JPH0441462A - Polymerizable compound and resin composition produced therefrom - Google Patents

Abstract

NEW MATERIAL:Polymerizable compounds of formula I [R1 is H or methyl; A is formula II, III or IV; X is 2-4C alkylene, formula V, VI, etc.; R2 is H or 1-10C alkyl; R3 is -R6-(OR7)m-, etc.; R4 is 1-4C lower alkyl; R5 is -R6-(OR7)m-, etc.; R6 is 1-4C alkylene; R7 is 2-4C alkylene, etc.; m is 0, 1-4; n is 1-50]. USE:Amorphous, low viscosity, excellent in crosslinking properties and useful as a component of a curable resin composition capable of a high solid formation and capable of producing a cured material (e.g. high elastic film or rubber material) excellent in hydrolysis resistance, alkalline resistance, weather resistance, etc. PREPARATION:A ring-opening addition (polymerization) of beta-methyl-delta- valerolactone to a compound of formula VII having a polymerizable double bond and a hydroxyl group is carried out and the terminal hydroxyl group of the resultant addition (polymer) is acetoacetylated, thus giving the objective compound of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polymerizable compound and a resin composition obtained therefrom.

[Prior Art] Acrylic resin compositions are commonly used as curable resin compositions for paints and the like, but in recent years high solid compositions have been desired from the viewpoint of environmental pollution. For this purpose, the acrylic resin needs to have low viscosity.

However, in conventional acrylic resins, when the viscosity is lowered, the crosslinking reactivity during curing also decreases, making it impossible to obtain a cured film with sufficient hardness.

Therefore, U.S. Patent No. 4,504,635, JP-A-57-1
No. 85236 and No. 61-43623 disclose that a copolymer of a polymerizable macromonomer obtained by addition-polymerizing ε-caprolactone to a hydroxyl group-containing acrylic monomer and a general-purpose acrylic monomer is used as a curable acrylic resin. Something is proposed. This is an attempt to impart low viscosity by making the acrylic resin a flexible structure, and to impart high crosslinkability by providing the acrylic resin with multiple types of crosslinkable groups.

However, the above polymerizable macromonomer becomes solid at room temperature when the degree of polymerization of ε-caprolactone reaches 4 to 5 or more, and its copolymer acrylic resin also exhibits a similar tendency depending on the content of the polymerizable macromonomer.

Therefore, this acrylic resin is subject to limitations in terms of handling, is insufficient in terms of low viscosity, and has the problem that its cured product also has poor hydrolysis resistance, alkali resistance, weather resistance, etc.

Also, Japanese Patent Publication No. 55-40711, Japanese Patent Publication No. 60-502
23, Japanese Patent Publication No. 60-50224, etc., disclose a method for converting the hydroxyl group of a vinyl polymer into an acetoacetyl group, and a method for acetoacetylating a general-purpose hydroxyl group-containing acrylic monomer such as 2-ethylhexyl methacrylate. has been done. Furthermore, acetoacetoxyethyl methacrylate, which is obtained by acetoacetylating 2-ethylhexyl methacrylate, is commercially available from Eastman Kodak Company under the trade name AAEM.

However, even if such a method allows the use of curing methods and curing agents other than the melamine resins and polyisocyanate compounds commonly used for paints, it is insufficient in terms of reducing the viscosity of the resin, that is, making it highly solid. However, it is also insufficient in terms of flexibility.

Furthermore, Japanese Patent Publication No. 60-50223 discloses polyethylene glycol monomethacrylate and polypropylene glycol monomethacrylate having a degree of polymerization of 5 to 6 as acetoacetylatable monomers having a hydroxyl group and a polymerizable unsaturated bond. There is.

However, it remains to be seen whether the use of such compounds will be effective in reducing the viscosity and flexibility of the resin, and the polyethylene glycol and polypropylene glycol structures are susceptible to deterioration by light, and the weather resistance of the cured product will be affected. It had the disadvantage of being significantly inferior.

Furthermore, JP-A-1-151537 discloses a method using 2-hydroquine ethyl methacrylate as a starting compound, which has a polymerization-reactive double bond and a cross-linking-reactive hydroxyl group in one molecule.
Ring-opened polymers of β-methyl-δ-valerolactone are disclosed. The disclosed polymer can be copolymerized with other α,β-ethylenically unsaturated monomers and used as a curable acrylic resin with a curing agent having a functional group that reacts with a hydroxyl group.

