JP2003003091A - Polymerizable unsaturated resin coating material and formation of coating film thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material excellent in hardening characteristic and finish. SOLUTION: The polymerizable unsaturated resin coating material comprises (1) a resin (A) having a (meth)acryloyl group and/or a vinyl group, (2) an unsaturated monomer (B) selected from an unsaturated monomer having a (meth) acryloyl group and vinyltoluene, (3) an organic peroxide (C) and comprises no aromatic organic solvent. The formation of the coating film contains a process in which the coating material is applied on a substrate and hardened at 5-100 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polymerizable unsaturated resin coating material and a coating film forming method thereof.

[0002]

2. Description of the Related Art Conventionally, wood-based plywood such as natural wood or plywood, papers, and plastics have generally been subjected to color coating, sealer coating, top coating and the like. As a coating material used in such coating, a polymerizable unsaturated resin coating material has been widely used because it can be cured in a short time and can form a coating film having excellent coating film performance. However, since conventionally used polymerization type unsaturated resin coating materials contain organic chemical substances such as styrene, a coating film unsuitable for indoor coating may be formed.

Further, paints suitable as wood plywood paints have a problem in that the workability of coating with a curtain flow coater is poor.

An object of the present invention is to provide a coating material which can form a coating film particularly suitable as a coating film for wood plywood and which is excellent in coating workability by a curtain flow coater.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that (meth) acryloyl group and / or vinyl group-containing resins (A), (meth) At least one unsaturated monomer (B) selected from an acryloyl group-containing unsaturated monomer and vinyltoluene, an organic peroxide (C), and a metal catalyst (D)
Is contained as a curing component and does not contain an aromatic organic solvent, and a polymerizable unsaturated resin coating material and a substrate surface are coated with the above coating material and cured at a temperature of 5 to 100 ° C. The present inventors have found that the coating film forming method described above can solve all the conventional problems, and have completed the present invention.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The (meth) acryloyl group- and / or vinyl group-containing resin (A) used in the coating material of the present invention has an average of 1 or more, preferably 2 to 10 (in one molecule) Examples thereof include acrylic, polyester, alkyd, epoxy, vinyl, silicon, and fluorine resins containing a (meth) acryloyl group and / or vinyl group. Average number of unsaturated groups in unsaturated resin is about 1
When the number is less than the above, the properties of the cured film such as hardness, solvent resistance and weather resistance deteriorate. The weight average molecular weight of the resin is 500 to 2
The range of 0000, preferably 600 to 5000 is preferable. When the weight average molecular weight is less than 500, the hardness, processability, water resistance and other properties of the cured coating deteriorate, while
When it exceeds 00, the coating workability is deteriorated, which is not preferable.

The above-mentioned (meth) acryloyl group- and / or vinyl group-containing resin (A) is, for example, an acrylic-based, polyester-based, alkyd-based, epoxy-based, vinyl-based, or silicon-based resin having a hydroxyl group in the method molecule described below. system,
Unsaturated monomers containing a hydroxyl group-containing resin such as a fluorine-based resin and a functional group reactive with the hydroxyl group (for example, an isocyanate group, a carboxyl group, a silyl group) and a (meth) acryloyl group and / or a vinyl group (for example, Isocyanate ethyl (meth) acrylate, (meth) acrylic acid, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, etc.), a method of reacting with a carboxyl group in the molecule, acrylic or polyester , An alkyd-based, epoxy-based, vinyl-based, silicon-based, fluorine-based, etc. carboxyl group-containing resin and a functional group that reacts with the carboxyl group (for example, epoxy group, hydroxyl group) and (meth) acryloyl group and / or vinyl group Unsaturated monomers containing, for example, glycidyl (meth) acrylate, hydroxy The method of reacting the chill (meth) acrylate), acrylic containing silyl group in the molecule, vinyl,
An unsaturated monomer containing a silyl group-containing resin such as a silicon-based resin and a functional group that reacts with the silyl group (for example, a hydroxyl group, a carboxyl group, a silyl group) and a (meth) acryloyl group and / or a vinyl group (for example, , Hydroxyethyl (meth) acrylate, (meth) acrylic acid, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, etc.) and the like.

As the resin containing a hydroxyl group or a carboxyl group used for reacting with the above unsaturated monomer, a polyester resin or an alkyd resin is inexpensive,
It is preferable to use this from the viewpoint of coating workability and the like. The preferable resin will be described below.

