JPS5839188B2 - Hifukuyoujiyushisoseibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high non-volatile coating resin composition having excellent properties and comprising a hydroxyl group-containing modified resin obtained by novel graft copolymerization and a polyisocyanate compound.

Recently, due to the problem of air pollution caused by organic solvents and from the viewpoint of resource conservation, there has been a strong tendency to eliminate or minimize the use of solvents in paints, and the present invention fully meets this trend. It is something.

By the way, the technique of combining a hydroxyl group-containing resin and a polyisocyanate compound to form a urethane paint is well known.

Among these, polyester resins and acrylic resins are often used as polyol resins for urethane paints.

However, in the case of the former, it can be easily made into a high non-volatile content, and has a long life.
It has excellent chemical resistance, workability, and "shrinking" of the paint film, but it has poor drying properties, which is especially noticeable when using aliphatic polyisocyanate to make urethane paint.
When used in an air-dry condition, problems such as dirt and dust adhering during drying are likely to occur.

On the other hand, in the latter case, although drying properties are good, it is difficult to achieve high nonvolatility, and there are drawbacks such as stickiness, gloss, pot life, and abrasion resistance.

Also known is the technique of graft copolymerizing a vinyl monomer to an unsaturated oil-free alkyd or a drying oil-fatty acid-modified alkyd that has a polymerizable unsaturated bond in the main chain of the molecule, but when reacting with a high nonvolatile content, It is difficult to reduce the viscosity, and gelation tends to occur if you try to force it to have a high non-volatility.

By the way, in these conventional methods, carboxylic acids with relatively strong polymerization activity such as (anhydrous) maleic acid, fumaric acid, itaconic acid, and drying oil fatty acids are added to the molecular structure of the oil-free alkyd or oil-modified alkyd. A polymerizable double bond is introduced into the main chain or side chain by simultaneously reacting with other raw materials, and then a vinyl monomer is grafted in the presence of a radical polymerization initiator.

Among these methods, when drying oil fatty acid residues are not used,
Styrene must be an essential component from the viewpoint of copolymerizability.

Products obtained from these materials are often heavily colored, suffer from severe discoloration due to heat and ultraviolet rays, have poor weather resistance, and require relatively large amounts of styrene to prevent turbidity. Must be.

Furthermore, when grafting a vinyl monomer to a drying oil fatty acid residue, it is possible to graft the vinyl monomer without using styrene as an essential component, but the same drawbacks still exist in that case.

As a result of various studies, the present inventors added an acid anhydride having a double bond with relatively low polymerization activity to the hydroxyl group contained in a saturated oil-free alkyd or a non-drying oil-fatty acid modified alkyd, and the It has been discovered that the above-mentioned drawbacks can be improved by using a modified resin in which a vinyl monomer is grafted to the bond, leading to the present invention.

That is, in the present invention, (4) 10 to 90 parts by weight of a saturated oil-free alkyd or a non-drying oil-fatty acid modified alkyd having a hydroxyl value of 40 to 400 (shown below), (B) tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride. Acid, Endocys-5-norbornene-2,3 dicarboxylic acid anhydride, Endocys-5-methylnorbornene-2,3
- A zero-hydroxyl group-containing vinyl-based 7-mer mixture consisting of a monomer and another vinyl monomer 10-90
The present invention relates to a coating composition comprising a polyisocyanate compound blended into a hydroxyl group-containing modified resin obtained by addition polymerizing 100 parts of components (A, B, and C).

In this way, the present invention utilizes a saturated oil-free alkyd or a non-drying oil-fatty acid modified alkyd, which does not contain any drying oil-fatty acid residues and can be grafted without using styrene as an essential component. It is.

Therefore, the above-mentioned drawbacks of the conventional method are either non-existent or negligible.

Moreover, when styrene is not an essential component, the gloss is usually poor and the compatibility with other resins is also poor, but according to the present invention, even without the use of styrene, the conventional method has improved gloss, compatibility, etc. However, by using styrene in a specific range as described later, even better effects can be obtained.

