentadiene-modified unsaturated polyester refers to a resin obtained by using dicyclopentadiene or a derivative thereof in addition to the materials normally used for producing unsaturated polyesters. For example, hydroxylated dicyclopentadiene 1
1 mole of maleic anhydride, and 0.5 mole of propylene glycol, and is synthesized by a conventional unsaturated polyester manufacturing method. The amount of polymerizable monomer to be mixed with the polybutadiene-modified unsaturated polyester is not particularly limited, but it is determined based on curability, drying properties, water resistance, flexibility, flexibility, etc. per 100 parts by weight of the polybutadiene-modified unsaturated polyester. 50 to 100 parts by weight is preferred. Furthermore, when the above-mentioned polymerizable monomers, polybutadiene-modified unsaturated polyester and dicyclopentadiene-modified unsaturated polyester are mixed, there is no particular restriction on the ratio of their amounts, and they can be mixed as desired depending on the required physical properties. It is preferable that the polybutadiene-modified unsaturated polyester and the dicyclopentadiene-modified unsaturated polyester are each dissolved in advance in a polymerizable monomer having one or more polymerizable double bonds, and then mixed. The polybutadiene-modified unsaturated polyester resin composition obtained by the present invention uses organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, kyumene hydroperoxide, acetylacetone peroxide, and benzoyl peroxide as a curing agent. If necessary, naphthenic acid,
Metallic soaps containing octenoic acid, such as cobalt naphthenate, iron octenoate, lead naphthenate, etc., or a combination of two or more thereof as a curing accelerator,
Furthermore, dimethylaniline, diethylaniline, quaternary ammonium salts, acetylacetone, and the like may be used as curing accelerators. The polybutadiene-modified unsaturated polyester resin composition may contain inorganic fillers such as calcium carbonate, talc, clay, and silica, phenyl salicylate, 1-(2'-hydroxy-5
Ultraviolet absorbers such as -methylphenyl)benzotriazole, thermofusible substances such as polystyrene, polyethylene, polyvinyl acetate, and saturated polyester, dyes, pigments, etc. may also be used. In addition, 0.5 to 5 parts by weight of a photopolymerization initiator such as benzoin, benzoin alkyl ether, diphenyl disulfide, di-β-naphthyl disulfide, etc. is added to 100 parts by weight of the polybutadiene-modified unsaturated polyester resin composition. mercury lamp,
It is also possible to cure using a light source such as a tungsten lamp or a xenon lamp. Examples of the present invention are shown below. In the examples, parts mean parts by weight, and % means % by weight. Example 1 2 moles of maleic anhydride and 2 moles of trimethylolpropane diallyl ether were added in a nitrogen gas stream.
The reaction was carried out at 150°C to obtain a compound with an acid value of 180. This was cooled to 70°C and α,ω-polybutadiene glycol (manufactured by Nippon Soda, number average molecular weight 2000, PB-
G-2000) 0.5 mol, α, ω-hydrogenated polybutadiene glycol (manufactured by Shin Nippon Rika, number average molecular weight
2000) Added 0.5 mol and reacted at 170℃ to determine the acid value.
20 polybutadiene-modified unsaturated polyesters were obtained. Resin composition A was prepared by adding and dissolving 30 parts of styrene and 0.03 parts of hydroquinone to 70 parts of this resin. Resin composition A contains cobalt naphthenate (metal content 6
%) and 1.0% of Permec N (manufactured by NOF Corporation, 55% methyl ethyl ketone peroxide).
At 25℃, spray 2.0g/60× onto a 0.8mm thick cold-rolled steel plate ground with #150 waterproof paper using a gravity spray gun (manufactured by Iwata Painting Machine, Wider 60, diameter 2.5mm).
Painted to 150mm. Example 2 1 mole of glycerin and 3 moles of linseed oil fatty acid were transesterified at 200°C in a nitrogen gas flow. 2 moles of linseed oil fatty acid glyceride and 2 moles of maleic anhydride were reacted at 150°C in a nitrogen gas flow.
A compound with an acid value of 120 was obtained, cooled to 70°C, 1 mole of α,ω-polybutadiene glycol (PB-G-2000) used in Example 1 was added and reacted at 200°C, and a compound with an acid value of 17 was obtained. A polybutadiene-modified unsaturated polyester was obtained. 70 parts of this resin, 30 parts of styrene,
A resin composition B was prepared by adding and dissolving 0.03 part of hydroquinone. Resin composition B contains a curing accelerator as in Example 1,
A hardener was added and painted. Example 3 2 moles of maleic anhydride and 2.2 moles of hydroxylated dicyclopentadiene were heated at 150°C in a nitrogen gas stream.
A compound with an acid value of 200 was obtained. 50 of this
The mixture was cooled to 1 mol of α, ω-polybutadiene glycol (PB-G-2000) used in Example 1 and reacted at 200°C to obtain a polybutadiene-modified unsaturated polyester having an acid value of 15. Resin composition C was prepared by adding and dissolving 30 parts of styrene and 0.03 parts of hydroquinone to 70 parts of this resin. A curing accelerator and a curing accelerator were added to the resin composition C in the same manner as in Example 1.
A hardener was added and painted. Example 4 2 moles of maleic anhydride and 2 moles of hydroxylated dicyclopentadiene were heated at 100°C in a nitrogen gas stream.
A compound with an acid value of 200 was obtained. this
Cool to 50°C and add α, ω-polybutadiene glycol (manufactured by Nippon Soda, number average molecular weight 1000, PB-G-
1000) and 0.6 mole of dipropylene glycol were added and reacted at 180°C to obtain a polybutadiene-modified unsaturated polyester with an acid value of 25. This resin
Resin composition D was prepared by adding and dissolving 30 parts of styrene and 0.03 parts of hydroquinone to 70 parts. An accelerator and a curing agent were added to Resin Composition D in the same manner as in Example 1, and coating was carried out. Example 5 0.9 mol of maleic anhydride, 0.1 mol of adipic acid,
0.9 mol of propylene glycol and 0.4 mol of hydroxylated dicyclopentadiene were reacted at 170°C in a nitrogen gas stream to obtain a dicyclopentadiene-modified unsaturated polyester with an acid value of 30. This resin
To 70 parts, 30 parts of styrene and 0.03 part of hydroquinone were added and dissolved, and 100 parts of resin composition D was added and mixed to prepare resin composition E. Resin composition E was coated with an accelerator and a curing agent added in the same manner as in Example 1. Comparative Example 1 1 mole of maleic anhydride and 1 mole of α,ω-hydrogenated polybutadiene glycol (manufactured by Shin Nihon Rika, number average molecular weight 2000) were added and reacted at 160°C.
A polybutadiene-modified unsaturated polyester having an acid value of 25 was obtained. Resin composition F was prepared by adding and dissolving 30 parts of styrene and 0.03 parts of hydroquinone to 70 parts of this resin. A curing accelerator was added to the resin composition F in the same manner as in Example 1,
Painted with a hardener added. Comparative Example 2 0.8 mol of maleic anhydride, 0.2 mol of phthalic anhydride, 0.7 mol of ethylene glycol, 0.1 mol of linseed oil fatty acid glyceride used in Example 2, and 0.4 mol of dicyclopentadiene were mixed at 200 mol in a nitrogen gas stream.
The reaction was carried out at ℃ to obtain a dicyclopentadiene-modified unsaturated polyester having an acid value of 39. Resin composition G was prepared by adding and dissolving 30 parts of styrene and 0.03 part of hydroquinone to 70 parts of this resin. A curing accelerator and a curing accelerator were added to the resin composition G in the same manner as in Example 1.
Painted with a hardener added. Comparative Example 3 0.8 mol of fumaric acid, 0.2 mol of isophthalic acid, and 1.1 mol of hydrogenated bisphenol A were reacted at 210°C under a nitrogen gas stream to obtain an unsaturated polyester with an acid value of 30. A resin composition H was prepared by adding and dissolving 30 parts of styrene and 0.03 parts of hydroquinone to 70 parts of this resin. A curing accelerator and a curing accelerator were added to the resin composition H in the same manner as in Example 1.
Painted with a hardener added. Table 1 shows the characteristics test results of the coating film.

