JPH09286822A - Thermosetting resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin which can form a coating film excellent in weather, water and solvent resistances as well as flatness. SOLUTION: This resin is prepared by copolymerizing 0.1-10wt.% compound having at least two α,β-ethylenic unsaturations in the molecule (e.g. polyethylene glycol) with 1-30wt.% hydroxylated α,β-monoethylenic monomer (e.g. hydroxymethyl methacrylate) and 60-98.9wt.% other α,β-monoethylenic monomer(s) (e.g. styrene or methyl methacrylate).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel thermosetting resin which is excellent in weather resistance, water resistance and solvent resistance as well as matting property. The thermosetting resin is useful as a raw material for a matte coating for exterior of buildings, finishing of woodworking products and plastic products, and the like.

[0002]

2. Description of the Related Art In recent years, a matte coating finish has been frequently used in the above applications from the viewpoint of designability. At that time, conventionally, silica powder or the like is added to the coating material to make the surface of the coating film uneven to form a matte coating film. However, in this method, the silica powder is present in the surface layer portion of the coating film, and the silica powder is detached by friction, so that the matte effect of the portion is deteriorated.

The present invention resides in the development of a matte coating which does not require the addition of silica powder as in the prior art, and further a thermosetting resin which forms a coating film excellent in weather resistance, water resistance and solvent resistance. Is to provide.

[0004]

[Means for Solving the Problems] As a result of intensive studies for solving the above problems, the present inventors have found that it contains two or more α, β-ethylenic double bonds such as polyethylene glycol dimethacrylate. The present invention has been completed by finding the fact that a thermosetting resin obtained by copolymerizing a compound of the above with an α, β-monoethylenic monomer in a specific ratio is effective. That is, the present invention provides (a) α,
Compound containing two or more β-ethylenic double bonds 0.1
To 10% by weight, (b) 1 to 30% by weight of α, β-monoethylenic monomer having a hydroxyl group, and (c) other α, β-
It is a thermosetting resin characterized by being obtained by copolymerizing 60 to 98.9% by weight of a monoethylenic monomer.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, α,
Examples of the compound (a) containing two or more β-ethylenic double bonds include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerol di (meth) acrylate, polybutylene glycol di ( (Meth) acrylate, polyethylene di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol modified bisphenol A di (meth) acrylate, propylene glycol modified bisphenol A di ( (Meth) acrylate, polyethylene glycol modified bisphenol A di (meth) acrylate, polypropylene glycol modified bisphenol A di (meth) acrylate, polyethylene glycol modified hydrogenated bis Enol A di (meth) acrylate, polypropylene glycol modified hydrogenated bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane polyethylene glycol tri (meth) acrylate, Trimethylolpropane polypropylenelenglycol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate may be mentioned, and one or more of them may be used.

These compounds are added to thermosetting resins in an amount of 0.1
It is suitable to contain ~ 10% by weight. If this amount is less than 0.1% by weight, the desired matte effect cannot be obtained because the matte effect cannot be obtained, and if it exceeds 10% by weight, gelation occurs during copolymerization and thermosetting. The resin itself cannot be obtained, which is not preferable.

In the present invention, α, β- having a hydroxyl group
Examples of the monoethylenic monomer (b) include hydroxyethyl (meth) acrylate and hydroxypropyl (meth)
Acrylate, hydroxybutyl (meth) acrylate, etc., and addition products of polycaprolactone and hydroxyethyl (meth) acrylate (Placcel F series:
Trade name, manufactured by Daicel Chemical Industries, Ltd., addition product of polyethylene glycol and methacrylic acid (Blenmer PE series: trade name, manufactured by NOF CORPORATION), addition product of polypropylene glycol and methacrylic acid (Bremmer PP series: trade name, (Manufactured by Nippon Oil & Fats Co., Ltd.), and one or more of these may be used. The amount of these used is preferably in the range of 1 to 30% by weight in the thermosetting resin. This amount is 1
If it is less than 10% by weight, the reaction with the curing agent is not sufficiently performed,
The solvent resistance of the resulting coating film is poor, and when it exceeds 30% by weight, the water resistance of the coating film is poor, and neither is preferable.