However, the terminal hydroxyl group of this ring-opened polymer is derived from β-methyl-δ-valerolactone, and the
It is known that it depolymerizes violently at temperatures above ℃. Therefore, with other α,β-ethylenically unsaturated monomers at 100 °C
If copolymerization is carried out at a temperature above 100°C, depolymerization will occur, and the molecular weight of the ring-opened polymer will decrease, and the original properties of the ring-opened polymer will be lost. However, the disadvantage of this method is that the molecular weight of the acrylic resin increases, making it difficult to obtain a low-viscosity resin.

In addition, even if the resin obtained in this way is crosslinked with a curing agent to form a film, the temperature must be kept at 100°C.
Only hardening agents that react with the following can be used.
It had the disadvantage that its range of use was extremely limited.

In view of the above circumstances, the present inventors have proposed
No. 0968 discloses that a copolymer of a polymerizable macromonomer obtained by ring-opening addition polymerization of β-methyl-δ-valerolactone to a compound containing a polymerizable double bond and a hydroxyl group and another polymerizable monomer is used as a curable resin. I suggested that it be used as a. The curable resin disclosed herein has a methyl group at the β-position of the ester, making it difficult to form a crystalline structure and therefore being amorphous, and exhibits low viscosity due to its flexible structure. Furthermore, since it has a hydroxyl group located at the end of a long graft chain, it exhibits high crosslinking properties. Furthermore, since the methyl group at the β-position protects the ester bond with steric hindrance, the cured product has many advantages such as excellent hydrolysis resistance, alkali resistance, weather resistance, and water resistance. The same publication also disclosed a method for preventing depolymerization of polymerizable macromonomers.

[Problems to be Solved by the Invention] The present invention further develops the invention disclosed in JP-A No. 63-280968, and provides a polymerizable compound with further improved depolymerization prevention properties, and an amorphous low-activity compound obtained therefrom. It is possible to produce a resin composition with further improved cross-linking properties, and a cured product (e.g., a highly elastic film or rubber-like material) with further improved hydrolysis resistance, alkali resistance, weather resistance, etc. An object of the present invention is to provide a curable resin composition.

[Means for Solving the Problems] In order to achieve the above object, β-methyl-δ-valerolactone is ring-opened and added (polymerized) to a monomer containing a polymerizable double bond and a hydroxyl group, and the resulting addition ( The inventors have discovered that excellent results can be achieved by using a resin composition obtained by polymerizing a compound in which the terminal hydroxyl group of the polymer is further acetoacetylated. A group represented by the formula, R, CH3 / [1] 0 0 (wherein, R1 is a hydrogen atom or a methyl group; A is 111] OOR1; X is a C1-4 alkylene.

R, R, R.

R4R.

or -C12-C-CI(, -0-C-C-Cl, -
R,OR represented by R,-.

group, R3 is a hydrogen atom or a C8-lo alkyl group; R
3 is -R6-(OR7)m- or -Ra-(o-c
-Rs)m, R4 is the same or different lower alkyl group of Cl to 4; R6 is -Re
A group represented by (OR,)m or -Re (OCR-)m-.

R8 is alkylene of 01-4, R7 is alkylene of C7-4, R11 is alkylene of C7-; m is 0 or 1
An integer of ~4; n represents an integer of 1-50. ), a method for producing the same, and a resin composition obtained by polymerizing the polymerizable compound.

The polymerizable compound represented by the above general formula [I] is represented by the general formula R.

/ CH2=CA OH...[II] (in the formula, R
1 and A have the same meanings as above. ) Ring-opening addition (polymerization) of β-methyl-δ-valerolactone to a compound containing a polymerizable double bond and a hydroxyl group represented by
and then acetoacetylation of the terminal hydroxyl group of the addition (polymer) product.

The compound represented by the above formula [11] can be easily derived from (hydroquine) alkyl esters (or amides) of acrylic acid and methacrylic acid, hydroquine styrene, etc. by a conventional method, and can also be obtained manually as a commercially available product. be.

In the synthesis of the addition (polymer), 1 to 50 times the mole, preferably 1 to 3
0 times the mole of β-methyl-δ-valerolactone was added to a ring-opening addition polymerization catalyst (for example, a known catalyst used for the ring-opening polymerization of lactones, specifically, mineral acids such as sulfuric acid and phosphoric acid, p-
Organic acids such as toluenesulfonic acid, alkali metals such as lithium, sodium and potassium, metal alkoxides such as t-butquine potassium, alkyl metal compounds such as n-butyllithium, tetrabutyltin, tetraoctyltin,
Tin-based compounds such as stannous chloride, and JP-A-1-151
Ring-opening addition (polymerization) is carried out in the presence of a positive ion exchange resin (such as the positive ion exchange resin disclosed in Japanese Patent No. 537). The catalyst is usually 0.01-1 mol or β-methyl-
It can be used in an amount of 0.0001 to 20% by weight based on the weight of δ-valerolactone. Further, the reaction can be carried out in the presence or absence of an inert solvent that does not contain active hydrogen. Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, and ethers such as diethyl ether, tetrahydrofuran, and dioxane, and tetrahydrofuran is particularly preferably used. It is desirable that the solvent used be dehydrated using molecular sieves or the like. The reaction also needs to be carried out in an inert gas atmosphere such as nitrogen, helium, or argon, and is exothermic so that the stability of β-methyl-δ-valerolactone is not compromised.
It should be carried out at temperatures not exceeding 00°C. The reaction is usually continued for about 10 minutes to several hours, and is terminated by adding an aqueous mineral acid solution or water.

