JPS6333766B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a novel synthetic resin useful as a paint resin. Currently, rosin-based hard resins are widely used for woodworking, lacquers, printing inks, bases, traffic paints, adhesives, etc.; On the other hand, it has disadvantages in weather resistance, flexibility, solvent resistance, etc. On the other hand, acrylic copolymers have advantages in weather resistance, flexibility, solvent resistance, hardness, drying properties, etc., but they also have gloss, solvent repellency, abrasiveness, etc.
It has drawbacks such as solubility. Furthermore, when attempting to blend the two in order to compensate for their shortcomings, problems tend to occur in terms of compatibility. As a result of intensive research, the present inventors have come up with a manufacturing method that provides a new resin that can compensate for the drawbacks of rosin-based hard resins and acrylic copolymers. That is, the present invention uses a radical polymerization initiator in the presence of 5 to 95% by weight (hereinafter simply referred to as %) of a rosin-based hard resin having a specific number average molecular weight to produce 95 to 5% by weight of a polymerizable monomer. Provided is a method for producing a rosin-based hard resin modified copolymer by graft copolymerizing %. The copolymer (resin) obtained by the present invention is suitable as a paint, especially for woodworking, plywood, and traffic. According to the present invention, defects in rosin-based hard resins are dramatically improved, there are no problems with compatibility, and depending on the polymerization method and post-treatment method, high solids or solvent-free types can be used. A paint with a high solids content when applied can be easily obtained. The rosin-based hard resin used in the present invention is generally an oligoester of rosin and polyhydric alcohol, and may be partially modified with carboxylic acids other than rosin, if necessary. Specifically, these are known in the art as ester gum, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, rosin-modified pentaester, or rosin-modified phenol resin, and have a number average molecular weight of 600 to 600. A value within the range of about 4000 is preferable. At that time, if a material with a molecular weight of less than 600 is used, the solvent resistance, abrasiveness, flexibility, chemical resistance, impact resistance, etc. of the coating film will be inferior; In this case, during graft copolymerization, thickening or gelation may easily occur, or compatibility may decrease, which are both undesirable. Therefore, it is appropriate to use a rosin-based hard resin having a number average molecular weight within the range of about 600 to 4,000, preferably about 800 to 3,000. On the other hand, the polymerizable monomers used in carrying out the method of the present invention include, for example, styrene, aromatic vinyl compounds such as vinyltoluene, (meth)
Acrylic acid and esters of this with monohydric alcohols, monoesters of polyhydric alcohols and monoepoxy compounds such as Cardiura E (manufactured by Ciel Chemical Co., Ltd.), maleic acid or fumaric acid, itaconic acid, and 1 of these Commonly known compounds include alcohols, polyhydric alcohols, esters with epoxy compounds, (meth)acrylamide, diacetone acrylamide, and the like. In the present invention, the rosin-based hard resin and the polymerizable monomer are used in an amount of 5-95% of the former and 95-5% of the latter, but if the rosin-based hard resin is less than 5%, the effect of the rosin-based hard resin is reduced. does not grow sufficiently,
On the other hand, if the polymerizable monomer content is less than 5%, the modification effect will not be sufficient and troubles will easily occur in terms of compatibility.