In the present invention, other α, β-monoethylenic monomers (c) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and n-butyl (meth) acrylate. ,
Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) Acrylate, glycidyl (meth) acrylate,
Methyl glycidyl (meth) acrylate, allyl glycidyl ether, (meth) acrylic acid, maleic acid, maleic anhydride, itaconic acid, N, N'-dimethylaminoethyl (meth) acrylate, N, N'-diethylaminoethyl (meth) Acrylate, N, N'-dimethylaminopropyl (meth) acrylate, (meth) acrylamide,
N-methoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, Nn-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth)
Acrylamide, N-sec-butoxymethyl (meth) acrylamide, N-tert-butoxymethyl (meth) acrylamide, (meth) acrylonitrile, styrene, α-methylstyrene, vinyltoluene, vinyl acetate, vinyl propionate, ethylene, propylene, Α with 4 to 20 carbon atoms
-Olefin and the like can be mentioned, and one or more of them can be used.

In the present specification, (meth) acrylate, (meth) acrylic acid, (meth) acrylamide and (meth) acrylonitrile mean methacrylate, acrylate; methacrylic acid, acrylic acid; methacrylamide, acrylamide; methacryloyl. Means nitrile and acrylonitrile, respectively.

The thermosetting resin according to the present invention can be produced by using the above-mentioned components (a), (b) and (c) in a known polymerization method, that is, a solution polymerization method, a suspension polymerization method, a bulk polymerization method or an emulsion. It can be produced by a polymerization method or the like. At that time, as the polymerization initiator, azobisisobutyronitrile, 4,4'-
Azobis (4-cyanopentanoic acid), benzoyl peroxide, tert-butylperoxy-2-ethylhexanoate,
Cumene hydroperoxide, potassium persulfate, hydrogen peroxide, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], etc. Also, if necessary, as a chain transfer agent, dodecyl mercaptan , Mercaptoethanol, α-methylstyrene dimer and the like can be used.

In the present invention, in order to satisfy the desired performance of the coating film, it is preferable to add a curing agent to the thermosetting resin obtained as described above. The amount of the curing agent is appropriately 5 to 50 parts by weight based on 100 parts by weight of the thermosetting resin. Further, examples of the curing agent include amino resins and isocyanate prepolymers. Here, the amino resin is a resin synthesized from at least one kind of melamine, urea, benzoguanamine glycoluril and the like and formaldehyde, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n- Butyl alcohol,
An alkyl ether of a part or all of the methylol group is used with a lower alcohol such as isobutyl alcohol.

Further, the isocyanate prepolymer is
It is a compound containing two or more free or blocked isocyanate groups in one molecule, for example, it is an adduct of isocyanates and a polyhydric alcohol. As the isocyanates, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and trimethylhexane diisocyanate;
Aliphatic diisocyanates such as isophorone diisocyanate and 4,4′-methylenebis (cyclohexyl isocyanate); aromatic diisocyanates such as xylene diisocyanate and tolylene diisocyanate; and other isocyanates. As polyhydric alcohol,
Examples thereof include ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane and the like. Other isocyanate prepolymers include adducts of the above isocyanates with a low molecular weight polyester resin having a functional group capable of reacting with isocyanate groups; the above isocyanates and water adducts; burettes; Coupling; Examples thereof include blocking agents such as lower monohydric alcohols and methylethylketoxime that block the isocyanate groups of the above isocyanates.

As the solvent in the present invention, toluene,
Aromatic hydrocarbons such as xylene; Aliphatic hydrocarbons such as hexane, heptane, mineral spirits; Isobutene and n
-Hydrogenated isoparaffins of butene copolymers; esters such as ethyl acetate, butyl acetate, ethylene glycol diacetate, 2-ethoxyethyl acetate; ketones such as acetone and methyl isobutyl ketone; alcohols such as butyl alcohol Is mentioned.