As the polyester resin or alkyd resin containing a hydroxyl group or a carboxyl group, conventionally known resins can be used.

The polyester resin is, for example, a polybasic acid component, a polyhydric alcohol component and, if necessary, a monobasic acid (P-ter benzoic acid, etc.) component with good stirring.
It is obtained by holding at 0 to 250 ° C. for 10 to 100 minutes.

The alkyd resin is, for example, 200-200 with well stirring the polybasic acid component, polyhydric alcohol component and fatty acid (saturated or unsaturated fatty acid (oil)) component.
It is obtained by holding at 250 ° C. for 10 to 100 minutes.

Polyhydric alcohols that can be used include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polyethylene glycol or polypropylene glycol having a number average molecular weight of 150 to 6000, monoalkyl ethers thereof, neopentyl glycol. , Diethyl propane diol, ethyl butyl propane diol, cyclohexane dimethanol, butylene glycol, pentane diol, hexane diol, hydrogenated bisphenol A, ethylene glycol adduct of bisphenol A, trimethylol propane, trimethylol ethane, glycerin, pentaerythritol, etc. Can be mentioned.

As the polybasic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic anhydride, pyromellitic anhydride, succinic acid, adipic acid, sebacic acid,
Examples thereof include monovalent and polyvalent carboxylic acids such as benzoic acid, alkylbenzoic acid, maleic anhydride, itaconic anhydride and fumaric acid. These may be used alone or in a mixture of several kinds at any ratio.

As the unsaturated fatty acid, any of natural or synthetic unsaturated fatty acids can be used. For example, from tung oil, linseed oil, castor oil, dehydrated castor oil, safflower oil, tall oil, soybean oil and coconut oil. The unsaturated fatty acid obtained is mentioned. The above fatty acids may be used alone or in combination of two or more.

Examples of the saturated fatty acid include caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and the like.

Examples of the (meth) acryloyl group-containing unsaturated monomer (B) used in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate and butyl acrylate ( n-, i-, t-), hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, N-propyl methacrylate,
Isopropyl methacrylate, butyl methacrylate (n
-, I-, t-), hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, and the like having 1 to 1 carbon atoms. 18 (1-24) alkyl or cycloalkyl ester: C2-C8 hydroxyalkyl ester of acrylic acid or methacrylic acid such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; like allyl ether Unsaturated ether compounds; (meth)
Acrylic acid; glycidyl (meth) acrylate and the like can be mentioned.

In the present invention, the blending ratio of the resin (A) / unsaturated monomer (B) is about 40 to 95% by weight / about 5 to 60% by weight based on the total solid equivalent amount of both. %,
It is preferably in the range of about 60 to 90% by weight / about 10 to 40% by weight. When the compounding ratio is more than 95% by weight of the resin (A) and less than about 5% by weight of the unsaturated monomer (B), coating performance and roll coater or spray coating workability are deteriorated. If A) is less than 40% by weight and unsaturated monomer (B) is more than about 60% by weight, the coating film becomes brittle, which is not preferable.

Examples of the organic peroxide (C) used in the present invention include hydroperoxides such as ter-butyl peroxide and cumene peroxide, dialkyl peroxides such as diter-butyl peroxide and dicumyl peroxide, Examples thereof include perester type such as ter-butyl peracetate, diacyl peroxide type such as benzoyl peroxide and lauroyl peroxide, and ketone type such as methyl ethyl ketone peroxide and cyclohexanone peroxide.

The mixing ratio of the organic peroxide (C) is such that the total solid content of the resin (A) and the unsaturated monomer (B) is 100.
0.1 to 10 parts by weight, preferably 0.5
~ 5 parts by weight. If it is less than 0.1 part by weight, the curability is lowered, while if it exceeds 10 parts by weight, the light resistance is lowered, which is not preferable.

Metal catalyst (D) used in the present invention
As, cobalt oleate, cobalt stearate, dibutyltin oxide, monobutyltin hydroxide, tetrabutyl zirconate, tetrabutyl titanate, stannous chloride, zinc oleate, tin oleate,
Examples include zinc acetate. Of these, cobalt-based catalysts are preferable.