Thereafter, the product is separated and purified by solvent extraction using a conventional method to obtain a polymerizable adduct (polymer) as a pale yellow to colorless viscous liquid. In this case, if the amount of β-methyl δ-valerolactone exceeds 50 moles relative to the compound represented by the above formula [II], the viscosity of the resulting adduct increases and synthesis becomes relatively difficult. Furthermore, as the molecular weight of the resulting adduct (polymer) increases, the acetoacetyl value after acetoacetylation also decreases, making it undesirable to obtain sufficient crosslinking properties as a raw material for paints. i.e. β-methyl-δ-
The polymerization degree of valerolactone is preferably 1 to 50.

Therefore, for paint applications, the amount of β-methyl-δ-valerolactone is preferably limited to 1 to 50 times the mole, preferably 1 to 30 times the mole.

Next, the terminal hydroxyl group of the addition (polymer) obtained above is acetoacetylated to obtain a polymerizable compound represented by the above formula [1] of the present invention. The method of acetoacetylation may be a conventional method and is not particularly limited, but examples thereof include a method of adding diketene, a method of adding acetoacetate, and the like.

The reaction in the case of adding diketene is carried out, for example, by adding diketene to the addition (polymer) and heating and stirring. Note that dimethylaminopyridine, pyrinone, triethylamine, etc. may be used as a catalyst. Moreover, a solvent can also be used in the above reaction. Such solvents include, for example, hydrocarbons, esters, ethers,
Although inert solvents such as ketones and halogen-containing solvents can be used, it is desirable to avoid solvents containing active hydrogen, such as alcohol and water. Preferably, the reaction conditions are, for example, 30 to 100°C for 0.5 to 5 hours. Although it is also possible to carry out the process under atmospheric conditions, it is preferable to carry out the process under dry conditions. The amount of diketene used may be essentially stoichiometric. Thereafter, the polymerizable compound of the present invention is obtained by post-treatment by a conventional method.

The reaction in the case of adding the acetoacetate is similarly carried out, for example, by adding the acetoacetate to the addition (polymer) and heating and stirring.

Examples of acetoacetic acid esters include methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, and monobutyl acetoacetate.
Butyl is preferably used.

Regarding the solvent, it is the same as in the case of the diketene described above. Further, the reaction conditions can be, for example, 50 to 100°C for 1 to 8 hours. The stoichiometry of the acetoacetate used is also the same as in the case of diketene. Thereafter, the polymerizable compound of the present invention is obtained by post-treatment by a conventional method.

The resin composition of the present invention is prepared by homopolymerization or copolymerization with other copolymerizable monomers of the polymerizable compound obtained above and represented by formula [17].

Various polymerization methods can be used, such as bulk polymerization, solution polymerization, and emulsion polymerization, but solution polymerization is usually conveniently used.

General-purpose initiators can be used as the radical polymerization initiator, but azo initiators such as azobisisobutyronitrile, peroxide initiators such as t-butyl-peroxy-2-ethylhexanoate, etc. is conveniently used.

In the case of copolymerization, examples of the copolymerizable motumer include α,β-ethylenically unsaturated monomers. Specifically, methyl (meth)acrylate,
(Meth)acrylic acids such as ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. Ester monomer, styrene monomer such as styrene, α-methylstyrene, p-chlorostyrene, pt-butoxystyrene, (meth)acrylic acid, 2
Examples include hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; amide monomers such as (meth)acrylamide; and acrylonitrile. As a solvent, for example, xylene, Tsurpetz-100 (manufactured by Shell Oil Co., Ltd., aromatic solvent)
etc. may also be used.