The composition of the present invention can be used for coatings where two-component urethane paints or block polyisocyanate-based urethane paints have been used up until now, such as for metals, wood, plywood, and plastics. dryness, meatiness, hardness,
It has excellent pot life, color retention, pigment dispersibility, weather resistance, abrasion resistance, physical properties, and "shimmer" of the coating film.

In addition, this composition can have a high nonvolatile content, so it has high application solids and good stickiness, just like when using conventional polyester polyols, and has much higher drying properties and hardness than when using polyester polyols. Are better.

(4) Alkyd used in the present invention can be obtained by reacting an alcohol component that does not have a polymerizable unsaturated bond with a carboxylic acid component in a conventional manner, or by reacting them with a non-drying oil fatty acid component. It is something.

Examples of alcohol components that can be used include ethylene glycol, diethylene glycol, polyethylene glycol,
Propylene glycol, dipropylene glycol, polypropylene glycol, neopentyl glycol, butylene glycol, 2,2.4-1-limethyl-1,3-bentanediol, bis(β-hydroxyethyl) terephthalate, hydrogenated bisphenol A1 glycerin, trimethylol Polyhydric alcohols such as ethane, trimethylolpropane, and pentaerythritol; adducts made by adding ethylene oxide, propylene oxide, etc. to phenol compounds, amine compounds, etc. in addition to these polyhydric alcohols; trishydroxymethylaminomethane; Cardura E ( Monoglycidyl compounds such as Shell Chemical ■ product); Epiclon 1050.4050 (Inu Nippon Ink Chemical ■ product), Epicort 190,815,871゜1001.1
There are epoxy resins such as 004 (product of Shell Kagaku ■).

Examples of carboxylic acid components include (anhydrous) phthalic acid, hexahydrophthalic anhydride, (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, isophthalic acid, terephthalic acid, adipic acid, and methyltuthalic acid (a product of Yojin ■). ), octylic acid, pt-butylbenzoic acid, benzoic acid, cot-9 acid, cepatic acid, domecandicarphonic acid, etc. Examples of non-drying oil fatty acid components are agonism, coconut oil fatty acid, and castor oil. These include fatty acids, olive oil, coconut oil, castor oil, and hydrogenated coconut oil.

Regarding oil length when oil is modified using non-drying oil fatty acid components, there is a marked tendency for the resulting modified resin to become soft when 60% is rubbed, resulting in a decrease in hardness, drying properties, stain resistance, etc. On the other hand, if it is less than 3%, the effect of introducing a fatty acid structure into the modified resin is difficult to produce.

Therefore, the preferred oil length range is 3 to 60%, especially 5 to 60%.
It is 50%.

Saturated oil-free alkyds are applicable to applications where it is disadvantageous to use non-drying oil fatty acids or fats as raw materials.

The use of these alkyds improves the solubility of the modified resin and facilitates differentiation with high non-volatility.

An addition reaction occurs between the hydroxyl groups contained in these alkyds and the polymerizable unsaturated polycarboxylic anhydride, and the amount of hydroxyl groups is as follows.

If the hydroxyl value is less than 40, the content of hydroxyl groups in the alkyd is low and there are few grafting points, so the modified resin may become cloudy or not have balanced physical properties.On the other hand, if it exceeds 400, the content of hydroxyl groups in the alkyd is low. If the amount is too large, the hydroxyl group content of the final modified resin will increase, requiring a large amount of curing agent, and there will also be problems in terms of the balance of physical properties.

Therefore, considering the desired physical properties and economic efficiency, the
, preferably in the range of 50 to 300.

If the amount used in (4) to (q) is less than 10% by weight (hereinafter expressed as %), the characteristics of alkyd cannot be sufficiently imparted to the modified resin;
%, the characteristics of the acrylic resin cannot be sufficiently imparted.

Therefore, the usage range is 10 to 90%, particularly preferably 20 to 80%.

CB) Polymerizable unsaturated polycarboxylic anhydrides include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endo-cis-5-norbornene-2,3-dicarboxylic anhydride, endo-cis-5-methylnorbornene-2 ，
3-dicarboxylic acid anhydride and methylcyclohexene tricarboxylic anhydride.These have relatively slowly polymerizable double bonds, and in the grafting reaction, the double bond that becomes the grafting point is added to the alkyd. It is something.

