JPS619462A - Resin composition for woodwork coating - Google Patents

Abstract

PURPOSE:The titled composition having excellent gloss, drying characteristics, thinner resistance, build, and sanding characteristics, containing a specified vinyl copolymer modified with a fatty acid of a drying oil as an essential component, a cellulose derivative, an ultraviolet absorber, drier, etc. CONSTITUTION:The titled composition prepared by incorporating an ultraviolet absorber (A) in an amount of 0-40wt% of a mixture of D and E mentioned below solely or in combination with a drier (B) and/or a polyisocyanate (C) into a mixture which comprises 60-100wt% modified vinyl monomer (D) obtained by the addition of 5-60pts. fatty acid of a drying oil having an iodine value of 100-200 to 100pts. vinyl copolymer containing epoxy groups obtained by the copolymerization of 5-25wt% vinyl monomer containing epoxy groups, 0- 60wt% aromatic vinyl monomer, 0-10wt% alkyd resin containing copolymerizable unsaturated bonds, and 5-95wt% other vinyl monomer copolymerizable with these, and 0-40wt% cellulose derivative (E).

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a new and useful resin composition for wood coatings, and more specifically to a resin composition containing a specific drying oil fatty acid modified vinyl copolymer as an essential component. , a cellulose derivative, an ultraviolet absorber, a dryer and/or a polyisocyanate, and the present invention relates to a resin slag for wood coatings which has excellent gloss, drying properties, thinner resistance, texture and abrasive properties.

1. Prior Art Conventionally, paints for woodworking include lacquer-based paints that do not participate in crosslinking, and acid-curing aminoalkyd-based paints or urethane-based paints that participate in crosslinking.

Among these, lacquer-based ones are quick-drying and easy to use, but their coating performance, gloss, and appearance are inferior to urethane-based ones. It's a lot worse than that. On the other hand, acid-curing aminoalkyds dry quickly, have relatively good abrasiveness, and are hardenable, but on the other hand, they are hard and brittle.
It has the disadvantage of being prone to cracks in cycle tests, and the biggest disadvantage is that it generates harmful free formalin from the paint and cured coating. Urethane-based products are also curable, and while they have excellent coating performance, they are generally not quick-drying, and when the environmental temperature is low, such as in winter, the crosslinking reaction progresses slowly and is insufficiently cured. However, it is desired that a coating system that can compensate for the deficiencies of both lacquer systems and urethane systems is desired.

Separately, British Patent No. 767,476 discloses a method in which an air-curing resin is obtained by adding a drying oil fatty acid to an epoxy group-containing acrylic copolymer. In order to solve the problem that the resulting rosin lacks gloss due to insufficient moisture for pigments, Japanese Patent Application Laid-open Nos. 53-51232 and 53-9923
An improved method as described in Publication No. 1 has been proposed.

However, in each of the above improvement methods, the drying oil fatty acid is added to the glycidyl group in the all-acrylic resin, and then further esterified with a dicarboxylic anhydride such as tetrahydrophthalic anhydride. (1) Production of an acrylic copolymer, (2) Modification by adding a drying oil fatty acid to the copolymer, and (3) Esterification of the fatty acid-modified copolymer with dicarboxylic anhydride. This method cannot be said to be a preferable method because it lengthens the total reaction period consisting of three steps and complicates the reaction control, resulting in increased production costs.

[Problems to be Solved] In view of the above-mentioned circumstances, the present inventors have developed a drying oil fatty acid that has good wettability to pigments and excellent gloss using a simpler method. In order to obtain a modified vinyl copolymer, we also use the modified copolymer to create a resin for wood coatings that is quick-drying, has excellent gloss and texture, and does not attack the base coating or old coating. As a result of intensive studies to obtain a composition, the present invention was completed.

"Structure of the Invention" That is, the present invention comprises epoxy group-containing vinyl monomers 5-
25% by weight, aromatic vinyl monomer 0-60%,
Copolymerizable l-f alkyd resin with saturated bonds 0 to 1
0% by weight, and 5 to 95% by weight of other vinyl copolymerizable with each of the above-mentioned vinyl monomers, and then based on 100 times Jtnl+ of the resulting epoxy group-containing vinyl copolymer. , iodine value is 100
~200 drying oil fatty acids to 5~60 heavy parts 0
Modified vinyl copolymer (NNO 6) obtained by adding
0 to 100% by weight, and cellulose derivative (0 to 4% of Bl)
In addition to the mixture with ON amount %, 0 to 10% of the ultraviolet absorber (C1) is blended based on the weight of the mixture, or a dryer (D+ and/or polyisocyanate (Dog) is also blended). The present invention provides a resin composition for wood coating that has excellent gloss, drying properties, thinner resistance, texture, and abrasive properties.

Here, typical drying oil fatty acids with an iodine value of 100 to 200 include natural oils such as cotton oil, soybean oil, rice sugar oil, dehydrated castor oil, linseed oil, tall oil, or Chinese tung oil. fatty acids, [-hygiene],
``Hygiene H'', ``Hygiene S'', ``8 to conjugated fatty acid ≠ 20'' [all Soken Chemical products] or [PA'MOLYN 200, . Synthetic drying oil fatty acids such as 300J (product of Percules, Inc., USA) can be used alone or as a mixture in any proportion, and in order to adjust the iodine value of such fatty acids, In some cases, coconut oil fatty acids, castor oil fatty acids, octyl acid, °lauric acid, "persatic acid" (synthetic drying oil fatty acids manufactured by Shell in the Netherlands),
Fatty acids and saturated fatty acids with an iodine value of less than 100, such as stearic acid or hydroxystearic acid, can be added to the resulting modified vinyl copolymer (as long as the amount is within a range that does not impair the air drying properties of Al), drying oils such as those listed above can be used. Of course, it can also be used in combination with a fatty acid.

