JPS60149667A - Coating composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent curability and gives a coating film having good toughness, adhesion and resistance to hydrolysis, containing a specified unsaturated polyurethane resin. CONSTITUTION:An org. polyisocyanate, a polyol, an ethylenically unsaturated compd. contg. active hydrogen such as ethylene glycol and a chain extender contg. at least two active hydrogen atoms and at least one tert-amino group and having an MW of 500 or above, such as N-methyldiethanolamine, are reacted together in a equivalent ratio of the NCO group to the active hydrogen atom of 0.9-1.4 in the presence or absence of an org. solvent at 30-130 deg.C to obtain an unsaturated polyurethane resin. 0.001-2.5wt% thermal polymn. inhibitor is added to a mixture of 20-95wt% said resin and 80-5wt% ethylenically unsaturated compd. of the formula [wherein A is a 2-4C (halo)alkylene].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating composition that is flexible and tough, with excellent adhesion, heat resistance, and hydrolysis resistance.

In recent years, radiation-curable resins have been attracting attention as materials using curing systems using radiation such as electron beams and ultraviolet rays in response to the progress of environmental pollution, increases in energy costs, and restrictions on energy use. Such a photosensitive composition has a backbone of polyester resin, polyurethane resin, epoxy resin, etc., and contains two polymers that can be polymerized by radiation.
Resin compositions having multiple bonds are often used, but they generally do not contain volatile organic solvents or contain only a small amount of volatile organic solvents, which is very preferable from the point of view of environmental protection, and also helps in saving energy and curing. It is also superior in terms of overall economic efficiency, taking into account various factors such as time reduction, so it can be used for paints, printing inks, adhesives, overlays of flexible circuits and other coating materials, hard resists for printed circuit boards, and etching. It has been put into practical use in a wide range of fields, including resists, metal resists, and inks for printed circuits.

However, the photosensitive compositions of ``Second Edition'' have problems in either curability, the toughness of the resulting coatings, or the adhesion to various adherends, and improvements have been desired.

The purpose of the present invention is to provide a coating composition that provides flexibility and toughness to the resulting cured product by modifying the unsaturated polyurethane resin itself, and that also has significantly improved adhesion to various adherends. Our goal is to provide the following.

The present invention has two or more terminal groups having a polymerizable double bond, and has a quaternary ammonium base of 0.05+++ eq.
The present invention relates to a coating composition characterized in that it contains an unsaturated polyurethane resin having a polyurethane resin of at least /g.

The coating composition of the present invention has excellent curability, and the resulting coating has excellent toughness and adhesion. In particular, the presence of quaternary ammonium bases provides excellent adhesion to metals, and the presence of quaternary ammonium bases is thought to improve the reactivity of ethylenic double bonds.As a result, even thick coating layers can be coated uniformly and Strong curing is now possible.

The unsaturated polyurethane resin of the present invention includes, for example, organic polyisocyanate (A), polyol (B), ethylenically unsaturated compound (U) having active hydrogen, two or more active hydrogen and at least one tertiary amine. Compounds with 7 groups (
C) and, if necessary, a chain extender (D), by treating the polyurethane obtained with a quaternizing agent (E). As another method, polyisocyanate (A), polyol (B), ethylenically unsaturated compound (J) having active hydrogen, two or more active hydrogens and at least one tertiary amine 7 Polyurethane obtained using a chain extender (F) having a molecular weight of 500 or less and, if necessary, a normal chain extender (D), is treated with a quaternizing agent (E).
) can also be obtained by processing. In addition, in the above, the compound (C) or the chain extender (F) can also be treated with the quaternizing agent (E) in advance.

Various organic polyisocyanates (A) can be used in the present invention, including diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), and lysine diisocyanate (TODI).
), xylylene diisocyanate ('MDI), naphthylene diisocyanate (NDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (IIDI), dicyclohexylmethane diisocyanate (IIMDI), lysine diisocyanate (old ), polyisocyanates such as enylmethane triisocyanate, polymethylene polyphenylinocyanate (P to PI), and carposiimide-modified H old, and these may be used alone or in combination of two or more. I can do it.