The mixing ratio of the metal catalyst (D) is the resin (A).
And 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the total solid content of the unsaturated monomer (B). If it is less than 0.1 parts by weight, the curability is lowered, while if it exceeds 10 parts by weight, the light resistance is lowered and the coating film is colored, which is not preferable.

In the coating material of the present invention, it is preferable to add a wax (E). As the wax that can be used, the wax conventionally used in the polymerization-curable resin coating composition can be used without particular limitation.
As such a wax (E), for example, paraffin wax is particularly preferable. The mixing ratio of the wax (E) is 0 to 1 part by weight, preferably 0 to 0.2 part by weight, based on 100 parts by weight of the total amount of the resin (A) and the monomer (B). If the amount exceeds 1 part by weight, the coating film performance and the coating film appearance are deteriorated, which is not preferable.

It is important that the coating material of the present invention does not contain organic substances such as styrene and aromatic organic solvents.
When a coating material containing these is used, these substances remain in the cured coating film, and therefore, it is particularly unsuitable as a coating film.

The coating composition of the present invention may further contain a polyfunctional unsaturated compound (particularly a bifunctional unsaturated compound) as a curable component other than the above-mentioned resin (A) and unsaturated monomer (B), if necessary. Compounds, trifunctional unsaturated compounds, tetrafunctional unsaturated compounds, etc.) can be added. If necessary, an organic solvent (ketone-based, ester-based, etc.), a fluidity modifier, a cissing inhibitor, a colorant, a filler, a matting agent, an anti-slip agent, etc. can be added.

The above-mentioned polyfunctional unsaturated compounds include
What is conventionally used as a polymer resin paint can be used without particular limitation. Specifically, for example,
(Poly) ethylene glycol, (poly) propylene glycol, hexanediol, neopentyl glycol,
Examples include monomers having two or more polymerizable unsaturated groups in one molecule obtained by esterifying a polyhydric alcohol compound such as trimethylolpropane or glycerin and a carboxyl group-containing monomer such as (meth) acrylic acid. be able to. Moreover, as a trade name, for example, as a trade name manufactured by Toagosei Co., Ltd., for example, Aronix M-210, same left M-215, same left M-220, same left M-233, same left M-240, same left M. -245, same as the left M
-260, Same as left M-270, Same as left M-305, Same as left M-
309, same left M-310, same left M-315, same left M-3
20, same left M-350, same left M-360, same left M-40
0, same as left M-450, same as left M-1100, same as left M-12
00, same left M-1210, same left M-1310, same left M-
1600 and the like.

The mixing ratio of the polyfunctional unsaturated compound is 0 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the total amount of the resin (A) and the unsaturated monomer (B). Is the range.

Examples of the above-mentioned organic solvent include low boiling point ketone type organic solvents such as acetone, ketyl ethyl ketone and methyl isobutyl ketone, methyl acetate,
Ester-based organic solvents such as ethyl acetate, propyl acetate and butyl acetate are particularly preferable.

The coating composition of the present invention can be used as a polymerization-curing sealer, a polymerization-curing intermediate coating composition or a polymerization-curing top coating composition. The polymerization-curable sealer is used to fill the pores on the surface of the wood plywood, which is porous and has high absorbency. As the sealer, a polymer-curable unsaturated polyester resin of the present invention diluted with an organic solvent to a solid content of 5 to 90% by weight is used for roller coating.

The above-mentioned polymerization-curing intermediate coating composition and polymerization-curing top coating composition can be used in an appropriate combination in the coating process of wood plywood, if necessary. The polymerization-curable intermediate coating composition is used for improving adhesion to a colored coating film, a sealer, a colored coating film, or a top coating film, and imparting a design property, and is usually an extender pigment or the like. Is blended. Polymerization-curable topcoat is provided on the top layer of the coating film and is required for building material coatings (slip prevention, etc.)
It is used for exhibiting the above-mentioned properties and imparting design properties (making the coating film surface semi-glossy, matte, etc.).

The coating film forming method of the present invention is a method for forming a coating film, which comprises coating the above-mentioned coating material on the surface of a substrate and curing the coating material at room temperature or by heating. In particular,
For example, it can be applied to the surface of a substrate such as plastic, paper (for example, paper impregnated with phenol), wood plywood, or the like. Further, it is also possible to sequentially apply colored coating, polymerization-curing sealer coating, polymerization-curing intermediate coating, polymerization-curing top coating, and the like. Further, in the above step, each coat may be cured at room temperature or by heating, or after coating two or more coats, it may be cured at room temperature or by heating.