In the polymerization reaction composition, the amount of the polymerization initiator is 0.5 to 100 parts by weight of the polymerizable compound represented by the above formula [I].
Parts by weight of IO are preferred. In the case of copolymerization, the composition ratio (molar ratio) of the copolymerizable monomer and the polymerizable compound represented by the above formula [I] is from 0/100 to 80/20. That is, in consideration of curability, the polymerizable compound represented by [1] above is required to be present in the resin composition in an amount of 20 mol % or more. Polymerization conditions are appropriately selected, for example, 80 to 15
Preferably 3 to 8 hours at 0°C.

The polymer in the resin composition of the present invention prepared as described above has a number average molecular weight of 10 (10 to 100.000). A resin composition in this molecular weight range is suitable for coatings.

The resin composition of the present invention can be prepared as a curable resin composition by further adding a curing agent, a curing catalyst, and the like.

The curing agent may be one commonly used, such as melamine resin, urethane curing agent, aldehyde compound, titanium,
Examples include metal compounds such as iron, aluminum, and tin.

Further, the curing catalyst is not particularly limited, and for example, the above-mentioned catalyst used in the addition (polymerization) of the compound represented by -Funazura [11] and β-methyl-δ-valerolactone can be used.

In the composition of the curable resin composition, the above resin composition 10
With respect to 0 parts by weight, the amount of the curing agent is preferably 1 to 100 parts by weight, and the amount of the curing catalyst is preferably 0.01 to IO parts by weight.

The above-mentioned composition may be prepared by a conventional method, for example, by stirring and mixing the above-mentioned ingredients using a disper or the like.

The curable resin composition of the present invention is suitable for molding and coating various articles.

For coating applications, the above components may be formulated as a clear coating composition, or they may be formulated with pigments to form a paint. Pigments may be of any conventional type, such as iron oxide, lead oxide, strontium chromate, carbon black, cold dust, titanium dioxide, talc, barium sulfate or color pigments such as cadmium yellow, cadmium red, chromium. Yellow and metallic pigments such as aluminum flakes may also be used.

In the case of coating compositions, a liquid diluent is usually present in the composition. Liquid diluents are volatile, removed after application, and require a reduction in viscosity so that the coating can be applied to the desired uniform and controllable thickness by a simple application method, ie, by spraying. Liquid diluents also aid in substrate leakage, polymer component compatibility, package stability and coalescence or film formation. Examples of suitable diluents include aromatic hydrocarbons such as toluene and xylene,
Mention may be made of ketones such as methyl ethyl ketone and methyl isobutylethyl ketone, monoether glycol acetates such as 2-ethoxyethyl acetate, or compatible mixtures thereof.

In addition to the above ingredients, various fillers, plasticizers, antioxidants,
Ultraviolet absorbers, flow control agents, surfactants, and other formulation additives may be used as desired. These materials may be optionally present, typically up to about 10% by weight, based on the non-volatile content of the composition.

When the composition of the present invention is used for coating, it may be applied by spray coating, brush coating, dip coating, roll coating, flow coating, or the like. The coating composition may be applied to essentially any substrate, such as wood, metal, glass, cloth, plastic, foam, etc., or to various brimer surfaces. The paints are particularly advantageous for plastic and metal surfaces, such as steel and aluminum. Generally, the film thickness will vary depending on the desired application. Often 0.5 to 3 mils are useful. After coating the base material, the coating film is cured.

Curing can be carried out at various temperatures including room temperature, but at temperatures ranging from 50 to 20
A cured coating film with a high degree of crosslinking is obtained at 0°C, preferably from 80 to 160°C. Curing time varies depending on curing temperature, etc., but
A suitable time is 0 to 160°C for 10 to 60 minutes.

[Effect of the invention] Since the polymerizable compound used as a raw material monomer for the resin composition of the present invention has a terminal hydroxyl group converted to an acetoacetyl group, depolymerization due to heat etc. can be prevented, and therefore restrictions on polymerization temperature etc. can be avoided. Desired resin compositions can be easily prepared without receiving.

The polymer contained in the resin composition of the present invention has a flexible structure because it is synthesized from the above-mentioned relatively long-chain polymerizable compound, and has no hydroxyl group at the end, so it has an effect of inhibiting viscosity reduction due to hydrogen bonding. prevent. As a result, the resin composition of the present invention has
Excellent low viscosity. Since the father polymer has an acetoacetate group located at the end of a long graft chain, it has high crosslinking properties, and therefore, the cured product obtained from the curable resin composition of the present invention has good chemical resistance, weather resistance, etc. Excellent in Furthermore, the polymer of the present invention has a methyl group at the β position of the ester bond in the graft chain, which protects the ester bond with steric hindrance, so that the cured product has excellent water resistance, alkali resistance, etc.

Since the curable resin composition of the present invention uses the above-mentioned resin composition excellent in low viscosity, it can be made into a high solid composition, and curing agents other than melamine resins and polyisocyanate compounds can also be used.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.