% or more is required. When grafting a polymerizable monomer to a rosin-based hard resin, it is possible to use the rosin-based hard resin as is, but in order to proceed more reliably, it is necessary to use (methyl)glycidyl (meth)acrylate. , (meth)allyl glycidyl ether, a monoester of a polymerizable unsaturated group-containing monocarboxylic acid and a diepoxy compound using 0.1 to 10% of an epoxy group-containing polymerizable monomer, a small amount of a polymerization inhibitor, and an epoxy group opener. It is preferable to use one that has undergone an addition reaction in the presence of a ring catalyst. After dissolving the rosin-based hard resin or grafted rosin-based hard resin obtained in this way in a solvent, a mixture of a polymerizable monomer, a radical polymerization initiator, and in some cases a small amount of solvent is heated. Polymerization can be carried out by adding it all at once or adding it gradually. Modified copolymer (resin) produced by the present invention
is useful as a Lutzker-type paint vehicle as it is, but if a "polymerizable monomer having an OH group" is selected as the polymerizable monomer, a modified copolymer having an OH group is produced, and in this case, Useful in combination with a crosslinking agent as a vehicle for curable paints. Therefore, the present invention also provides the "rosin-based hard resin-modified copolymer having OH group", polyisocyanate, amino resin, polyepoxy compound, polymerizable monomer, and polymerizable crosslinkable prepolymer produced according to the present invention. A resin composition for coating material is provided, which contains a crosslinking agent selected from the group consisting of: a polymerization initiator, a curing accelerator, and a cellulose compound, if necessary. In this case, examples of crosslinking agent components include the following. (1) Polyisocyanates: Organic polyisocyanates such as tolylene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate (IPDI), and these polyisocyanates are converted into polyhydric alcohols such as ethylene glycol, glycerin, and trimethylolpropane. Added prepolymer,
A reaction product of 1 mole of water and 3 moles of diisocyanate, such as Burnock D-750, DN-950
(Dainippon Ink Chemical Industries, Ltd.), Desmodeleur N
(Bayer AG). (2) Amino resin: Compounds containing amino groups such as melamine, urea, and guanamine are methylolated with formaldehyde, and then at least two or more methylol groups are etherified with lower aliphatic alcohols, such as Betsukamine P-138 Super Betu. Kamin J-820, G-821, L-105-
60 [a product made by Dainippon Ink and Chemicals Co., Ltd.] or Cymel 300 [a product made by Mitsui Cyanamid Co., Ltd.]. (3) Polyepoxy compounds: compounds having at least two or more epoxy groups in one molecule, such as diglycidyl ethers such as ethylene glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, and other Epiclon 1050 ,
Epichlorohydrin-bisphenol condensates such as 4050, 7050 (Dainippon Ink Chemical Co., Ltd.), Epicote 1001, 1004 (Siel Chemical Co., Ltd.). (4) Polymerizable monomers: Compounds having one radically polymerizable α,β-unsaturated bond in one molecule, such as aromatic vinyl compounds such as styrene and vinyltoluene, methyl methacrylate, ethyl acrylate, and butyl methacrylate. Acrylic esters such as. (5) Polymerizable and crosslinkable prepolymers: Polymerized and crosslinkable α,β-nonpolymers such as esters of (meth)acrylic acid and polyhydric alcohols such as ethylene glycol, glycerin, and trimethylolpropane, liquid polybutadiene, and drying oils. A compound that has two or more saturated bonds in one molecule. In addition, as polymerization initiators that can be used for curing, peroxides and azo compounds that can be used for radical polymerization can be used, but from the standpoint of low temperature curing, methyl ethyl ton peroxide, benzoyl peroxide, tert-butyl peroxide, etc. Particularly preferred are low-temperature decomposition types such as tate and azobisisobutyronitrile. As the curing accelerator, known ones such as organic acid metal soaps such as cobalt naphthenate and lead octenoate, and amines such as aniline and triethylamine can be used. Known cellulose compounds such as nitrified cotton and cellulose acetate butyrate can be used. Also, known coating methods such as roll coater and spray can be used. The present invention will be explained below with reference to Examples. However, the present invention is not limited thereby. Parts indicate parts by weight. Production example (1): Synthesis of ester gum (A) 1020 parts of Chukyo rosin was charged into a four-necked flask equipped with a stirrer, a thermometer, an inert gas inlet, and a formed water removal port, and the temperature was raised to make the rosin. It melted. Next, after gradually adding 115 parts of glycerin, a small amount of antifoaming agent was added and the temperature was raised to 260℃, and the acid value reached 8 at 260℃.
The reaction continued until When the acid value reached 8, the mixture was maintained under reduced pressure at 260°C for 1 hour to remove unreacted glycerin. The obtained ester gum has a softening point
The temperature was 82°C, the hue was WG, the oxidation was 4.5, the OH value was 30, and the number average molecular weight was about 1050. Production Example (2): Synthesis of Ester Gum (B) The softening point was 95 in the same manner as Production Example (1) except that 1161 parts of polypale resin (Hercules Co., Ltd.: polymerized rosin), 92 parts of glycerin, and 32 parts of trimethylolpropane were used. ℃Hue WG~N, acid value 5.5, OH value 40,
and an ester gum (B) with a number average molecular weight of approximately 1200.
I got it. Production example (3): Synthesis of fumarized rosin ester.
510 parts of fumaric acid, 30 parts of fumaric acid, 10 parts of 1,4-cyclohexanedimethanol, 60 parts of glycerin, and a small amount of antifoaming agent were added, and the temperature was raised to 180°C. After holding at 180℃ for 2 hours, add 16.2 parts of glycerin and heat to 260℃.
The temperature rose to . Continue the reaction at 260℃ until the acid value reaches 10,
When the acid value reached 10, vacuum distillation was performed at 260°C for 1 hour to remove unreacted substances. The obtained ester has a softening point of 105℃, a hue WG, an acid value of 7.8, and an OH value of 50.