【table】

[Table] The polybutadiene-modified unsaturated polyester resin composition of the present invention has the same curability and drying properties as general air-drying unsaturated polyester resins even at room temperature, and also has water resistance, adhesion to metals, and Toughness and blister properties are improved. Furthermore, a resin composition containing a dicyclopentadiene-modified unsaturated polyester also exhibits similar properties.

Claims (1)

[Claims] 1 (1) α,β-unsaturated dicarboxylic acid or its anhydride (2) (i) Air-drying allyl compound (ii) Animal or vegetable oil or its derivative (iii) Dicyclopentadiene or its derivative ( 3) α, ω-polybutadiene glycol and/
or α, ω-hydrogenated polybutadiene glycol (4) polyhydric alcohol or polybasic acid at least one of (1) and (2) in a molar ratio of (1) and (2) (2)/(1) )of
0.8 to 1.2 and then reacting (3) and optionally (4) to obtain a polybutadiene-modified unsaturated polyester and a polymerizable monomer having one or more polymerizable double bonds. A polybutadiene-modified unsaturated polyester resin composition. 2 (1) α, β-Unsaturated dicarboxylic acid or its anhydride (2) (i) Air-drying allyl compound (ii) Animal or vegetable oil or its derivative (iii) Dicyclopentadiene or its derivative (3) α, ω- Polybutadiene glycol and/or
or α,ω-hydrogenated polybutadiene glycol (4) polyhydric alcohol or polybasic acid at least one of (1) and (2) in the molar ratio of (1) and (2), (2)/( 1)
Polybutadiene-modified unsaturated polyesters, dicyclopentadiene-modified unsaturated polyesters, and polymers having one or more polymerizable double bonds obtained by reacting 0.8 to 1.2 and then reacting (3) and optionally (4). A polybutadiene-modified unsaturated polyester resin composition obtained by mixing polybutadiene monomers.