(Production of polymerization-reactive compound) (Example 1) A 100 (1+ The removed tetrahydrofuran (hereinafter referred to as ITI (PJ)) 2509 and p-hydroxyethylstyrene 509 were charged, and a 1.6M hexane solution of n-BuLi (hereinafter referred to as rn-BuLi solution) was prepared with stirring under a nitrogen gas stream. )17
xQ was added. After the exothermic reaction subsided, the mixture was cooled to 5°C, and while stirring was continued, β-methyl-δ-valerolactone (hereinafter abbreviated as rMVLJ) 1279 was added dropwise through a dropping funnel over 1 hour. The reaction continues even after the dropwise addition, and I
After confirming that the absorption based on the MVL monomer disappeared in the R spectrum, it was taken out into a 1000 iu2 eggplant flask after 1 hour, and heated for 30 to 30 minutes using a rotary evaporator.
THP was removed under reduced pressure at 40°C. Then toluene 3
00g to dissolve the residue, 1000iff9J
Transferred to liquid funnel. Another 5% saline solution 100I? was added and shaken vigorously. After standing, remove the aqueous layer, add ion exchange water 1009, shake vigorously again, and leave to stand,
The aqueous layer was removed. Thereafter, the same washing operation was repeated several times using ion-exchanged water. After removing the toluene layer and removing water with anhydrous sodium sulfate, toluene and remaining THF were completely removed using a vacuum pump at 80° C. under reduced pressure of 1 to 5 mmHg. By the darning operation, 1165 g of pale yellow transparent viscous liquid A-1 was obtained.

As measured by H-NMR1''C-NMR,
Absorption nobnal based on MVL monomer was not observed, and chemical shift confirmed that this liquid was a polymer obtained by ring-opening addition of MVL to p-hydroxyethylstyrene. The hydroxyl value was 114.4, and the average degree of polymerization of MVL determined from the hydroxyl value was 3. Further, the viscosity of this viscous liquid al was 1.6 voids.

Furthermore, this viscous liquid a-11009, turny butyl acetoacetate (hereinafter abbreviated as rt-BAAJ) 32
．． Mix 3g in a 300ml flask and heat at 90-95℃ for 5 minutes.
Allowed time to react. IR during reaction.

'H-NMRS' M
No absorption based on VL monomer was observed. The obtained reaction product was dissolved in 200 g of methylene chloride, ion-exchanged water 1009 was added, and liquid/liquid extraction was performed using a separating funnel.
After removing methylene chloride, a pale yellow transparent viscous liquid B-11
I got 149. No absorption based on hydroxyl groups was observed in IR, and 'H-NMR and C-NMR measurements revealed that this viscous liquid b-1 was a polymerized product in which the hydroxyl groups of the viscous liquid a-1 were acetoacetylated. The viscosity of this viscous liquid b-1 was 1.1 poise.

In addition, the weight loss rate of viscous liquid a-1 and viscous liquid b-1 before and after heating, which is thought to be based on depolymerization of MVL, is 1
Measurement was performed at 05°C for 3 hours.

As a result, the weight loss rate of a-1 was 8.5%, while the weight loss rate of bl was 0.3%.

(Example 2) Using the same apparatus as in Example 1, THF25 was prepared in the same manner as in Example 1.
09, Prepare p-hydroxyethylstyrene 509,
After adding n-BuLi solution 17jIQ, MVL21
2 g was added dropwise. After the reaction was completed, the product was purified in the same manner as in Example 1 to obtain a pale yellow transparent viscous liquid a-22429, which is a ring-opening addition of MVL to p-hydroxyethylstyrene.

The hydroxyl value of this viscous liquid a2 was 78.0, and the average degree of polymerization of MVL determined from the hydroxyl value was 5. Further, the viscosity of this viscous liquid a-2 was 3.6 poise.

Furthermore, in the same manner as in Example 1, viscous liquid a-21009, t
-BAA22.19 was reacted to obtain pale yellow transparent viscous liquid b-21109. As a result of measurement in the same manner as in Example 1, this viscous liquid b-2 was a polymerizable compound in which the hydroxyl group of viscous liquid a-2 was acetoacetylated, and the viscosity was 2.
．． It was 8 poise.

In addition, as a result of measuring the weight loss rate in the same manner as in Example 1, a
-2 was 8.8%, while b-2 was 0.2%.