As the polyol (B), various polyester polyols, polyether polyols, and other polyols can be used. Examples of polyester polyols include aliphatic dicarboxylic acids having 4 to 20 carbon atoms such as adipic acid, superric acid, sebacic acid, and brassylic acid, terephthalic acid, and isophthalic acid as acid components, and ethylene glycol, propylene glycol, and neopentyl. glycol,
C1-C6 aliphatic diols such as hexamethylene glycol, ether glycols such as noethylene glycol and dipropylene glycol, spiroglycols, N-
N-alkyl dialka such as methyljetanolamine/
- A polyester polyol having a polyol component such as amine, polycaprolactone polyol, etc. can be used, and specific examples include adipate polyols such as polyethylene adipate polyol, polybutylene adipate polyol, polyethylene propylene adipate polyol, and terephthalic acid. polyols (e.g., Toyobo Co., Ltd., trade name: Vylon RuX, Vylon RV-, 200L), polycaprolactone polyols (
Examples include Gwissel Chemical Co., Ltd., trade names: Plaxel 212 and Plaxel 220).

Specific examples of polyether polyols include polyoxyethylene polyol, polyoxypropylene polyol, polyoxytetramethylene polyol, and the like.

In addition, other polyols include polycarbonate polyol (e.g., Bayer AG, West Germany, trade name Desmoreen 2020E), polybutadiene polyol (e.g., Nippon Soda, trade name G-1000, G-2000, G-
3000, Idemitsu Petrochemical, trade name Poly bd R-
45HT), polypentadiene polyol, castor oil polyol, and the like. These polyols can be used alone or in combination of two or more.

In the present invention, various types of ethylenically unsaturated compounds (U) having active hydrogen can be used, but representative examples include ethylene glycol, propylene glycol, 1.3-7'lovandiol, and 1.3-butane. Diol, 1,4-butanediol, diethylene glycol,
Dihydric alcohols such as dipropylene glycol, polyethylene glycol, and polypropylene glycol, mono- and di(meth)acrylates of trihydric alcohols such as mono/(meth)acrylate, trimethylolethane, trimethylolpropane, and glycerin, pentaerythritol, etc. Examples include di- and tri(meth)acrylates of alcohols having a valence of 4 or more, and these may be used alone or in combination of two or more.

Examples of the compound (C) having two or more active hydrogens and one tertiary amino group include N-methylgetanolamine, N-ethylgetanolamine, N-
Butyljethanolamine, bis-hydroxyethylpiperazine, N-phenyldiethanolamine, N,N-
N- such as dimethylamine/-2,2-bishydroxymethylethylamine and N-methyljetanolamine
Examples include polyesters containing furkylnoalcoholic acid amine as a polyol component.

In the synthesis of the unsaturated polyurethane resin of the present invention, it is optional to use a chain extender (D) in addition to the above-mentioned components.
Examples include the following 2- to 6-functional polyols and diamines having a primary or secondary terminal amine/group having a molecular weight of 500 or less. Suitable chain extenders include, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol,
Polyols such as 1,4-cyclohexanediol, 1゜4-cyclohexane dimetatool, and xylylene glycol (b) Diamines such as hydrazine, ethyleneamine, tetramethylenediamine, hexamethylenediamine, and 1,4-cyclohexanediamine (c) Alkaline aminos such as ethanolamine, diethanolamine, triethanolamine, etc. (d) Hydroquinone, pyrogaroll, 4,4'-isopropylidenediphenol, aniline and the above polyols, diamines, alkali/
- Molecular weight 500 obtained by adding propylene oxide and/or ethylene oxide to ruamino in any order
Examples include the following polyols.

Examples of the quaternizing agent (E) include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, methyl chloride, iof/1f
Various compounds can be used, such as halogenated hydrocarbons such as chloride, ethyl bromide, and benzyl chloride, organic acids such as acetic acid, propionic acid, and monochloroacetic acid, and various other inorganic acids.

Furthermore, as the chain extender (F) having a molecular weight of 500 or less and having two or more active hydrogens and at least one tertiary amine 7 group, compounds similar to those listed for the above compound (C) can be used. can.