During the reaction between these acid components and the alkyd, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether may be added in an amount of about 10 to 1QQppm, but polymerization will not occur even if it is not added.

Furthermore, an example of an acid anhydride having similar polymerizability is maleic anhydride, and although it is a matter of course that this invention can also use this anhydride, this It has stronger polymerizability than polycarboxylic anhydride [F]), and this phenomenon is particularly remarkable when combined with styrene.

Moreover, styrene is an essential component to improve graph efficiency, and when used in large quantities, it tends to thicken or gel.However, in the present invention, the above acid anhydrides are not used, so styrene is an essential component. Needless to say, there are no drawbacks.

If the amount of unsaturated polycarboxylic anhydride (4) to (0) is less than 0.5% of the total component, there will be few graft points, and the resulting modified resin will tend to be cloudy;
If it exceeds 100%, the number of grafting points will increase and it will be easier to obtain a transparent product, but the acid value will increase and there is a possibility of gelation.

Therefore, the amount used is suitably in the range of 0.5 to 20%, particularly preferably in the range of 1 to 10%.

By the way, as mentioned above, if a large amount of unsaturated polycarboxylic acid anhydride is used, a large number of carboxyl groups will be generated, and the acid value will become high, so when used in a two-component urethane paint, the pot life may be shortened or the physical properties may be affected. more likely to have negative effects.

Therefore, in order to avoid such troubles, it is better to convert the high acid value into a lower desired acid value by esterifying with a monoepoxy compound.

The esterification may be carried out separately or simultaneously with the graft reaction of the vinyl monomer, but it is preferable to carry it out at the same time considering the rationality of the process.

Monoepoxy compounds that can be used for this purpose include alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, α-olefin oxides, styrene oxides; neopentanoic acid, neoheptanoic acid, neodecanoic acid, and neoheptanoic acid. C4 to C2 glycidyl esters such as Iic acid (product of Engai), Cardura E (product of Shell Chemical ■), etc.
Glycidyl esters of aliphatic tertiary carboxylic acids of No. 2 are suitable.

When carrying out this esterification reaction, in order to promote esterification, boron trifluoride complex compounds such as boron trifluoride etherate, amines such as triethylamine and 2-methylimitazole, and quaternary compounds such as benzyltrimethylammonium hydroxide are used. Known esterification catalysts such as bases can also be used.

(An example of a vinyl monomer having a hydroxyl group that is a component of the q monomer mixture is β-hydroxylethyl (
Mech) acrylate, β-hydroxypropyl (meth)
Acrylate, 4-hydroxybutyl (meth)acrylate, N-methylolated (meth)acrylamide, Mettsuk E1 Mettsuk P (Nissin Chemical ■ product: Hydroxyallyl methacrylate), Chloro-hydroxypropyl (
Meth) acrylate; hydroxyl group-containing polymerizable products obtained by adding a saturated dicarboxylic anhydride to such a hydroxyl group-containing vinyl monomer, and then adding a monoepoxy compound or monoglycidyl compound such as ethylene oxide or Cardura E. can be mentioned.

Examples of other vinyl monomers that are copolymerizable with the vinyl monomer having a hydroxyl group include aromatic vinyl compounds such as styrene and vinyltoluene; dialkyl esters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; C1 to C18 monovalent alkanols such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pendel (meth)acrylate, and cyclohexyl (meth)acrylate. and (meth)acrylic acid; alkoxyalkyl (meth)acrylate, (methyl)glycidyl (meth)acrylate, (meth)acrylamidodialkylaminoalkyl (meth)acrylate; (meth)acrylic acid or maleic acid, fumar Examples include monoalkyl esters of acids, itaconic acid, and monohydric alcohols; and vinyl monomers having carboxyl groups, such as equimolar adducts of hydroxyl group-containing vinyl monomers and saturated dicarboxylic anhydrides.