The amount of the drying oil fatty acid used is 5 to 6 parts by weight per 100 parts by weight of the epoxy group-containing vinyl copolymer.
A suitable proportion is 0 parts by weight, preferably 10 to 50 parts by weight.

If the amount used is less than 5 parts by weight, the purpose-modified copolymer (Al) will have poor air curability, and the coating film will not have a sufficient three-dimensional structure, resulting in poor physical properties and acid resistance. On the other hand, if it exceeds 60 parts by weight, it becomes easy to yellow, weather resistance decreases, and as a result of excessive crosslinking of the resulting coating film, Either the properties of the coating would be impaired or the coating would become brittle, making it impossible to put it to practical use.

Next, when discussing the above-mentioned epoxy group-containing vinyl copolymers, first, typical epoxy group-containing vinyl monomers include glycidyl (meth)acrylate, β
- unsaturated mono- or dicarboxylic acids such as methylglycidyl (methanoacrylate or (meth)allyl clycidyl ether, (meth)acrylic acid, fumaric acid, maleic acid or itaconic acid, or monovalent with such unsaturated dicarboxylic acids) α, β-ethylenically unsaturated carboxylic acids such as monoesters with alcohol, l'
HOA-MPJ or 1noA-11sJ Meta) acrylate, 2
-Hydroxypropyl (meth)acrylate is also combined with hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl fumarate, maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydronthalic acid, benzenetricarboxylic acid, "Himic acid" [Hitachi 6-glaze unsaturated carboxylic acids such as Kasei Kogyo ■ products], todecinyl succinic acid, succinic acid, or phthalate obtained by equimolar addition reaction with polycarboxylic acids (anhydrides) such as succinic acid or tetrachlorophthalic acid, ``Epicron 200, 400, 441.850 Mogha 1050J [epoxy resin manufactured by Dainippon Ink and Chemicals], ``Epicor) 828.1001 or 100
4J (epoxy resin manufactured by Shell), "Araldite 6"
o71 or l160B4J (epoxy m& manufactured by Ciba Geigy, Switzerland), r-1-Tunonox 221J
(Chick@J Ten's epoxy compound) Also, various polyepoxy compounds having at least two epoxy groups in one molecule, such as Hartechol EX-611J (Nagao Sangyo [manufactured epoxy compound]), etc. Epoxy group-containing polymerizable compounds obtained by addition reaction at a molar ratio can be used alone or in a mixture of 28 or more, but depending on the reactivity, number of reaction steps, and viscosity of the final product. Taking into consideration factors such as price, monomers with relatively low molecular weights such as glycidyl (meth)acrylate and β-methylglycidyl (meth)acrylate are easiest to use.

The epoxy group-containing vinyl monomer is used in a range of 5 to 25% by weight, but since the epoxy group in the monomer participates in the reaction with the drying oil fatty acid as mentioned above, the amount of the monomer Needless to say, the amount to be used should be determined mainly depending on the amount of the drying oil fatty acid used, and it is usually in the range of 1.0 to 1.25 equivalents per 100 weight of the drying oil fatty acid carboxyl group. It is preferable to use the epoxy resin in such a proportion that the epoxy resin is used from the viewpoint of reaction rate and the fact that residual carboxyl groups do not reach the coating film, thereby preventing adverse effects.

In addition, the alkyd resin having a copolymerizable unsaturated bond as described above can be used not only for pigments with low oil absorption such as titanium oxide and Bengara, but also for quinacridone series and phthalocyanine series.

It is used when it is desired to improve the dispersibility of organic pigments such as azo pigments and pigments with relatively large oil absorption that have poor dispersibility such as carbon black, and in that sense, the alkyd resin is It can be said that this does not have any influence on the coating film performance itself.

The alkyd resin may be one modified with oil or fatty acid, or a so-called oil-free alkyd resin that is not modified with these. A type having an unsaturated bond copolymerizable with a vinyl monomer is suitable in the present invention.

Examples of the alkyd resin include octyl acid and lauric acid.

Saturated fatty acids such as stearic acid or "persatic acid"; unsaturated fatty acids such as oleic acid, linoleic acid, lyluic acid, eleostearic acid or ricinoleic acid; [Vamoline 200,300J, Chinese tung oil (fatty acids)]
, linseed oil (fat P), dehydrated castor oil (fatty acid), tall oil (fatty acid), cottonseed oil (fatty acid), soybean oil (fatty acid)
, olive oil (fatty acids)% safflower oil (fatty acids), (semi-)drying oils (fatty acids) such as castor oil (fatty acids) or rice sugar oil (fatty acids) and L-hydrogenated coconut oil (fatty acids), palm Ethylene glycol, propylene glycol, glycerin, with or without the use of one or a mixture of two or more oils or fatty acids, such as oils (fatty acids) or non-drying oils (fatty acids) such as palm oil (fatty acids). Trimethylolupurone, trimethylolpropane, neopentyl glycol, 1,6-hexanediol% 1,2
．． One or more kinds of polyhydric alcohols such as 6-hexahydriol, pentaerythritol or flubitol, and benzoic acid, p-t=nibutylzoic acid, (
phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic acid, tetrahyrophthalic anhydride, hexachlorophthalic anhydride,
Carboxylic acids such as tetrabromo phthalic anhydride, trimellitic acid, hymic acid, succinic anhydride, maleic anhydride, itaconic acid, fumaric acid, adipic acid, cepatic acid or oxalic acid One or more acids are added to the chamber, and if necessary, a monoepoxy compound such as a glycidyl ester of a fatty acid such as "Cardura E" (Shell Co., Ltd. Tanuki 1 product), [Epiclon 2
00,400J, [polyepoxy compounds such as Epicoat '328.1o01J, diisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate or ij4.4'-meblene bis(cyclohexyl isocyanate); 1 m or 2 types of polyisocyanates obtained by addition reaction of each diisocyanate with the above-mentioned polyhydric alcohols or water, or incyanuric ff1t-containing polyisocyanates obtained by (co)polymerization of diisocyanates with each other. In this case, it is appropriate to replace a part of the polyhydric alcohols and carboxylic acids mentioned above and carry out the reaction in a conventional manner.
The alkyd resin has no copolymerizable unsaturated bonds or is of a saturated fatty acid or non-drying oil (fatty acid) modified type, or is an oil 7 Li alkyd resin that is not modified with oil or fatty acid. It is necessary to introduce copolymerizable unsaturated bonds, which should serve as raft points for other vinyl monomers, into the alkyd resin using an unsaturated carboxylic acid such as (anhydrous) maleic acid or fumaric acid. Needless to say.