The unsaturated polyurethane resin of the present invention is synthesized by various methods using the above-mentioned components. For example, urethane is synthesized from organic polyisocyanate (A), polyol (B), ethylenically unsaturated compound (U) and compound (C),
Then, a method of adding a quaternizing agent (E) and reacting, (A)
A method of synthesizing a terminal NGO prepolymer from (B) and (U), reacting it with a chain extender (F), and then reacting (E), and a method of synthesizing a terminal NCO prepolymer from (A) and (C). A method of synthesizing a polymer, adding (tJ) to synthesize urethane, and reacting this with (E), or (A> and (
Examples include a method in which a terminal NCO prepolymer is synthesized from B) and (U), and on the other hand, (F) and (E) are reacted in advance, and both are reacted.

In the present invention, the ratio of each component can be appropriately determined from a wide range depending on the desired polyurethane, but usually the chemical equivalent ratio of NCO groups to active hydrogen groups is about 0.9 to 1.4,
The reaction is preferably carried out in a range of about 0.95 to 1.2, and the reaction is usually carried out at about 30 to 130°C, preferably about 40 to 120°C. Further, it is preferable that the treatment with the quaternizing agent of the present invention is normally carried out at a temperature in the range of about 40 to 100''C.

In the present invention, the concentration of quaternary ammonium base is 0.
05 meq/g or more is necessary in order to quickly and uniformly cure the coating film, and is also necessary in order to ensure sufficient adhesion to various adherends including metals.

In the present invention, the unsaturated polyurethane resin can be synthesized without a solvent, in the presence of an organic solvent, or in the presence of an ethylenically unsaturated compound used as a crosslinking agent, which will be described later. Examples of organic solvents include ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and methyl propionate, ethers such as dioxane and cellosolve acetate, and dimethylformamide and dimethyl sulfoxide.

In the present invention, an ethylenically unsaturated compound can be used as a crosslinking agent if necessary when curing the unsaturated polyurethane resin. Various known compounds can be used as ethylenically unsaturated compounds, but typical examples include styrene, vinyltoluene, chlorostyrene,
t-Butylstyrene, α-methylstyrene, divinylbenzene, acrylic acid, methacrylic acid, methyl, ethyl, isopropyl acrylic acid or methacrylate, n7
'tyl, t-7'tyl, α-ethylhexyl, n-nonyl, 11-tecyl, lauryl, stearyl ester, etc., 11-butoxyethyl acrylic acid or methacrylic acid, cyclohexyl, 7ethylhexyl, tetrahydrofurfuryl, glycidyl , allyl, benzyl, tribromophenyl, 2,3-dichloropropyl, 3-chloro-2-hydroxypropyl, N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N-t-butylamino/ethyl ester, etc. Ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)
Acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, molecular weight (hereinafter referred to as MW) 200 to 10 (10
polyethylene glycol mono(meth)acrylate,
Polyethylene glycol monoethyl ether mono(meth)acrylate with MW200~1000, MW200~
1000 polypropylene glycol mono(meth)acrylate, MW200-1000 polypropylene glycol monoethyl ether mono(meth)acrylate,
N11I200-1000 polyethylene glycol monoethyl ether mono(meth)acrylate, MI12
00-1000 polypropylene glycol monoethyl ether mono(meth)acrylate, ethylene glycol di(meth)acrylate, propanediol di(meth)acrylate, 1,3-propanediol di(meth)acrylate
Acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanesiolno(meth)acrylate, polyethylene glycol di(meth)acrylate,
Polypropylene glycol di(meth)acrylate, glycerin + 7in (meth)acrylate, glycerin tri(
meth)acrylate, trimethylolethanedi(meth)
Acrylate, trimethylolethane tri(meth)acryle-F1 trimethylolpropane tri(meth)acrylate, acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, ethylenebisacrylamide, noaryl 7-thalerate, triallyl isocyanurate , dibutyl heptamalate, vinyl acetate, and the like. However, when present during the urethanization reaction, ethylenically unsaturated compounds having active hydrogen among the above should be excluded.

Particularly preferable compounds among the above crosslinking agents are represented by the general formula % (in the formula, the human represents a fullkylene group or a haloalkylene group having 2 to 4 carbon atoms), and specific examples include ethylene glycol, propylene glycol, 1 Examples include monomethacrylates such as 3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol, and 3-chloro-2-hydroxybutanediol methacrylate.