In a vinyl monomer mixture containing a vinyl monomer having a hydroxyl group and another vinyl monomer copolymerizable with it, either the vinyl monomer having a hydroxyl group or the other vinyl monomer copolymerizable with it. Although they can be used alone, in the present invention, it is preferable to use two types of vinyl monomers together from the viewpoint of economical efficiency as a coating material and coating film performance.

In other words, when a large amount of vinyl monomers having hydroxyl groups are used, hydroxyl groups are also introduced from saturated oil-free alkyds or non-drying oil-fatty acid-modified alkyds, so the amount of hydroxyl groups in the modified resin increases, and the crosslinking component polyisocyanates Since a large amount has to be used, the coating film becomes brittle, and the cost of the paint becomes high, the amount of vinyl polymer having hydroxyl groups used should be at most 99%, preferably in the range of 1 to 60%. Therefore, the amount of other vinyl monomers used is at least 1%, preferably 4%.
A range of 0 to 99% is suitable.

However, when vinyl monomers with carboxyl groups and dialkylaminoalkyl (meth)acrylates are used in large amounts, they shorten the pot life in systems using polyisocyanates with free incyanate groups, so these monomers with other vinyl monomers At most 5% of
In particular, it is preferable to keep it to 2% or less.

Furthermore, aromatic vinyl monomers such as styrene and vinyltoluene do not necessarily need to be used in the present invention, and if used in large amounts, they will cause discoloration, weather resistance, solvent resistance, etc., but if used in small amounts There are no such defects, but even if there are, they are negligible.

Such a range is about 0.1 to 20%, particularly about 0.1 to 15%, and when an aromatic vinyl monomer is used as desired, it is preferably used within this range.

If the amount of these vinyl monomer mixtures (Q) is less than 10% of the total amount used, the characteristics of acrylic resins cannot be sufficiently imparted to the modified resin, and if the amount exceeds 90%, it will not be possible to provide saturated oil-free alkyds or unsaturated oil-free alkyds. The characteristics of the drying oil fatty acid modified alkyd cannot be sufficiently imparted to the modified resin, and it becomes difficult to make the modified resin highly non-volatile.

Therefore, the usage range is 10-90%, preferably 20-80%.
%.

The modified resin used in the present invention contains a hydroxyl group that reacts with a polyisocyanate compound.

Its number average molecular weight is 1,500 to 25,000. Preferably, when the molecular weight is in the range of about 2,000 to 20,000, high non-volatile differentiation can be easily achieved, and there is no or only a slight decrease in physical properties due to a decrease in molecular weight, resulting in good results. It will be done.

Polymerization solvents for obtaining modified resins include aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons such as toluene, xylene, and ethylcyclohexane; methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexanone; Acetate esters such as ethyl acetate, butyl acetate, and cellosolve acetate; When using block polyisocyanate, alcohols such as propyl alcohol, butanol, and isobutanol; Methyl cellosolve, ethyl cellosolve, butyl cellosolve Cellosolves such as can be used as appropriate.

If necessary, a mixed solvent of these can also be used.

Azobisisobutyronitrile, 2.2'-azobis-2-methylcapronitrile, 2 as a radical polymerization initiator
．． 2'-azobis-2-methylvaleronitrile, 2,2
Azo compounds such as '-azobis-2,4-dimethylvaleronitrile, benzoyl peroxide, t-butyl perbenzoate, t-butyl hydroperoxide, di-t-butyl peroxide, cumene hydroperoxide, t-butyl peroxide Peroxides such as octoate and lauroyl peroxide are suitable.

In addition, if necessary, well-known chain transfer agents such as mercaptans such as mercaptoethanol, lauryl mercaptan, and thioglycolic acid ester, dipentene, cyclopentadiene, pinene, α-methylstyrene, and allyl carbamate may be added to the solid content of the resin. When used in the range of .1 to 10%, preferably 0.3 to 7%, the molecular weight of the modified resin can be further lowered and better results can be obtained due to high non-volatile differentiation.