In addition, the number average molecular weight was approximately 950. Example (1) 200 parts of the ester gum (A) synthesized in Production Example (1), 200 parts of methyl methacrylate, 38 parts of butyl methacrylate, β-hydroxyethyl methacrylate
100 parts of methacrylic acid, 2 parts of toluene, 240 parts of butyl acetate, and 7 parts of benzoyl peroxide were placed in a four-necked flask equipped with a stirrer, thermometer, and _N2 gas inlet, and ester gum (A) was added. After dissolving, the temperature was raised to 90°C. After holding at 90℃ for 1 hour, the temperature was raised to 110℃ over 30 minutes, and when it reached 110℃, 300 parts of methyl methacrylate, 38 parts of butyl methacrylate, and β-hydroxyethyl methacrylate were added.
118 parts, 4 parts of methacrylic acid, 300 parts of xylene, 160 parts of butyl acetate, 5 parts of benzoyl peroxide,
A mixture of 5 parts of t-butyl perbenzoate and 6 parts of azobisisobutyronitrile was heated at 110°C to 4 parts.
It dripped over time. Once the dropwise addition was completed, the mixture was kept as it was to obtain a resin solution with a nonvolatile content of 50%, a viscosity of Z-Z ₁ , an OH value of 50, an acid value of 4.0, and a color number of 1. Example (2) Add ester gum to the same four-necked flask as Example (1).
Add 300 parts of (B), 7 parts of glycidyl methacrylate, 400 parts of xylene, 0.1 part of 2-methylimidazole, and 0.005 part of hydroquinone methyl ether, dissolve the ester gum (B) with stirring, and then heat to 110°C.
The temperature was raised to 1 and maintained for 4 hours. Then styrene 310
parts, isobutyl acrylate 220 parts, β-hydroxyethyl methacrylate 158 parts, acrylic acid 5 parts
parts, benzoyl peroxide 14 parts, azobisisobutyronitrile 14 parts, ditertiary butyl peroxide 5 parts, xylene 400 parts, butyl acetate
A mixture consisting of 200 parts was added dropwise over 4 hours while gradually increasing the temperature from 110°C to 120°C. Once the dropping is complete, hold it as it is and make sure that the non-volatile content is 50%, the viscosity is X, the OH value is 40, the acid value is 4.2, and the number of colors is 1 to
Two resin solutions were obtained. Example (3) In the same four-necked flask as in Example (1), add 400 parts of fumarized rosin ester, 500 parts of xylene, and 300 parts of toluene.
The fumarized rosin ester was dissolved while raising the temperature to 120°C. At 120°C, 100 parts of methyl methacrylate, 250 parts of styrene, 83 parts of β-hydroxyethyl acrylate, 200 parts of ethyl acrylate, 50 parts of butyl methacrylate, 200 parts of butyl acetate, 10 parts of benzoyl peroxide,
A mixture of 10 parts of azobisisobutyronitrile and 10 parts of t-butyl perbenzoate was heated at 120°C for 4 hours.
Drop it over a period of time, and once it is finished, hold it as it is until the non-volatile content is 50%, the viscosity is Y-Z, and the OH value is
30, a resin solution with an acid value of 3.5 and a color number of 1 was obtained. Comparative example: 310 parts of styrene, 22 parts of methyl methacrylate,
220 parts of isobutyl acrylate, 128 parts of β-hydroxyethyl methacrylate, 5 parts of acrylic acid,
A mixture consisting of 10 parts of benzoyl peroxide, 10 parts of azobisisobutyronitrile, 5 parts of ditertiary butyl peroxide, and 285 parts of xylene,
Butyl acetate 137 was added to the same four-necked flask as in Example (1).
After charging 263 parts of xylene and raising the temperature to 120°C, the mixture was added dropwise over 4 hours. Once the dripping is finished, hold it as it is and make sure that the non-volatile content is 50%, the viscosity is V-W,
A control resin solution having an OH value of 40, an acid value of 3.0, and a color number of 1 or less was obtained. Tables 1, 2, and 3 show the results of performance tests on the resin solutions obtained in Examples (1) to (3).

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Claims (1)

[Claims] 1. Using a radical polymerization initiator in the presence of 5 to 95% by weight of a rosin-based hard resin with a number average molecular weight of 600 to 4000, 95 to 5% of polymerizable monomers are added.
A method for producing a rosin-based hard resin modified copolymer, which comprises graft copolymerizing % by weight.