In the present invention, the weight ratio of the unsaturated polyurethane resin and the ethylenically unsaturated compound is 20: the former: 20:
80 to 95:5 is preferred, 50:50 to 80
:20 is more preferable.

For the purpose of stably storing the composition of the present invention, a known thermal polymerization inhibitor can be added. It is desirable that these thermal polymerization inhibitors prevent only the thermal polymerization reaction (dark reaction) without inhibiting the light curing (1r reaction), and therefore the amount added should be equal to the total amount of the unsaturated polyurethane resin and the crosslinking agent. 0.001-2.5% by weight, good*
It is desirable that L < lio, 005-1% by weight. Furthermore, in the present invention, commonly used additives such as colorants, dispersants, lubricants, abrasives, and antistatic agents can be added as necessary.

The composition of the present invention can be obtained by mixing the above-mentioned components by various known methods, and for example, a mixer, roll mill, ball mill, sand mill, high-speed impeller, etc. can be used.

The composition of the present invention can be cured by a known method. For example, when curing with an electron beam, an acceleration voltage of 10
0-1000KeV, preferably 150-300KeV
The total absorbed dose is 0.5 to 20 Mrad, preferably 2 to 15 Mrad in an inert gas atmosphere using
A cured product can be obtained by irradiating to achieve ad.

In addition, in the present invention, other curing means such as those using thermal energy such as infrared rays, high frequency waves, or microwaves, that is, methods of curing by heating, methods of curing with ultraviolet rays obtained from mercury lamps, xenon lamps, etc., or methods of curing using X-rays, gamma rays, etc. It is also possible to use other methods of curing by irradiating with radiation.

In the present invention, when using high-energy ionizing radiation that has the effect of emitting 2* electrons when absorbed by a substance, such as the electron beam, xi, or gamma ray described above, there is no need to add a polymerization initiator. However, when curing by heating or ultraviolet rays, it is preferable to add a thermal polymerization initiator or a photopolymerization initiator.

As described above, the composition of the present invention is characterized by containing an unsaturated polyurethane resin containing a hydrophilic quaternary ammonium base in its molecular chain, and has excellent curability.
The resulting coating is strong, has excellent adhesion to metals, and can be applied thickly.

A detailed explanation will be given below with reference to synthesis examples and examples. still,
A simple part or % indicates a part or % by weight.

Synthesis Example 1 TDI (13B, 5[1) was placed in a reactor equipped with a stirring device and heated to 80°C to obtain 807.2 g of Hi-O 7 RV200L (molecular weight 2030).

A mixed solution of 0.2 g of cyphtyltin dilaure) and 261.0 g of methyl ethyl ketone (Ok) was gradually added dropwise,
The reaction was allowed to proceed for about 3 and a half hours with stirring, and then a mixed solution of 45.1 g of 2-hydroxyethyl acrylate (11[8) and 2.18 g of hydroquinone was added dropwise in the same manner, and the reaction was continued for about 3 hours.
After 1L reaction, N-phenyldiethanolamine 3
Add 4.0Fi gradually. After reacting for about 2 hours,
Lower the liquid temperature to 60°C, add 16.9g of dimethyl sulfuric acid little by little and react for about 30 minutes until the solid content is 80%.
, the concentration of quaternary ammonium base in the solid content is 0.10
+neq/g unsaturated polyurethane resin solution (1) was obtained.

Synthesis Example 2 MDI (212.0 g) was placed in a reactor equipped with a stirring device, heated to approximately 80°C, and 112.3 g of polyoxytetramethylene glycol (molecular weight 1000) and Vylon RUX (
Molecular weight +920) 327.3g, dibutyltin dilaurate 0.15g.

A mixed solution of 196.2 g of MEK was added dropwise and reacted for about 4 hours with stirring, and then a mixed solution of 55 g of IIEΔ62', 5H, hydroquinone 1,' was added dropwise,
After reacting for an additional 3 hours, a solution of 95 WL% of N-methyljetanolamine treated with dimethyl sulfuric acid was added.
Gradually add g and let it react for about 2 hours until the solid content is 80%.
An unsaturated polysurekne resin solution (It) having a concentration of quaternary ammonium base in the solid content of 0.35 eq/g was obtained.