(Example 3) THP [
After charging 50 g of p-hydroquine ethyl styrene 309 and adding n-BuLi solution 10111σ, MVL
2809 was added dropwise. After the reaction was completed, the product was purified in the same manner as in Example 1 to obtain a pale yellow transparent viscous liquid a-32849, which is a ring-opening addition of MVL to p-hydroxyethylstyrene. The hydroxyl value of this viscous liquid a3 was 398, and the average degree of polymerization of MVL determined from the hydroxyl value was 11. Further, the viscosity of this viscous liquid a-3 was 7.0 poise.

Furthermore, in the same manner as in Example 1, viscous liquid a-3100g, t
-BAAl 1.39 was reacted to obtain b-31059, a pale yellow transparent viscous liquid. As a result of measurement in the same manner as in Example 1, this viscous liquid b-3 was a polymerizable compound in which the hydroxyl group of viscous liquid a-3 was acetoacetylated, and the viscosity was 6.1 poise.

In addition, as a result of measuring the weight loss rate in the same manner as in Example I, a
-3 was 9.4%, while b-3 was 0.2%.

(Example 4) Using the same apparatus as in Example 1, THP50
9. Prepare 10 g of p-hydroquine ethyl styrene, n
-After adding 3.4i of BuLi solution (!), MVL23
0g was added dropwise. After the reaction was completed, purification was performed in the same manner as in Example 1 to obtain a pale yellow transparent viscous liquid a-42209 in which MVL was ring-opened and added to p-hydroquinoethylstyrene.

The hydroxyl value of this viscous liquid a4 was 18.1, and the average degree of polymerization of MVL determined from the hydroxyl value was 27. Further, the viscosity of this viscous liquid a-4 was 36.8 poise.

Furthermore, in the same manner as in Example 1, viscous liquid a-41009, t
- React with BAA5.29 to produce pale yellow transparent viscous liquid b
-41029 was obtained. As a result of measurement in the same manner as in Example 1, this viscous liquid b-4 was a polymerizable compound in which the hydroxyl group of viscous liquid a-4 was acetoacetylated, and the viscosity was 35.
．． It was 9 poise.

In addition, as a result of measuring the weight reduction rate in the same manner as in Example 1, s
-4 was 9.5%, while b-4 was 0.3%.

(Example 5) Using the same apparatus as in Example 1, THF 2
509, prepared with hydroxypivalic acid neopentyl glycol ester monoacrylate 509, n-BuL
i solution 10. After adding Oi+Q, 97 g of MVL was added dropwise. After the reaction was completed, it was purified in the same manner as in Example 1,
A colorless and transparent viscous liquid a-51389 was obtained by ring-opening addition of MVL to hydroxypivalic acid neopentyl glycol ester monoacrylate. The hydroxyl value of this viscous liquid a-5 was 78.5, and the average degree of polymerization of MVL determined from the hydroxyl value was 4. Further, the viscosity of this viscous liquid a-5 was 2.8 poise.

Furthermore, in the same manner as in Example 1, viscous liquid a-51009, t
-Reacted with 22.2g of BAA to produce a colorless and transparent viscous liquid b
-51109 was obtained. As a result of measurement in the same manner as in Example 1, this viscous liquid b-5 was a polymerizable compound in which the hydroxyl group of viscous liquid a-5 was acetoacetylated, and the viscosity was 2.
It was 1 voice.

In addition, as a result of measuring the weight loss rate in the same manner as in Example I, a
-5 was 8.2%, while b-5 was 0.1%.

(Example 6) Using the same apparatus as in Example 1, THF 2
509, prepared with hydroxypivalic acid neopentyl glycol ester monoacrylate 509, n-BuL
i solution 10. After adding Oi+I2, MVL 195
9 was added dropwise. After the reaction was completed, the product was purified in the same manner as in Example 1 to obtain a6 2289, a colorless and transparent viscous liquid in which MVL was ring-opened and added to hydroxypivalic acid neopentyl glycol ester monoacrylate. This viscous liquid a-
The hydroxyl value of No. 6 is 48.0, and M calculated from the hydroxyl value
The average degree of polymerization of VL was 8. Also, this viscous liquid a-
The viscosity of No. 6 was 5.7 voids.

Furthermore, in the same manner as in Example 1, viscous liquid a-61009, t
-BAAl 3.59 was reacted to obtain a colorless and transparent viscous liquid 1)-61069. As a result of measurement in the same manner as in Example 1, this viscous liquid b-6 was a polymerizable compound in which the hydroxyl group of viscous liquid a-6 was acetoacetylated, and the viscosity was 50 voids.

In addition, as a result of measuring the weight loss rate in the same manner as in Example 1, a
-6 was 9.0%, while b-6 was 0.2%.