The alkyd resin thus obtained is D
It is used in the range of ~10% by weight, but when it is used in a large amount exceeding 10% by weight, Vc becomes inferior such as solvent resistance and stain resistance. Moreover, during polymerization, the carboxyl group in the alkyd resin and the epoxy group in the epoxy group-containing vinyl monomer react with each other, resulting in undesirable problems such as easy gelation.

Therefore, the amount of the alkyd (② fat) to be used is within the range described above, and the acid value, oil length, amount of copolymerizable unsaturated bonds, and the It is preferable to determine the molecular weight of the alkyd resin and the molecular weight of the modified copolymer (Al) to be obtained.

Next, typical aromatic vinyl monomers mentioned above include styrene, α-methylstyrene%p'
-Butylstyrene or vinyltoluene, etc.
Among these, styrene is most preferred in terms of cost.

If the aromatic vinyl monomer is used in a large amount exceeding 60%, the resulting paint film will have poor weather resistance and will be unsuitable as an outdoor paint resin. When used, it should be determined within 60% by weight depending on the required performance such as gloss, texture, weather resistance, etc., from the balance of gloss, texture, leveling property, and weather resistance. is preferably in the range of 10 to 50% by weight.

Furthermore, representative vinyl monomers that can be copolymerized with the epoxy group-containing vinyl monomers, aromatic vinyl monomers, and alkyd resins having copolymerizable unsaturated bonds include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, 1-propyl (meth)acrylate, n-butyl (meth)acrylate, i-
Butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,
Various (meth)acrylates such as lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dibromoglopyl (meth)acrylate, tribromophenyl (meth)acrylate or alkoxyalkyl (meth)acrylate; Maleia Wp % diesters of unsaturated dicarboxylic acids and monohydric alcohols such as fumaric acid or itaconic acid; vinyl esters such as vinyl acetate, vinyl benzoate or "Beoba" (vinyl ester manufactured by Shell);
[Viscoat BF, BFM, 3F or 3FMJ [fluorine-containing acrylic monomer manufactured by Osaka Organic Chemical Industry Co., Ltd.], perfluorocyclohexyl (meth)acrylate, ciba-fluorocyclohexyl fumarate or N-1-globilver fluorooctane sulfone Vinyl esters and vinyl ethers containing (bar)fluoroalkyl groups such as amidoethyl (meth)acrylate (meth)
Fluorine-containing compounds such as acrylates or unsaturated carboxylic acid esters; or olefins such as (meth)acrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, or vinylidene fluoride.

Typical hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. -Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)
acrylate, di-2-hydroxyethyl fumarate,
Hydroxyalkyl esters of α,β-ethylenically unsaturated carboxylic acids such as mono-2-hydroxyethyl-motsputyl fumarate or polyethylene glycol mono(meth)acrylate; (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid acids, unsaturated monomers or dicarboxylic acids such as itaconic acid or citraconic acid, and α, β-ethylenically unsaturated carboxylic acids such as mononisdels of these dicarboxylic acids with monovalent alcohols; Carboxylic acid hydroalkyl esters and various polycarboxylic acids (anhydrides) as described above
[Cardura EJ, monoglycidyl esters of monovalent carboxylic acids such as coconut oil fatty acid glycidyl ester or octylic acid glycidyl ester, or adducts with monoepoxy compounds such as butyl glycidyl ether, ethylene oxide or propylene oxide; In addition, methylol-based compounds such as 1-jN-methylolated acrylamide or hydroxyethyl vinyl ether can also be used;
It is a matter of heat theory that it is necessary to determine the usage price so as not to result in gelation.
Care should be taken to avoid gelation due to reaction between the groups and the (β-methyl)glycidyl groups in the (β-methyl)glycidyl (meth)acrylate.

Next, as the cellulose derivative (Bl) mentioned above, any one that is normally used for coating and i can be used.

Among these, particularly representative ones are nitrocellulose, cellulose acetate, cellulose acetate globionate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose, and benzyl cellulose.

The cellulose derivative may be used when it is safe to further improve drying properties, abrasive properties, gasoline resistance, and adhesion properties, but in such cases, the amount used should be 4.
0% by weight or less, preferably 30% by weight or less, and optionally a known plasticizer such as dibutyl phthalate or dioctyl phthalate.
This does not preclude the use of all 101.

If this usage amount exceeds the AO kyostoichiometry, surface 1 contamination occurs.
This is not preferable because water resistance, moisture resistance, etc. are noticeably reduced.

The above-mentioned ultraviolet absorber (C1) is a component used when it is necessary to further improve the durability of the composition of the present invention, and it can be added and mixed each time, but in that case, may be used in a range of 0 to 10% based on the total amount of the modified copolymer (At and cellulose derivative (Bl)).

If the amount used is more than 10%, the effect is great, but on the other hand, it often becomes a disadvantageous VC in terms of cost due to reduced side wood properties.