Synthesis Example 3 MDI (247.0 g) was placed in a reactor equipped with a stirring device and heated to about 80°C, and Plaxel 210 (molecular weight 980
) 277, 3g.

Vine RV-20OL (molecular weight 1840) 18
0.18
A mixed solution of 357.5 g of dioxane was added dropwise, and about 3
Let react for half an hour, then +1E^68.78, hydroquinone 1. ．． After dropping 69 g of the mixed solution and reacting for about 2 hours, 5.7 g of ethylene glycol and 24.0 g of 8-methyljetanolamine were added. Og was gradually added dropwise and the reaction was allowed to proceed for about 1.5 hours. After cooling to 60°C, add 25.
4Fi was added little by little and reacted for about 2 hours until the solid content was 7.
0%, the concentration of quaternary ammonium base in the solid content is 0.
24 meq/g unsaturated polyurethane resin solution (III
) was obtained.

Synthesis Example 4 An unsaturated polyurethane resin solution (IV) was obtained in the same manner as in Synthesis Example 1 except that dimethyl sulfate was removed.

Synthesis Example 5 An unsaturated polyurethane resin solution (V) was obtained in the same manner as in Synthesis Example 2, except that N-methyljetanolamine was used without being treated with dimethyl sulfuric acid.

Synthesis Example 6 Produced in the same manner as in Synthesis Example 3 except that ethylene glycol was used instead of N-methyljetanolamine.
An unsaturated polyurethane resin solution (VI) was obtained.

Examples 1 to 5 and Comparative Examples 1 to 5 Using the unsaturated polyurethane resin solutions obtained in the above synthesis examples, the compositions shown in Tables 1 and 2 were mixed, kneaded in a ball mill for 40 hours, and coated. A composition for use was obtained.

Regarding the preparation of the coating film, the above composition was applied to a 50μ thick steel plate with a degreased surface using an applicator so that the dry thickness was 30μ, and dried for 5 minutes in an open air at 80°C. After that, the coating film was cured by irradiation using a curtain beam type electron beam irradiation device at an acceleration voltage of 150 KeV and a beam current of 7.4 mA to give an irradiation dose of 10 Mrad.

The physical properties of the resulting coating film were measured in accordance with IIS K5400. In the table, PU is unsaturated polyurethane resin solution (parts are solid content n), IIEMΔ is hydroxyethyl methacrylate, IIPM81 is droxypropyl methacrylate, EMΔ is ethyl methacrylate, H
D8 is 1,6-hexanediol diacrylate, TM
P-v8 is trimethylolpropane triacrylate,
THF-A represents tetrahydrofurfuryl acrylate. DuPont impact uses a load of 500g, and the unit is am
It is.

Table 1 Table 2 Procedural amendment (method) 1. Case 9 Display ° 1982 Patent M No. 6845 2 Name of the invention Coating composition 3 Person making the amendment Relationship to the case Patent applicant Toyo Rubber Industries Co., Ltd. 4 Attorney 5 Date of amendment order I τ1 January 9, 1985 (shipment date January 29, 1985) 6
, @ Original subject specification and power of attorney 7, Contents of amendment 1, As shown in the engraving of the specification originally attached to document i (no change in content) 2. Attach the power of attorney.

Claims (6)

[Claims] (1) It has two or more terminal groups with a polymerizable double bond, and the 411k ammonium base is O', 05meq
1. A coating composition characterized by containing an unsaturated polyurethane resin having a polyurethane resin of at least /g. (2) Part or all of the polyol component of the unsaturated polyurethane resin is a compound having two or more active hydrogens and at least one tertiary amine 7 group.
The composition described in Section. (3) The unsaturated polyurethane resin is obtained using a chain extender having a molecular weight of 500 or less and having two or more active hydrogen atoms and at least one tertiary amine 7 group. The composition described in Section. (4) The composition according to claim 3, wherein the chain extender is treated with a quaternizing agent in advance. (5) The composition according to claim 11, characterized by an ethylenically unsaturated compound represented by the following general formula % formula % (wherein A represents an alkylene group or a haloalkylene group having 2 to 4 carbon atoms). thing. (6) Claim 1 which is cured by radiation
The composition described in Section.