The coating can be carried out by a conventional coating method such as spray coating (electrostatic or non-electrostatic), brush coating, roll coater coating or curtain flow coater coating.

The above-mentioned colored coating is used for coloring the base material so as to give it cosmetic and design properties and to improve the durability of the base material. Conventionally known ones can be used.

The coating amount may be appropriately selected depending on the type of coating material used (for sealer, overcoating, etc.), but the dry weight is about 3 to 15 g / 30 cm ² , preferably about 5 to 12.
It is in the range of g / 30 cm ² .

The coated substrate obtained by the present invention can be applied to a wide range of applications such as pianos, wallboards, floorboards, furniture and crafts.

[0035]

EXAMPLES The present invention will be described in detail with reference to examples. The invention is not limited to the examples provided.

Production Example of Unsaturated Alkyd Resin 300 parts of flaxseed oil was added to a clean container in which nitrogen gas was refluxed.
250 parts of soybean oil, 20.5 parts of glycerin, 78.1 parts of pentaerythritol 0.05 parts of lithium hydroxide were charged and kept at 250 ° C. for 1 hour with stirring, then 200 ° C.
Then, 50 parts of pentaerythritol and 300 parts of phthalic anhydride are charged and the temperature is raised to 230 ° C. to obtain an acid value of 30 mgKO.
After reacting for 4 to 5 hours until reaching H / g, 56 parts of glycidyl methacrylate was added and reacted at 100 ° C. for 5 hours to obtain an unsaturated alkyd resin.

Production Example of Unsaturated Polyester Resin To a reaction vessel, 73 parts of neopentyl glycol, 37 parts of trimethylolpropane, 59 parts of phthalic anhydride and 73 parts of adipic acid were added, and after reacting at 200 to 230 ° C. for 5 hours, After adding 77 parts of trimellitic anhydride and reacting at 180 ° C. for another hour, glycidyl methacrylate 28
Parts were added and reacted at 100 ° C. for 5 hours to obtain an unsaturated polyester resin.

Production Example of Unsaturated Acrylic Resin In a reaction vessel containing 100 parts of methyl isobutyl ketone, 55 parts of methyl methacrylate, 8 parts of styrene, 9 parts of n-butyl acrylate, 5 parts of 2-hydroxyethyl acrylate, 1 part. , 6-hexanediol diacrylate
After reacting a mixture consisting of 2 parts and 4 parts of methacrylic acid in the presence of 1 part of an azoisobutylnitrile initiator at 180 ° C. for 8 hours, 4 parts of glycidyl methacrylate are added,
The reaction was carried out at 100 ° C. for 5 hours to obtain an unsaturated acrylic resin.

Example 1 Size vertical 1200 mm × ground with abrasive paper of No. 240 well
400 mm wide × 30 mm thick on the surface of wood plywood, KP
M stain (manufactured by Kansai Paint Co., Ltd., trade name, colorant) was roller coated.

Next, the above-mentioned unsaturated alkyd resin 80
Parts, 20 parts by weight of vinyltoluene, 2 parts by weight of cobalt octylate catalyst, 2 parts by weight of peroxide catalyst (NOF CORPORATION, Permec N, trade name, polymerization catalyst), 0.1 part by weight of paraffin wax (125 ° F). 10 g of a polymerization-curable alkyd resin composition obtained by mixing the above parts with a spray coating machine
After applying / 30 cm ^2, it was left to stand at 20 ° C. for 16 hours.

Example 2 On the surface of the coating film obtained in Example 1, 80 parts by weight of the above-mentioned unsaturated alkyd resin, 20 parts by weight of vinyltoluene, 2 parts by weight of cobalt octylate catalyst, peroxide catalyst (NOF Corporation) , Permek N, trade name, polymerization catalyst) 2 parts by weight and paraffin wax (125 ° F.) 0.1 parts by weight to obtain a polymerization-curable alkyd resin composition, which is applied with a curtain flow coater at 10 g / 30 cm ^2. After that, it was left to stand at 20 ° C. for 16 hours.

Example 3 The same composition as in Example 1 was used except that the unsaturated polyester resin was used as the unsaturated alkyd resin in Example 1, and then a coating film was formed in the same manner as in Example 1. did.