To produce a modified resin, first add an unsaturated polycarboxylic acid anhydride to a saturated oil-free alkyd or a non-drying oil-fatty acid modified alkyd at 80 to 120°C to create a graft point, and then add a portion of the vinyl monomer mixture. 8 parts in the presence of a radical polymerization initiator with or without charging
This is possible by graft polymerization at 0 to 200°C, preferably 90 to 150°C.

The basic technology of the present invention can also be applied to resins with non-volatile content ranging from 30 to 60%, such as those currently commonly used.

However, one of the features of the present invention is high non-volatile content, and if such conditions are taken into consideration, the non-volatile content can be freely selected within the range of 60 to 100%, but the performance when making it into a paint, In view of the balance between conditions and painting workability, it is particularly preferable to select the amount in the range of 65 to 90% depending on the desired coating conditions.

In the present invention, examples of polyisocyanate compounds that can be used include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate,
Diisocyanates such as hexamethylene diisocyanate, tetramethylene diisocyanate, isopropylidene dicyclohexyl diisocyanate, lysine diisocyanate, inphorone diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, dimer acid diisocyanate; copolymers of these, or Adducts of diisocyanates with polyhydric alcohols such as glycerin, trimethylolmethane, and trimethylolpropane, such as Burnock D-750 (a product of Inu Nippon Ink Kagaku ■), Desmodur (a product of Bayer AG), Burnock DN-
950 (a product of Inu Nippon Ink Kagaku ■), Desmodur IL (a product of Bayer AG), which is a trimer of tolylene diisocyanate, Desmodur N (a product of Bayer AG), a biuret form of hexamethylene diisocyanate, and hexamethylene diisocyanate. Desmodur HLj (product of Bayer), which is an adduct of 2 moles of tolylene diisocyanate and 3 moles of tolylene diisocyanate, or Coronate, which is a homopolymer of each diisocyanate such as tolylene diisocyanate, hexamethylene diisocyanate or isophorone diisocyanate. 2030j
Alternatively, there are "Coronate EH, J" (products of Nippon Polyurethane Industries) and "T-1890J" (products of Femu Hemy Co., Ltd.).

In addition, so-called moisture-curing urethane resins having free incyanate groups, such as Burnock 6-443 (product of Inu Nippon Ink Kagaku ■), can also be used.

Blocked polyisocyanates having blocked isocyanate groups obtained by reacting these polyisocyanates with a suitable isocyanate group blocking agent by a conventional method can also be used.

Suitable isocyanate group blocking agents include alcohols such as methanol and ethanol; phenolic compounds such as phenol and cresol; acetoacetic esters, lactic esters, malonic esters, mercaptans, oxime compounds, carbamate compounds, and imide compounds. ,
Acid amide compounds, amine compounds, urea compounds, δ
-There are lactams such as caprolactam.

When these block polyisocyanates are used, known block dissociation catalysts such as organotin compounds, organozinc compounds, and organic amine compounds can be used in conventional amounts.

Regarding the blending ratio of these polyisocyanate compounds and modified resins, considering the coating film performance and economical efficiency as a paint, OH/NC0 = 110.5 to 1.5, especially 170.8 to 1.5.
It is preferably in the range of 1.2.

The composition obtained by the present invention can also be used as a clear paint.
It can also be used as an enamel paint using well-known pigments used in urethane paints, and can also be used in combination with well-known additives for urethane paints and other resins for urethane paints.

Paints can be applied using normal painting methods such as brushing, roller painting, and spray painting, and the painted ones can be dried at room temperature, forced drying, or baked dry depending on whether the isocyanate groups in the polyisocyanate compound used are blocked or not. Curing can be carried out as appropriate by a desired method from among well-known curing methods such as , far infrared drying and the like.

The present invention will be explained below with reference to Examples.

The present invention is not limited thereby.

Synthesis of saturated oil-free alkyd 100 parts of p-couchary-butylbenzoic acid, 501 parts of phthalic anhydride, 66 parts of 2,2.4-)limethyl-1,3-bentanediol, 254 parts of trimethylolfuropane,
150 parts of neopentyl glycol and a very small amount of antifoaming agent were charged into a reactor equipped with a stirring device, an inert gas inlet, and a thermometer, and the temperature was raised to 160°C.