The ultraviolet absorbers (representative examples of C1 include benzophenone, 2.4-dihydrobenzophenone, 2.2
', 4゜4'-tetrahydroxybenzophenone, 2-
Hydroxy-4-methoxybenzophenone, 2.2'-
dihydroxy-4゜4'-dimethoxybenzophenone,
2.2'-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-
4-dobutyloxybenzophenone, 2-hydroxy-4
-methoxy-5-sulfobenzophenone, 5-chloro-
2-hydroxybenzophenone, 2゜2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-(2-hydroxy-3 -Methyl-acryloxyisoprophoxydibenzophenone; 2-(2'-hydroxy-5'-methruphenyl)-benzotriazole, 2-(2-hydroxy-3
,5-di-t-amyl-phenyl)-2B-benzotriazole, 2-(2'-hydroxy-6',5'-di-t-butyl-phenyl)benzotriazole, 2-(
2'-hydroxy-3', 5'-di-t-butyl-5'
-methyl-phenyl)benzotriazole, 2-(2'
-Hydroxy-6',5'-di-t-butyl-phenyl)-5-40roben7')
2'-hydroxy-3',5'-di-t-inamyl-
phenyl)benzotriazole, (2-hydroxy-5
-t-butylphenyl)benzotriazole; phenyl salicylate, 4-t-butylphenyl salicylate F
bP-octyl-phenyl salicylate; ethyl-2-
Cyano-3,3'-diphenyl-acrylate, 2-ethylhexyl-2-cyano-3,3'-diphenyl-acrylate: Hydroxy-5-methoxy-acetophenone, 2-hydroxy-naphthophenone; 2-ethoxyethyl- p-methoxycinnamate; nickel and suoctylphenyl sulfide; 4-benzoyloxy-2
,2,6,6-titramethylpiveridine, bis-(2,
2,6,6-tetramethyl-4-piperidyl) sebacate or [Tinuvin 292J (FPA Geigy product)
Etc., etc. may be used alone or in combination of two or more types.

To further increase effectiveness, or [Sumilizer B
HTJ [Sumitomo Chemical Co., Ltd. product], [Seenox BC8]
J [Shiraishi Calcium ■ Product], “Irganopux 101
0 or Fi1076J (Ciba Geigy product), [
It is also possible to use a well-known and commonly used antioxidant such as Tsukurizer TNPJ (produced by Shinko Ouchi) or KBJ (antioxidant) (produced by Bayer AG, West Germany).

Next, the above-mentioned dryer (Di may be any one commonly used for paints, but the most representative ones include cobalt, vanadium, manganese, cerium, lead, iron, calcium,
Zinc, zirconium, cerium, nickel, nickel, tin, etc. are nanthenate, octylate or resinate, and the amount used depends on the type of dryer, the silkiness of each ingredient, etc. It may be determined as appropriate depending on the combination or required performance.

At this time, a small amount of an organic peroxide such as benzoyl peroxide, methyl ethyl ketone peroxide or t-butyl perbenzoate may be used in combination to enhance the effectiveness of the dryer.

Further, all known and commonly used paint additives such as pigment dispersants and leveling agents can be used in combination.

In general, the above-mentioned polyisocyanates (typical examples of El include aromatic diincyanates such as tolylene diisocyanate, xylylene diisocyanate, or diphenylmethane diisocyanate; tetramethylene diisocyanate, hexamethylene diisocyanate, or hatrimethylhexamethylene) aliphatic diincyanates such as diisocyanate; or inphorone diisocyanate, methylcyclohexane-2,4-(or 2,6-)7'/ane-), 4. /! '-methylenebis(cyclohexyl isocyanate) or 1.
Diisocyanates such as alicyclic diisocyanates such as 6-di(incyanate methyl)cyclohexane, or each of these diisocyanates, the polyhydric alcohols, and a low molecular weight polyester resin having a functional group that reacts with the incyanate group. (We also sell oil-modified types.), acrylic copolymers (including those containing styrene as a total comonomer component), or adducts with water, etc.
Furthermore, there are biuret bodies and (co)polymers (including oligomers) of the above-mentioned diisocyanates.

By the way, when using the polyisocyanate, aromatic diincyanates and their derivatives that yellow or crack due to ultraviolet rays are unsuitable for outdoor use, and should be used only for weather resistance. Suitable for indoor paints that do not require too much. Therefore, in such a case, for outdoor use, aliphatic diincyanates, alicyclic diincyanates, or various derivatives thereof, which have good weather resistance, may be used.

The amount of polyinsyanate used is OH/NC.
An equivalent ratio of o=110.1 to 1/1.2 is suitable.

In order to obtain the composition of the present invention, the epoxy group-containing vinyl copolymer is first prepared usually by solution polymerization, and then the drying oil fatty acid described above is added to this copolymer to obtain the desired fatty acid modification. Vinyl copolymer (Although it is used to obtain Al, in the copolymerization reaction, which can be called the first stage reaction, the polymer conversion rate of the epoxy group-containing vinyl copolymer is usually secured at 95% or more. It is advantageous that the drying oil fatty acid can be added to proceed with the addition reaction, which can be called the second stage reaction, without having to wait for the completion of the copolymerization reaction.

In addition, the reaction temperature is not particularly limited, as long as it is at a temperature suitable for the polymerization of each component compound as described above during the copolymerization reaction, and is within the commonly used range of 50 to 140 degrees Celsius. On the other hand, during the addition reaction, the temperature suitable for the addition of each reaction component as described above, that is, 110
The temperature may be in the range from 180 DEG C. to 180 DEG C., which is also advantageous, especially during addition reactions, since high temperatures can be used to accelerate this reaction.

Furthermore, in order to promote the addition reaction, a ring-opening catalyst of an epoxy group may be used, and in that case, any known and commonly used catalyst can be used, but the most representative ones include triethylamine, diethylenetriamine, and imidazole. Tertiary amines such as BF, complexes, or acids such as phosphoric acid or sulfur.