Example 4 The same composition as in Example 1 was used except that the unsaturated acrylic resin was used as the unsaturated alkyd resin in Example 1, and then a coating film was formed in the same manner as in Example 1. did.

Comparative Example 1 A coating film was formed in the same manner as in Example 1 except that vinyl toluene was not added in Example 1 and the same composition as in Example 1 was used.

Table 1 shows the test results for the examples and comparative examples. In Table 1, the test method is as follows.

Defoaming property: (Spray or roll) A coater wraps bubbles during coating, but it is preferable that the wrapped bubbles disappear during drying, while the bubbles caught by the coater during coating become dry. Those that did not disappear and remained in the coating film and causing coating film defects such as blisters, scratches, and foaming were rated as x.

Curtain Flow Coater Applicability: Good for coating without curtain defects, foaming, etc., coating film defects,
On the other hand, those with coating defects such as curtain breakage, foaming, etc. and coating film defects were regarded as defective.

Roll coater washability: The roller after coating was washed with an organic solvent (methyl isobutyl ketone). Those with a short cleaning time were regarded as good, and those requiring more than twice the cleaning time were regarded as defective.

Cold Repeat Test: The coated plywood obtained above was left at 80 ° C. for 2 hours, then left at −20 ° C. for 2 hours, repeated twice, and then allowed to stand at room temperature (20 ° C.). Then, the evaluation was performed by the following method.

The coating was visually observed and evaluated based on the following criteria. 5 points are good without any film defects such as cracks, cracks, discoloration, 4 points are good with some film defects such as cracks, cracks, discoloration, etc., and 3 points are film defects such as cracks, cracks, discoloration, etc. 2) indicates that the number of film defects such as cracks, cracks and discoloration is large and inferior, and 1 indicates that the film defects such as cracks, cracks and discoloration significantly occur and is inferior.

Water resistance test: The coated plywood obtained above was 6
After soaking in warm water of 0 ° C for 2 hours, then taking out from the warm water and drying at 60 ° C for 2 hours, repeating twice, and then leaving to stand at room temperature (20 ° C), the following method was used. evaluated. The coating was visually observed and evaluated based on the following criteria. 5 points are good with no film defects such as cracks and cracks, 4 points are good with 1 to 2 film defects such as cracks and cracks, and 3 points are 3 film defects such as cracks and cracks.
Inferior to 9 places or less, 2 points are inferior to 10-19 or more film defects such as cracks and cracks, and 1 point is significantly inferior to 20 or more film defects such as cracks or cracks. Show things. Table 1

[0052]

[Table 1]

[0053]

EFFECTS OF THE INVENTION The coating composition of the present invention has excellent coating workability and coating film performance, and can form a coating film particularly suitable for coating plywood for building materials.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4D075 BB26Z BB62Y BB93Z CA02                       CA38 CA47 DA04 DA06 DB18                       DB21 DB31 DC02 DC38 EA07                       EA37 EA39 EB13 EB16 EB20                       EB22 EB24 EB33 EB35 EB36                       EB38 EB43 EB45 EC07 EC08                       EC30 EC37 EC54                 4J038 FA042 FA112 FA221 JA66                       KA04

Claims (5)

[Claims] 1. At least one selected from the following components (1) (meth) acryloyl group- and / or vinyl group-containing resin (A), (2) (meth) acryloyl group-containing unsaturated monomer and vinyltoluene: Polymerization type containing unsaturated monomer (B), (3) organic peroxide (C), and (4) metal catalyst (D) as a curing component, and containing no aromatic organic solvent Unsaturated resin paint. 2. The coating composition according to claim 1, wherein the metal salt catalyst (D) is a cobalt salt catalyst. 3. The wax (E) for 100 parts by weight of the total amount of the resin (A) and the monomer (B) in the coating composition.
The paint according to claim 1 or 2, wherein the paint is blended in an amount of 0 to 1 part by weight. 4. The paint according to claim 1, 2 or 3, wherein the paint is a polymer sealer, a polymer undercoat paint, a polymer intermediate coat paint, or a polymer top coat paint. 5. A method for forming a coating film, which comprises coating the surface of a base material with the coating composition according to claim 1, 2, 3 or 4 and curing the coating material at a temperature of 5 to 100 ° C.