Then, the temperature was raised to 220°C over 5 hours, and the reaction was continued at 220°C until the acid value of the 60% butyl acetate solution reached approximately 4. After cooling, the butyl acetate solution was diluted with a mixed solvent of %IBK = 80/20. did.

The resulting resin solution had a nonvolatile content of 79.8% and a viscosity of z3'-
z4, color number 1-2, oxidation 5.4, and hydroxyl value 104.

Synthesis of non-drying oil fatty acid modified alkyd A with oil length 40% 373 parts of coconut oil fatty acid, 354.8 parts of phthalic anhydride, 91.2 parts of neopentyl glycol, 154.1 parts of trimethylpropane, 100 parts of pentaerythritol. A very small amount of antifoaming agent was charged into the same reactor as above, and 160
The temperature was raised to ℃.

Then, the temperature was raised from 160℃ to 220℃ over 5 hours, and the temperature was increased to 220℃ over 5 hours.
2200 until the acid value of the 0% butyl acetate solution is approximately 4.
The reaction was carried out at c and diluted with butyl acetate.

The resulting resin solution had a nonvolatile content of 80.0%, a viscosity of Z2, a color number of 1 to 2, an acid value of 5.2, and a hydroxyl value of 73.

200 parts of synthetic coconut oil of non-drying oil fatty acid modified alkyd B with an oil length of 20%, 35.8 parts of trimethylolpropane,
2.5 parts of lithium naphthenate was charged into the same reactor as above and the temperature was raised to 250°C. Contents: Ethanol = 50:
Alcohol exchange reaction was carried out until the mixture became transparent.

After cooling, 431.8 parts of phthalic anhydride, 354.9 parts of neopentyl glycol, 26.2 parts of pentaerythritol, and a very small amount of antifoaming agent were charged, and the temperature was raised to 220° C. over 5 hours.

The reaction was continued at 220° C. until the acid value of the 60% butyl acetate solution reached about 4, and then diluted with butyl acetate.

The obtained resin solution has a nonvolatile content of 80.1% and a viscosity of Z2~
Z3', color number 2, acid value 5.2, and hydroxyl value 128.

Synthesis of unsaturated oil-free alkyd 407 parts of isophthalic acid, 200 parts of adipic acid, 25 parts of maleic anhydride, 166 parts of trimethylolpropane, 344.6 parts of neopentyl glycol and a very small amount of antifoaming agent were reacted in the same manner as above. The non-volatile content is 80.4% and the viscosity is Z.
A resin solution having a color number of 3 to zX, a color number of 1 to 2, an acid value of 5.8, and a hydroxyl value of 105 was obtained.

Synthesis of drying oil fatty acid modified alkyd with oil length 40% Dehydrated castor oil fatty acid 382.2 parts, maleic anhydride 5 parts, phthalic anhydride 349.2 parts, neopentyl glycol 133.
The non-volatile content was 79.7% in the same manner as in the synthesis of alkyd A, except that 8 parts of trimethylolpropane, 97.7 parts of pentaeryth IJ l--1, and a very small amount of antifoaming agent were used.
A resin solution having a viscosity of Z3, a color number of 6, an acid value of 5.5, and a hydroxyl value of 74 was obtained.

Production Example 1 The above-mentioned saturated oil-free
375 parts of Rekido solution and 40 parts of endo-cis-5-norbornene-2,3-dicarboxylic anhydride were charged, and 115 parts of
The temperature was raised to .degree. C. and held for 30 minutes to carry out an addition reaction.

Next, the temperature was cooled to 80°C, 87.7 parts of Cardura E was charged, and the temperature was raised to 125°C.
After dropping a mixture of 5 parts of methacrylic acid, 353 parts of butyl acetate, 25 parts of abisisobutyronitrile, 20 parts of di-t-butyl peroxide, and 5 parts of lauryl merbutane, the mixture was heated at 125°C. After holding for 7 hours, non-volatile content 70.6%, acid value 6.9, viscosity Z1-z2', color number 1
2-2, hydroxyl value 56 (7) modified resin solution (2) was obtained.