Furthermore, as the polymerization initiator used in the polymerization, any known and commonly used initiator can be used, but among them, particularly representative ones include azobisisobutyronitrile and benzoyl peroxide. , t-butyl barbenzoate, t-butyl peroctate, di-t-butyl peroxide, and the like.

Known and commonly used solvents can be used, but the most representative solvents include aromatic solvents such as toluene or xylene, ester solvents such as ethyl acetate, butyl acetate or cellosolve acetate, and methanol or butanol. Alcohol-based or ketone-based such as methyl ethyl ketone or methyl isobutyl ketone, etc., as well as hexane, heptane, cyclohexane, methylcyclohexane, petroleum naphtha, or mineral spirits! ! ! Aliphatic or alicyclic solvents can also be used.

As for the birch, the mixture, and the amount of use of such solvents.

02 The amount can be appropriately determined in consideration of the amount of the drying oil fatty acid used, the amount of vinyl moiety used in the epoxy group-containing vinyl copolymer, etc.

"Effects of the Invention" The drying oil-fatty acid modified vinyl copolymer obtained in this way is in the form of a drying oil-fatty acid modified vinyl copolymer grafted with an alkyd resin. Its wettability to pigments gives it excellent gloss, and its unique structure also has the advantage of being able to be air-cured by adding a dryer.

In addition, in the present invention, during the preparation of the epoxy group-containing vinyl copolymer, the alkyd resin is not only radically polymerized during the radical polymerization, but also the carboxyl groups in the alkyd resin within the specified amount range are the epoxy groups. As a result of the addition reaction with the epoxy group in the vinyl monomer contained, the resulting modified copolymer (All-j) has a wide molecular weight distribution, has excellent pigment dispersibility, and There is also the advantage of having a product that has the characteristics of quick drying in terms of texture and adhesion to the base material.

The composition of the present invention has been described above. This meets various demands in this industry. That is, the resin composition for wood coatings of the present invention can be said to be a third type of wood coating material, and is based on drying oil fatty acid residues contained in the modified copolymer fAl. Alternatively, there are three types of crosslinking reactions: the hydroxyl groups slightly present in the modified copolymer iAl and the polyisocyanate blended with it (crosslinking reaction with El, and further crosslinking reactions of both of them). The modified vinyl copolymer (Al) of the 1s class can be used as desired, and it can be said that it is a unique composition that can immediately obtain a coating film with excellent performance through such a crosslinking reaction. It goes without saying that it can be used as an enamel paint using all known pigments, or as a clear paint without using any known pigments.

Since drying oil fatty acids are introduced into the modified vinyl copolymer (Al) as an essential component of the composition of the present invention, the composition of the present invention as a whole is suitable for use in acrylic polyols used in urethane systems. Solvents with weaker enlightening power than each agent (
Since it is easily dissolved in weak solvents, it has the advantage that it can be used in weak solvents, so it is possible to obtain a wood coating that does not easily attack the base coat or old coat.

Furthermore, a modified copolymer which is an essential component of the composition of the present invention (Al has a hydroxyl group, and in addition In the present invention, in addition to the vinyl monomer having a epoxy group, a vinyl monomer having a hydroxyl group can also be used in combination with the vinyl monomer having a hydroxyl group. By blending polyisocyanate-1-(El7) with urethane crosslinking and curing,
Furthermore, a dryer (oxidative polymerization crosslinking curing with D+,
There is an advantage that a method of curing by two crosslinking reactions with this urethane crosslinking curing can be adopted.

Next, the present invention will be explained in detail with reference to all reference examples, examples, and comparative examples. In the following, all parts and percentages are based on weight unless otherwise specified. Example 1
[Preparation example of modified vinyl copolymer (AI)] 800 parts of xylene, "Beccosol P-
71 parts of long oil alkyd resin manufactured by Dainippon Ink and Chemicals Co., Ltd.] and 2 parts of di-t-butyl peroxide (hereinafter abbreviated as DTBPO) were charged and the temperature was raised to 125°C. When the temperature reached the same temperature, 400 parts of styrene (St) and methyl methacrylate (MA") were added.
300 parts of acrylonitrile (AN), 55 parts of glycidyl methacrylate (GMA), 70 parts of ethyl acrylate (EA), 1° part of azobisisobutyronitrile (AIBN), t-butylbar octane. )
(7 parts of (TBPO) and t-butylperbenzony)
A mixture of 4 parts of (TBPB)? Dropped in 5 hours,
After the dropwise addition, the same temperature was maintained for 5 hours to remove the non-volatile content (NV
) was 56.9%, 50 parts of oil fatty acid, 150 parts of soybean oil fatty acid, and 2-methylimidazole (
After 13 hours of adding 0.2 part of 2MIZ) and carrying out an addition reaction between the glycidyl group and the carboxyl group at the same temperature, the NV was 60.6%, the viscosity (Gardner; hereinafter the same) was z6, A bath solution of a fatty acid-modified vinyl copolymer having an acid value of 2.6 was obtained, and 400 parts of xylene was added to this solution to adjust the NY content to 50%.

The thus obtained resin bath liquid had an NV of 50.1%, a viscosity of Y-Z, a color number (Gardner; hereinafter the same) of 5 to 6, and a gel permeation chromatography (GP).
The number average molecular weight (hereinafter abbreviated as "A") according to C) is 8
．． A transparent melt R of +00 was obtained, and this is hereinafter abbreviated as a modified copolymer (A-1).