(Example 7) Using the same apparatus as in Example 1, THF 1
509, neopentyl glycol ester monomethacrylate 309, n-BuLi solution 9, Oz
(1), MVL2199 was added dropwise. After the reaction was completed, purification was performed in the same manner as in Example 1 to obtain a colorless and transparent viscous liquid a-72509 in which MVL was ring-opened and added to neopentyl glycol ester monomethacrylate. The hydroxyl value of this viscous liquid a-7 was 42.6, and the average degree of polymerization of MVl determined from the hydroxyl value was 10.The viscosity of this viscous liquid a-7 was 6. It was 8 poise.

Furthermore, in the same manner as in Example 1, viscous liquid a-71009, t
-BAAl 2,19 was reacted to obtain a colorless and transparent viscous liquid b-7106fl. As a result of measurement in the same manner as in Example 1, this viscous liquid b-7 was a polymerizable compound in which the hydroxyl group of viscous liquid a-7 was acetoacetylated, and the viscosity was 62 poise.

In addition, as a result of measuring the weight loss rate in the same manner as in Example 1, a
-7 was 99%, while b-7 was 0.4%.

(Example 8) Using the same apparatus as in Example 1, THF 2
00g, N-(n-butyl)-N-(2-hydroxyethyl)methacrylamide 409 was charged, and n-BuLi
After adding solution 11.7xQ, 206g of MVL was added dropwise. After the reaction, purification was performed in the same manner as in Example 1, and N
A colorless and transparent viscous liquid a-82229 was obtained by ring-opening addition of MVL to -(n-butyl)-N-(2-hydroxyethyl)methacrylamide. The hydroxyl value of this viscous liquid a-8 was 57.9, and the average degree of polymerization of MVL determined from the hydroxyl value was 7. The viscosity of this viscous liquid a-8 was 55 voids.

Furthermore, in the same manner as in Example 1, viscous liquid a-81009, t
-BAAl 6.39 was reacted to obtain a colorless and transparent viscous liquid b-81079. As a result of measurement in the same manner as in Example 1, this viscous liquid b-8 was a polymerizable compound in which the hydroxyl group of viscous liquid a-8 was acetoacetylated, and the viscosity was 4.
．． It was 9 poise.

In addition, as a result of measuring the weight loss rate in the same manner as in Example 1, a
-8 was 9.5%, while b-8 was 0.3%.

(Preparation of resin composition) (Example 9) In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas introduction pipe, and a dropping funnel, 80 parts of Tsurpetz 100 (aromatic solvent manufactured by Shell Oil Co., Ltd.) and xylene were added. Prepare 10 parts,
After heating to 140 to 150°C while introducing nitrogen gas, 270 parts of polymerizable compound b produced in Example 2, 15 parts of methyl methacrylate, and 15 parts of n-butyl acrylate were added.
part, t-butylperoxy-2-ethylhexanoate 5
A mixture consisting of 1.5 and 1.5 parts was added dropwise at a uniform rate over 3 hours using a dropping funnel. After the addition was completed, the mixture was kept warm for 30 minutes, and a mixed solution of 0.5 parts of t-butylperoxy-2-ethylhexanoate and 10 parts of xylene was added dropwise at a uniform rate over 30 minutes. After completion of dripping, 140
The reaction was further carried out at ~150°C for 1 hour. The solvent was removed under reduced pressure to obtain a predetermined solid content concentration to obtain a resin solution A-1 having a solid content of 90.1% and a Gardner viscosity of Z+ at 25°C. The mole% of polymerization-reactive compound b-2 contained in the polymer of this resin solution is 25% by mole as calculated from the formulation.
．． It was 0%.

(Examples 1O to 12 and Comparative Example 1) Using the same apparatus as in Example 9 and the same method, the first
Resin solutions A-2 to A4 and B-1 were obtained with the compositions shown in the table. Table 1 shows the solid content and viscosity of each resin solution.

(Comparative Example 2) Using the same apparatus as in Example 9 and using the same method, 20 parts of methyl isobutyl ketone and 20 parts of the kiln were charged into a reaction vessel, and heated to 90 to 95°C while introducing nitrogen gas. A mixture consisting of 270 parts of polymerization-reactive compound a-pre-acetoacetylated prepared in Example 1, 15 parts of methyl methacrylate, 15 parts of n-butyl acrylate, 5 parts of azobisisobutyronitrile, and 40 parts of methylisobutyl ketone. The solution was added dropwise at a constant rate over 3 hours using a dropping funnel.

After the addition was completed, the mixture was kept warm for 30 minutes, and a mixed solution of 0.5 parts of azohisisobutyronitrile and 20 parts of methyl isobutyl ketone was added dropwise at a constant speed over 30 minutes.