Production Example 2 Non-drying oil fatty acid modified alkyd A was placed in the same reactor as Production Example 1.
625 parts of the solution and 60 parts of tetrahydrophthalic anhydride were charged, the temperature was raised to 120°C, and the temperature was maintained for 30 minutes to carry out an addition reaction.

Next, it was cooled to 80°C, charged with 98.7 parts of Cardura E, and heated to 125°C, 50 parts of ethyl acrylate, 167.1 parts of methyl methacrylate, 50 parts of t-butyl methacrylate, and 26.7 parts of β-hydroxyethyl acrylate.
parts, 46.5 parts of β-hydroxyethyl methacrylate,
1 part of methacrylic acid, 303 parts of butyl vinegar, 30 parts of azobisisobutyronitrile, 2 parts of di-t-butyl peroxide
After dropping a mixture consisting of 0 parts of t-butyl peroctoate and 15 parts of t-butyl peroctoate little by little, the mixture was kept at 125°C for 8 hours, and when the nonvolatile content reached 69% or more, part of the butyl acetate was distilled off under reduced pressure. At least, non-volatile content 79.7%, viscosity z3 ~
A modified resin solution (2) having a Z color number of 22 to 3, an acid value of 8.5, and a hydroxyl value of 80 was obtained.

Production Example 3 Into the same reactor as above, 500 parts of non-drying oil-fatty acid modified alkyd B solution, methylcyclohexene, and 50 parts of tricarboxylic anhydride were charged, heated to 120° C., and held for 30 minutes to carry out an addition reaction.

Next, it was cooled to 800C, 398,119 parts of carf and 0.2 parts of boron trifluoride etherate were charged, and the temperature was raised to 120C, 80 parts of styrene, and 158.6 parts of methyl methacrylate.
parts, isobutyl acrylate 108 parts, β-hydroxyethyl methacrylate 83.4 parts, acrylic acid 1 part, butyl acetate 142 parts, MIBK 86 parts, azobisisobutyronitrile 25 parts, di-1-butyl peroxide 20 parts, t- After dropping a mixture of 15 parts of butyl peroctoate and 5 parts of lauryl mercapkun little by little, 120
'C for 8 hours, non-volatile content 70.5%, viscosity Y1
A modified resin solution (1) having 1 part of 7.2, color number of 2, and hydroxyl value of 77 was obtained.

Production Example 4 In the same reactor as above, 312 parts of non-drying oil fatty acid modified alkyd B solution and endo-cis-5-methylnorbornene-2 were added.
, 20 parts of 3-dicarboxylic anhydride were charged, and the temperature was raised to 120°C to carry out an addition reaction.

Next, cool to 80°C and methyl methacrylate 409.1
parts, inbutyl methacrylate 240 parts, 2-ethylhexyl acrylate 33.6 parts, β-hydroxyethyl methacrylate 46.3 parts, monobutyl itaconate 1
Of the 750 parts of the vinyl monomer mixture, 2
50 parts of BPO and 4 parts of BPO were heated to 125°C, and the remaining 500 parts of the vinyl monomer mixture and 366 parts of butyl acetate were added.
parts, azobisisobutyronitrile 25 parts, di-t-butyl peroxide 20 parts, t-butyl peroctoate-1-
A mixture consisting of 10 parts of t-dodecyl mercaptan, 5 parts of t-dodecyl mercaptan, and 5 parts of octyl thioglycolate was added dropwise little by little and held at 125°C for 8 hours to give a nonvolatile content of 70.1%, a viscosity of 11 parts, and a color of 12.9. A modified resin solution (2) having a number of 1 and a hydroxyl value of 55 was obtained.

Production Example 5 Unsaturated oil-free alkyd solution 3 was placed in the same reactor as above.
75 parts of styrene, 200 parts of butyl acetate, heated to 125°C, and 200 parts of styrene, 50 parts of butyl acrylate,
2232 parts of methyl methacrylate, 195 parts of inbutyl methacrylate, 71.8 parts of β-hydroxyethyl methacrylate, 5 parts of methacrylic acid, 153 parts of butyl acetate,
A mixture of 25 parts of azobisisobutylonitrile, 20 parts of di-t-butyl peroxide, and 5 parts of lauryl mercaptan was added little by little, but after the addition, the viscosity gradually increased, and finally it turned into a tailing state. became.