Reference Example 2 (same as above) In a flask similar to No. 111, “Betucosol 13,1” was added.
200 parts of 13J (medium oil alkyd resin manufactured by the same company), 1.300 parts of Turpentine and 3 parts of DTBPO were heated to 120°C, and at the same temperature 300 parts of St, MM
300 parts of A, 200 parts% of G kite 100 parts of n-butyl acrylate (BA), 15 parts of AIBN% TBPO
A mixture consisting of 10 parts of TBPB and 2 parts of TBPB was added dropwise over 5 hours, and the same temperature was further maintained for 12 hours to polymerize. When the process was continued, the NV was 42.0%, and at this stage, a white dextrous vinyl copolymer which had not been fermented into turpentine was obtained.

Next, to this copolymer were added 100 parts of cottonseed oil fatty acid, dehydrated castor oil) and 300 parts of fatty acid, and the mixture was heated at 150°C.
So, when the reaction was carried out at 1, which has an acid value of about 1, the NV was 50.
．． 8%, the viscosity is 2-2. A transparent resin bath liquid having an acid value of 1.1, a color number of 1 to 2, and an Mn of Z200 was obtained. Hereinafter, this 'i''L modified copolymer (A-2)
It is abbreviated as

Reference Example 6 (same as above) In a flask similar to Reference Example 1, 1,200 M of xylene was added.
, 29 parts of 1-Petscosol P-470-70, l)
'l' 4 parts of B P O were charged and heated to 125°C, and when the temperature reached the same temperature, 200 parts% of St 23 of MMA
0 parts, 125 parts of G M A, 100i of BA, 225 parts of n-butyl methacrylate (HMA), 100 parts of 2-hydroxyethyl methacrylate (2-HEMA), 5 parts of AIBN, 'l' B P O Part 6 and T
A mixture consisting of 5 parts of BPB was added dropwise over 5 hours, and the polymerization was continued at the same temperature until the NV reached 44%.
100 parts of linseed oil fatty acids and 10 parts of safflower oil fatty acids
0 part, BF, and 0.02 part of etherate were added and reacted until the acid value was around 1. NY was 50.5%, the viscosity was 24, the number of colors was 2, and the acid value was 18. A transparent resin solution with a hydroxyl value of 35 and an Mn of 14.000 was obtained. Hereinafter, this will be abbreviated as fully modified copolymer (A-3).

Reference Example 4 (same as above) Into a flask similar to Reference Example 1, 1.075 parts of xylene, 125 parts of Betsukosol J-571J (long oil alkyd resin manufactured by the same company) and 4 parts of DTBPO were charged and heated at 125°C. 400 of st.
After continuing BMA polymerization, the temperature was raised to 150'C, 100 parts of dehydrated castor oil fatty acid was added, and the addition reaction was continued until the acid value was around 1. NY was 493% and the viscosity was 2.
1, acid value 12, hydroxyl value 60, color number 5-6, Mn
A transparent resin solution with a value of 11.00.0 was obtained. Hereinafter, this will be abbreviated as fully modified copolymer (A-4).

Reference Example 5 (same as above) 545 parts of isophthalic acid, 248 parts of adipic acid, and 362 parts of neopentyl glycol were placed in the same flask as in Reference Example 1, except that a water separator was attached in place of the reflux condenser. ,) 10 parts of dimethylol, 2 parts of fumaric acid and 18 parts of fumaric acid were heated at 180°C in a stream of N gas.
The reaction was continued for 2 hours, then the temperature was raised to 220°C over 2 hours to continue the reaction, and the temperature was lowered when the solid content acid value reached about 6, and xylene/butyl acetate = 50
Diluted with a mixed solvent of 150 (weight ratio) to NV'z 60%, the viscosity was H-I%, the acid value was 6.8, and the hydroxyl value was 8.
1. An oil-free alkyd resin n liquid containing a polymerizable unsaturated bond and having a color number of 2 was obtained.

Then 34 parts of this resin solution and 1.200 parts of xylene
1 part and 5 parts of DTBPO were charged into the same flask as in Reference Example 1, heated to 125°C, and at the same temperature, S
t 300 parts, MMA 30 parts, t-butyl methacrylate (t-HMA) 100 parts, GMA 125 parts, DMA
285 parts, 2-HEMA 40 parts, BA 100 parts%AI
A mixture consisting of 8 parts of BN, 3 parts of TBPo, and 5 parts of TBPB was added dropwise over 5 hours, and the polymerization was continued at the same temperature until the NV reached 44%. When 100 parts of flower oil fatty acid and 0.04 part of BFA etherate were added and reacted until the acid value reached around 1, NY was 50.1% and the viscosity was Y-Z.

The acid value is 19, the number of colors is 2, the hydroxyl value is 25, and the number is 1.
A clear resin solution of 2.000% was obtained.

Hereinafter, this will be abbreviated as fully modified copolymer (A-5).

Reference Example 6 (same as above) Same procedure as Reference Example 2 except that the same amount of t-HMA was used instead of Si2, NY was 50.6%.
, the viscosity is Y, and the number of colors is 2. The acid value is 1.5 and the turtle is 7.
100 clear resin acid liquid? Obtained. Hereinafter, this will be abbreviated as a modified copolymer (A-(S)).

Reference Example 7 (same as above) Instead of 200 parts of st, 1,00 parts of t-DMA,
50 parts of N-1-propyl perfluorooctane sulfonamide ethyl acrylate and 50 parts of [Visco-
)8Fj [octafluorobutyl methacrylate manufactured by Osaka Organic Chemical ■] was used in the same manner as in Reference Example 6, with an NV of 498%, a viscosity of 28, a color number of 2, and an acid value of 1. 7. Hydroxyl value is 65 and Mn is 14
,000 was obtained. Hereinafter, this will be abbreviated as modified copolymer (A-7). Reference Example 8 (same as above) In a flask similar to Reference Example 1, 818 parts of xylene and D
After charging 2 parts of TBPO and raising the temperature to 125°C, after reaching the same temperature, the same procedure as in Reference Example 1 was performed except that the amount of BA was changed to 120 parts, and NY was 54.1%. 50 parts of linseed oil fatty acids and 15 parts of soybean oil fatty acids
Add 0 parts and 0.2 parts of 2-MIZ to form acid 1iTh 2
．． The addition reaction continued until around 5.