After completion of the dropwise addition, the reaction was further carried out at 90 to 95°C, and the solvent was removed under reduced pressure to reach a predetermined solid content concentration, resulting in a resin solution with a solid content of 90.1% and a cartoner viscosity of Z at 25°C. B-2 was obtained. The mole% of polymerization-reactive compound a-2 contained in the polymer of this resin solution is 26 as calculated from the formulation.
．． It was 6%.

Table 1 (Paint preparation and cured film performance evaluation results) (Example + 3) 150 parts of resin solution A obtained in Example 9, Kneepan 2ON
32 parts of -60 (butylated melamine manufactured by Mitsui Toatsu Co., Ltd.) and 1.9 parts of an isopropyl alcohol solution of p-toluenesulfonic acid (hereinafter referred to as rPTsJ solution) were placed in a stainless steel container, stirred and mixed with a disper, and then mixed to form the coating liquid P. -1 was created. Xylene/Tsurpetz-1 was added to the obtained coating liquid P-1.
A mixed solvent (hereinafter referred to as dilution thinner) of 00=1/l was added and the viscosity was adjusted to 23 seconds at 20° C. and 4 hood cups to obtain a diluted paint. This diluted paint was spray-painted onto a degreased tin plate and baked at 140°C for 30 minutes to create a cured film, after which the solid content, finished appearance, curability, and film performance of the diluted paint were evaluated. The results are shown in Table 2.

(Examples 14 to 16) 50 parts each of resin solutions A-2 to A-4 obtained in Examples 10 to 12 in the same manner as in Example 13, Kneepan 2ON-6
32 parts each of PTS solution and 1.9 parts each of PTS solution were placed in a stainless steel container, and the coating solutions P-2 to P- were prepared in the same manner as in Example 13.
4 was created. A diluted paint and a cured film were prepared in the same manner as in Example 13. The evaluation results are shown in Table 2.

(Example 17) Resin solution A obtained in Example 11 in the same manner as in Example 13
-350 parts of Sumidur N-3200 (urethane curing agent manufactured by Sumitomo Bayer), 9.4 parts of dibutyltin dilaurate, and 0.5 parts of dibutyltin dilaurate were placed in a stainless steel container and stirred and mixed using a disper to prepare a coating liquid P5. In the same manner as in Example 13, diluting thinner was added to obtain a diluted paint, which was then spray-painted on a tin plate and baked at 90° C. for 30 minutes.

Table 2 shows the evaluation results of the solid content of the diluted paint and its film.

(Comparative Example 3) Resin solution B- obtained in Comparative Example 1 in the same manner as in Example 13.
150 parts of Kneepan 2ON-6028, 6 parts of PTS solution, and 1.7 parts of PTS solution were placed in a stainless steel container and stirred and mixed using a disper to prepare coating liquid P-6. In the same manner as in Example 13, diluting thinner was added to prepare a diluted paint, which was then spray-painted onto a tin plate and baked at 140° C. for 30 minutes to create a cured film. Table 2 shows the solid content of the diluted paint and the evaluation results of its film.

(Comparative Example 4) The diluted paint obtained in Comparative Example 3 was spray-painted on a tin plate in the same manner as in Example 13, and baked at 160° C. for 30 minutes to create a cured film. The evaluation results are shown in Table 2.

(Comparative Example 5) Resin solution B- obtained in Comparative Example 2 in the same manner as in Example 13.
250 parts, kneepan 2ON-6032 parts, PTS solution 1
．． 9 parts were placed in a stainless steel container and stirred and mixed using a disper to prepare coating liquid P-8. In the same manner as in Example 13, diluting thinner was added to obtain a diluted paint, which was spray-painted on a tin plate and baked at 140° C. for 30 minutes to create a cured film. The evaluation results are shown in Table 2.

Claims (1)

[Claims] (1) General formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (In the formula, R_1 is a hydrogen atom or methyl group; A is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. etc. ▼ A group represented by ▼; ～_1_0 alkyl group; R_3 has ▲numerical formula, chemical formula, table, etc.▼-R
_6-(OR_7)_m- or ▲A group represented by ▼ that has a mathematical formula, chemical formula, table, etc.; R_4 is the same or different group and is a lower alkyl group of C_1 to _4; R_5 is -R
_6-(OR_7)_m- or -R_6-(O-C-
R_8) Group represented by_m-; R_6 is C_1 to_4
alkylene; R_7 is C_2-_4 alkylene; R
_8 is C_2-_7 alkylene; m is 0 or 1-4
an integer of 1 to 50; n is an integer of 1 to 50; ) A polymerizable compound represented by