Production Example 6 In the same reactor as above, add drying oil fatty acid modified alkyd solution 62
5 parts of ethyl acrylate, 225.8 parts of methyl methacrylate, 50 parts of t-butyl methacrylate, 100 parts of styrene, 26.7 parts of β-hydroxyethyl acrylate, and β-hydroxyethyl. 46.5 parts of methacrylate, 1 part of methacrylic acid, 303 parts of acetic acid, 30 parts of azobisisobutyronitrile,
A mixture consisting of 20 parts of t-butyl peroxide and 5 parts of t-butyl peroctoate was added dropwise little by little, and after the addition was completed, the mixture gradually thickened and gelled.

Production Example 7 In Production Example 5, which was carried out in the same manner as Comparative Example 1 except that methyl methacrylate was used as 423.2 parts and styrene was used as 0 parts, both the solution and the coating film were cloudy. Similar to Comparative Example 1, it showed a tendency to increase in viscosity.

Production Example 8 In Production Example 6, 325°8 parts of methyl meccrylate,
A sample prepared in the same manner as in Comparative Example 2 except that styrene was used at 0 parts increased in viscosity and finally gelled.

Examples 1 to 7 To the modified resin solutions 1 to 1 obtained in Production Examples 1 to 4 above, the first
As shown in the table, polyisocyanate compounds 1 to
H7/NGO=1. Each white enamel was mixed at a ratio of O/1.0 and further mixed with Tybake R-820 (Rutile type titanium oxide manufactured by Ishihara Sangyo ■) to give a PWC of 40%. 25
°C) and bond them with #144 dull type
The spray was applied to a steel plate of 180'0.
Other than 20 minutes, baking was performed at 80° CIO minutes.

Polyisocyanate compound I; Desmodur N-75 ■; Burnock D-750 ■; Burnock DN-950 ■; Desmodur N-75 blocked with methyl ethyl ketoxime, dibutyltin diacetate as a dissociation catalyst per 100 parts of resin. Used at a rate of 1.5 parts.

Comparative Examples 1 and 2 As shown in Table 1, the same procedures as in Examples were carried out except that commercially available polyester resins and acrylic resins for urethane paints were used.

Test method (1) Drying property: Determine drying property at 25°C, 75% RH, (2) Impact resistance: 500g, support (3) Chemical resistance: Judgment after 24 hours immersion, (4) Resistance Cracking property: 80'C2 hours/-20'C
Determine the presence or absence of cracks by a cold heat test with one cycle of 2 hours. (5) Gasoline resistance: Determined after 3 hours of immersion. (6) Contamination resistance: Determined after 24 hours. (7) (8) ) (9) Blocking resistance; 5 pieces of gauze, load 100, y1so
After baking for ℃XIO minutes, pot life: the time from mixing the curing agent until it gels. However, systems using polyisocyanate compounds do not gel at room temperature. Pigment dispersibility: Neo Spectra Mark (Columbia Carbon) Judgment using PWCl 0 (manufactured carbon black),

Claims (1)

[Claims] 1 (A) 10 to 90 parts by weight of a saturated oil-free alkyd or non-drying oil-fatty acid modified alkyd with a hydroxyl value of 40 to 400, (B) tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endocis-5-norbornene-2
, 3-dicarboxylic anhydride, endocis-5-methylnorbornene-2,3-dicarboxylic anhydride, and methylcyclohexene tricarboxylic anhydride.
．． C) 10 to 90 parts by weight of a monomer mixture consisting of a hydroxyl group-containing vinyl monomer and another vinyl monomer ((A), CB
) and (total of 0 components is 100 parts by weight) A coating resin composition comprising a hydroxyl group-containing modified resin obtained by addition polymerizing a polyisocyanate compound.