The thermosetting resin of the present invention may be blended with a synthetic resin such as an acrylic resin, an epoxy resin, a polyester resin, a polyamide, or a fibrin derivative to such an extent that the object of the present invention is not impaired. Flow additives, antiblocking agents, ultraviolet absorbers, benzoin, antistatic agents, antioxidants and other commonly used coating additives may be added. When it is used as a clear coat, a small amount of pigment may be added so that the hiding property is not fully developed.

When the thermosetting resin of the present invention is used as a paint, the above components are blended by a general method, the viscosity is adjusted with a diluting solvent to give a paint, and the paint is applied at room temperature or A coating film is formed by heating. As a coating method, a usual method, for example, bar coater coating, brush coating coating, spray coating, dip coating and the like can be mentioned.

[0016]

The present invention will be described in detail below with reference to Reference Examples, Examples and Comparative Examples. In the following, “parts” and “%” are based on weight. Reference example Glass 4-neck flask (with stirrer, thermometer, external heater, cooling tube, condenser and nitrogen inlet tube) toluene 1
00 parts were charged and the temperature was raised to 100 ° C. In this solvent, Table 1
The types and amounts of each component shown in are added dropwise over 5 hours, and then held at 100 ° C for 5 hours, and the thermosetting resin (S-1) ~
(S-4) and (S-6) were obtained.

[0017]

[Table 1] * 1: Ethylene glycol chain n = 4 * 2: Gelation occurred during copolymerization, and a thermosetting resin could not be obtained.

Examples 1 to 3 and Comparative Examples 1 and 2 As shown in Table 2, the thermosetting resin (S-
1) to (S-4) or (S-6) and a curing agent are mixed, and the viscosity is adjusted to 10 poise (25 ° C) with toluene to make 5 kinds of paint, and the steel plate to which white paint is applied in advance is applied. The paint was applied with a bar coater (# 55) to obtain 5 kinds of test plates. The coating film performance of these test plates was evaluated by the following method, and the results are shown in Table 2.

Comparative Example 3 In the same manner as in Example 3, except that silica powder was added to the thermosetting resin (S-3) and the amount of the curing agent was changed.
The same operation was performed to obtain a test plate. The performance of the coating film of this test plate was evaluated by the following method, and the results are shown in Table 2.

Test / Evaluation Method Gloss: Measured by 60 ° specular reflectance. -Weather resistance: After the test plate was left to stand for 1000 hours using a QUV tester, its coating film state was visually observed.・ Water resistance: After immersing the test plate in warm water of 50 ° C for 48 hours, visually observing the coating film state, 3 stages (○: no abnormality, △: somewhat inferior, ×: whitening or blistering occurred ).・ Solvent resistance: Reciprocating the xylol wipe on the coating of the test plate
After performing 50 times, visually observe the state of the coating film, and
The evaluation was made at a stage (◯: no trace, Δ: somewhat inferior, ×: trace).

[0021]

[Table 2] * 3: Trade name, Mitsui Toatsu Chemicals, butylated melamine resin, solid content 60% * 4: Trade name, Mitsui Toatsu Chemicals, urethane prepolymer, isocyanate group 17%, solid content 75%

[0022]

As is apparent from Table 2, the thermosetting resin of the present invention can form a coating film which is excellent in weather resistance, water resistance and solvent resistance as well as in matting property.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Kazuaki Saeki 1900 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. A compound containing 0.1 to 10% by weight of (a) a compound having two or more α, β-ethylenic double bonds in one molecule, (b)
1 to 30% by weight of α, β-monoethylenic monomer having a hydroxyl group, and (c) 60 to 98.9% by weight of other α, β-monoethylenic monomer are copolymerized. Thermosetting resin that does.