Next, add 400 parts of xylene to this and make 50 parts of NY.
%, NY was 498%, viscosity was Y1, color number was 5-6. A transparent resin solution with an acid value of 2.2 and an MH of s, ooo was obtained. Hereinafter, this material will be abbreviated as modified copolymer (A-8). Reference Example 9 (same as above) "The use of Betucosol 1343J was completely omitted, the amount of turpentine used was 1.400 parts, and NY was 41. 8%
The same procedure as in Reference Example 2 was carried out except that a white wax-like vinyl copolymer was obtained.
is 50.1%.

The viscosity is y-z, the acid value is 10, the number of colors is 1-2, and ji
'! A clear resin solution with a -n of 7,00 [1] was obtained. Hereinafter, this will be abbreviated as modified copolymer (A-9).

Reference Example 10 (same as above) 20 parts of BMA and 14 parts of xylene were used instead of 34 parts of an oil-free alkyd resin solution containing polymerizable unsaturated bonds, and the initial amount charged into the flask was 1.200 parts.
Reference Example 5 except that the amount of BMA added was changed from 285 parts to 1.214 parts and 305 parts from 285 parts.
Similarly, NY is 499%, viscosity is X-Y, acid value is 1
．． 8, color number is 1°, hydroxyl value is 25, and Mn is 12,
A clear resin solution of 0.000 was obtained. Hereinafter, this will be abbreviated as a modified copolymer (A-10).

Reference Example 11 (same as above) The same amount of t-BMA was used instead of 200 parts of stO, and 20 parts of HMA and 9 parts of xylene were used instead of 29 parts of "Betucosol P-470-70". In the same manner as in Reference Example 5, N
Y is 50°0%, viscosity is zt, color number is 1, acid value is 1.
9. A transparent resin acid i having a hydroxyl value of 65 and an i of 14,000 was obtained. Hereinafter, this will be referred to as a modified copolymer (A-1
It is abbreviated as 1).

Examples 1 to 30 and Comparative Examples 1 to 2 Modified copolymers (A-1) to (A-1) obtained in Reference Examples 1 to 11
A-11), and as shown in Tables 1 and 2, "Tie Bake CR-93JC Ishihara Sangyo ■ rutile type oxide≠tan], 6% cobal naphthenate) / 24% lead naphthenate = 50150 (weight ratio), a cellulose derivative, an ultraviolet absorber, and /Sotake polyisocyanate were also used to prepare a white enamel paint.However, Comparative Examples 1 and 2 were commercially available as n acrylic urethane wood paints. This is an example of using what is shown below.

In addition, these cellulose derivatives include nitrocellulose derivatives (NC) and rcAB-551.
-0,2j [cellulose φ acetate butyrate (CAB) manufactured by Eastman Kodak Company, USA]
In addition, as a UV absorber, [Tinuvin 292J/r
Tinuvin 900J = 50150 (weight ratio) mixture (both "Tinuvin" are products of Ciba Keigy, West Germany)
was used, and the polyinsyanate was "Burnock R".
N-950J [: Hexamethylene diisocyanate-based polyisocyanate 5-1- manufactured by Dainippon Ink & Chemicals ■],
"Coronate EH" [hexamethylene diisocyanate-based polyisocyanate manufactured by Nippon Polyurethane Industries, Ltd.] was used, but in Examples 2 and 22, 2 parts of a plasticizer called butylbenzyl phthalate was also used. All derivatives were used as 40% methyl ethyl ketone solutions.

To make white enamel into a paint, we used 100 parts of a modified copolymer, which is the main component of the paint face, a predetermined amount of Tybake CR-93J, 30 parts of xylene, and 20 parts of xylene.
A PWC of 35% was obtained by adding 0 parts of glass and 0 parts of glass and kneading them in a sand mill for 9 parts of 0 minutes.
However, in this case, xylene/
A mixed solvent of l-butyl acetate = 90/10 (weight ratio) was used.

Next, the painting was done by a spray painting method, but the base material for the evaluations in Tables 1 to 3 was a glass plate and teak wood that had been conditioned with an acrylic urethane sanding sealer. In Table 5, the tin plate is
The material is made of wood. Forced drying at 50° C. for 40 minutes was used as the curing condition, and each coating film performance test was conducted after being allowed to stand for 7 days after such forced drying. (1st~
(Table 3.5) Among the test items, the "adhesion" test involves removing the cellophane tape after making a cross cut, that is, after making a cross cut.

In addition, the "weather resistance" test is expressed by the gloss retention rate (%) when exposed for 1.500 hours using a Sunshine Weather-Ometer and when exposed outdoors for 2 years in Miyazaki City. It is.

The "drying" test was performed after painting on a glass plate and then drying it to the touch (
(unit: 2 minutes) and put 4 layers of gauze on the surface of the coating film,
A 100II weight was further placed on top of the gauze for 1 minute, and then the gauze marks were visually judged.The dryness evaluation criteria were as follows: .

0 ・・・・・・ No gauze marks at all○ ・・・・・・ Some gauze marks △ ・・・・・・ Lots of gauze marks× ・・・・・・
- Significant gauze marks The results of each Example and Comparative Example are shown in Table 1 for Examples 1 to 2o, and for Examples 21 to 3.
0 and Comparative Examples 1 and 2 are shown separately in Table 2, but only Comparative Examples 1 and 2 are shown in their respective tables.

Water whitening resistance and fleshy feeling were evaluated based on the following evaluation criteria.

0...Excellent○...Good △...Poor This is an example using a commercially available acrylic urethane wood paint.

Water whitening resistance was determined by visually determining the degree of gloss and whitening of the coating after immersion in tap water at 40°C for 5 days. Crack resistance was expressed as the number of cycles until cracks appeared in the coating film, where one cycle was holding at -20°C for 2 hours and then at 80°C for 2 hours.

The series of Examples 31 to 40 and Comparative Examples 3 to 3 were evaluated as clear paints, and the coating was performed by a spray coating method. The curing conditions were forced drying at 50° C. for 40 minutes.

Examples 41 to 47 and Comparative Examples 7 to 10 Each of the Examples and Comparative Examples in this series is for examining pigment dispersibility.
Also, each pigment was weighed out for 100 parts of modified copolymers (A-1) to (A-11) at a predetermined pwcK as shown below, and further 60 parts of xylene and 200 parts of The glass peas were added separately and kneaded for 2 hours in a sand mill for MW. Then, 4% of the solid content of the modified copolymer used therein was added to each of the kneaded enamel bases. %
Cobalt Nanthenate/24% Lead Nanthenate-5o15o
Add a mixture of (fril ratio) and apply various paints to tAM
It's L.

White --- [Tie Bake CR-93J, PWC: 35
% Black... "Royal Spectra Mark nJ
(Carbon black manufactured by Columbia Carbon Co., USA), PWC: 30% Red...[Firstken Super Red BN]
J (quinacridone pigment manufactured by Dainippon Ink & Chemicals ■).

PWC: 10% Green: "Firstken Green S" (cyanine green manufactured by the same company), PWC: 10% Next, we conducted a test for pigment dispersibility for each paint. 1. The evaluation criteria for the chickenness of paints and the presence or absence of pigment agglomeration are as follows.

◎・−・・No abnormality
△E) - is white/black/red/green - ID 01515
15 (weight ratio) of each of the above color enamel bases, and further added a mixture of 6% nandene, cobalt, 724% lead naphthenate = 50,750 (weight ratio). Separately, I first spray painted it on a tin plate and then let it dry to the touch'c)iA
This is done by measuring the color difference (ΔE) on a coated plate, and it can be said that the smaller this value is, the smaller the color difference is, and therefore the better the pigment dispersibility.

The above results are summarized in Table 4, and titanium oxide (
Chicken properties and pigment aggregation when using [Tie Bake CR-934] were not observed in any of the Examples and Comparative Examples, so they are not shown in the table.

Each series of Examples 48 to 56 and Comparative Examples 11 to 1 was evaluated as a sanding sealer, and four coats were applied using a spray coating method. The curing conditions were forced drying at 50° C. for 40 minutes.

The abrasiveness was tested by forced drying at 50°C for 40 minutes, and after 60 minutes, hand-sanded 20 times with +400 sandpaper to check the ease of sharpening and the condition of the paint film remaining on the vapor. Visual judgment was made using the following criteria.

Yu)...Excellent abrasiveness, no staining on vapor ○... Average abrasiveness, some staining on vapor Δ---Poor abrasiveness, maybe staining on vapor Shade × ・・・・・・ Significantly inferior abrasiveness, noticeable damage to vapor, and from the above results, the coating film obtained at each pH was 90% thicker than that of the comparative example. It can be seen that the dryness, thinner resistance, texture, and abrasiveness are well balanced.

Procedural amendment 7゜January 1980/^ Japan Patent Office Commissioner Manabu Shiga 1, Indication of the case 1982 Patent Application No. 129974 2, Name of the invention Resin composition for wood coating 3, Make amendments Relationship with the patent applicant 3-35-58 Sakashita, Itabashi-ku, Tokyo 174 (28
B) Dainippon Ink & Chemicals Co., Ltd. Representative Yo Mura
Kuni Shigeru 4, Agent: Oguchi Hon Ink Chemical Industry Co., Ltd., 3-7-20 Nihonbashi, Chuo-ku, Tokyo 103 Phone number: Tokyo (03) 272-4511 (main representative) 6
, Contents of amendment subject to amendment (l)' The statement on page 9, line 12 of the specification is corrected as follows.

2-Hydroxyethyl (meth)acrylic 1 (21 specification, page 14, line 9, and page 20, line 10 of the r-tylphthalate)
Correct "Cardura E" in the rows to rCardura E-10J.

(3) The statement on page 15, lines 13-14 of the specification is corrected as follows.

1 (4) Statement on page 20, line 8 of the specification, by using an unsaturated carboxylic acid such as maleic anhydride or fumaric acid to form a copolymerizable unsaturated bond in the alkyd resin. Correct as follows.

``Unsaturated carboxylic acids and the above α,β-unsaturated carboxylic acids 1 (5) The statement on page 26, line 1 of the specification is corrected as follows.

V A conventional antioxidant can be used in combination, and a conventional anti-skinning agent such as methyl ethyl ketoxime can also be used in combination. j (6) Description on page 44, line 15 of the specification rX-Y2
Correct J to 'X-Y2J.

that's all

Claims (1)

[Scope of Claims] (A) 5 to 25% by weight of an epoxy group-containing vinyl monomer,
Aromatic vinyl monomer 0-60% by weight, alkyd resin having copolymerizable unsaturated bonds 0-10%
% by weight, and 5 to 95% by weight of other vinyl monomers copolymerizable with these, and then, with respect to 100 parts by weight of the thus obtained epoxy group-containing vinyl copolymer, an iodine value of 10
Modified vinyl copolymer 60 obtained by addition reaction of drying oil fatty acids of 0 to 200 in a proportion of 5 to 60 parts by weight
~100% by weight, and (B) 0 to 40% by weight of a cellulose derivative, and (C) 0 to 10% by weight of an ultraviolet absorber based on the weight of the mixture, or Alternatively, a resin composition for wood coating further contains (D) a dryer and/or (E) a polyisocyanate.