JPS5829814A - Polymerizable resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful polymerizable resin composition, and more particularly, it is composed of a specific polymerizable prepolymer and a specific reactive diluent, and is composed of a metal surface. The present invention relates to an energy ray-curable polymerizable resin composition that exhibits excellent adhesion to.

In the fields of paints, printing inks, adhesives, etc., energy ray-curable resins are being actively used for the purpose of saving resources, saving energy, and reducing pollution. Along with the development, some resins have been developed that can meet the highly demanding lubrication requirements, but these vertically curable resins for energy curing, which are characterized by not containing organic solvents, are generally flowable. It has poor properties and tends not to drip onto the material, and when it is cured, the curing reaction is completed in an extremely short period of time, making it easy for the inside of the coating to sag. It is common for the adhesion of the coating to the substrate to be impaired.

Therefore, as a method to improve the adhesion of monopolymer resins, we have combined this rare polymerizable resin with epoxy resins, polyester resins, polyvinyl butyral poly(meth)acrylic esters, etc. is a resin blend that does not directly participate in the polymerization reaction, or a compound that has a functional group that can directly interact with the material, such as a methacrylate containing a phosphoric acid group, a titanium coupling agent, or a silane coupling agent. Although the adhesion to metal materials has been improved by this method, the adhesion is still inferior to that of this type.
It is highly dependent on the properties of the polymerizable prepolymer, which is also referred to as the basic component in the polymerizable resin, and is difficult to sufficiently modify by external modification as described above, that is, by adding a modifying component.

Additionally, polymerizable compositions that provide good adhesion to metals have already been described in US Pat.
Although it is mentioned in the specification of No. 6, it still cannot be said to be sufficient in terms of curability and adhesion.

However, as a result of intensive research to develop an energy ray-curable resin that has excellent adhesion to metal substrates, excellent curability, and good chemical and physical properties, the inventors found that a special By combining a polyester-based polymerizable prepolymer with a structural factor introduced and a diluent with monofunctional or higher hydroxyl group, we can create an extremely superior product that has never been seen before. It was discovered that a polymerizable composition having curability and adhesive properties could be obtained, and the present invention was completed.

That is, in the present invention, the dimer acid residue is 9-7oJk11
(meth)acryloyl group-containing polyester resin (kame-1) and/or (meth)acryloyl group-containing polyester urethane resin (a-2) C obtained using polyester polyol (a-1-1) containing % of Hereinafter, both resins will also be collectively referred to as polymerizable prepolymer (A). ] and a polymerization-reactive diluent (B) as essential components, the former resin (A) component being at least 20% by weight and the latter diluent (component 81 being at most 80.It%). a resin composition, and the polymerization-reactive diluent fBl
The object of the present invention is to provide a poultry housing resin composition in which 10% by weight or more is a hydroxyl group-containing-functional or higher polyfunctional diluent.

Here, the polyester polyol (a-1-
1) having a hydroxyl group capacity of 6000, preferably 400 to 1500, and 9 to 7011%, where the total tt of the starting materials of the polyester polyol is 100kWk%,
Those containing dimer acid residues derived from dimer acids with i < 419 to 453% and synthesized from acid components and alcohol components by conventional esterification and/or transesterification methods are applicable. , and is obtained by reacting both of these reaction components in the presence or absence of a catalyst, usually at 180 to 260°C. If the dimer acid residue content is less than 97% by weight, the coating film will be very hard and sufficient metal adhesion will not be obtained; Both of these are undesirable because they result in a significant decrease in the curability of the coating film.

Therefore, in the present invention, when obtaining the polyester polyol (a-1-1), dimer acid or dimethyl dimer acid is essentially used as a starting material for the acid component, and these dimer acids, etc. is used in an amount of 9 to 70% by weight based on the total of all starting materials.

Both dimer acid and dimethyl dimerate are commercially available, but are usually produced by trimerization of tall oil fatty acids and contain a mixture of trimers and monomers of approximately 25-50% by weight. Therefore, the polyester polyol (a-11) thus contains a dimer acid residue derived from di-1-acid, and is an aliphatic, alicyclic or aromatic compound having 4 to 20 carbon atoms as an acid component. Dicarboxylic acids such as maleic acid, adipic acid, fumaric acid, itaconic acid, sebacic acid,
Succinic acid, phthalic acid, tetrahydrophthalic acid, isophthalic acid or terephthalic acid can be used simultaneously with dimer acids or derivatives thereof.

Examples of the alcohol component, which is the other component for obtaining the polyester polyol (a-11), include ethylene glycol, diethylene glycol, glopylene glycol, diethylene glycol, 1,3-butylene glycol, 1,4- Butylene glycol, 1
．． 2-4 OH such as 6-hexanediol, neopentyl glycol, cyclohexane dimetatool, 2,2-bis(4-hydroxycyclohexyl)propane, glycerin, trimethylol goupane, hexanetriol, pentaerythritol or diglycerin and polyhydric alcohols having 2 to 18 carbon atoms, furthermore, ethylene oxide or propylene oxide adducts of epoxy group A (number of moles added is 2 to 4) or glycidyl ether of bisphenol A. This alcohol component is polyester polyol (a-1-1
) should be 75% by weight or less based on the total starting materials.

Such the above polyester polyol <ch-1-1)
For 2 to 4 hydroxyl groups, ・Organic diincyanate and a polymerizable monomer having hydroxyl groups are reacted to the extent that no NCO groups are included, or the above polyester polyol (a-1t) When the hydroxyl group is subjected to an esterification reaction with ethylenically unsaturated monocarboxylic acid, a polyester urethane resin containing a polymerizable (meth)acryloyl group (a
-1) It is possible to obtain a monopolymer prepolymer (Al) which is now a polyester resin (凰-2).

Among these polymerizable prepolymers (Al, the former resin (
As a practical method for obtaining a-1), in the first step, an organic diincyanate and a monomer having a hydroxyl group are reacted with a reaction product having an NCO group and the above-mentioned polyester. Is it better to introduce a double bond at the end? Of course, polyester polyol (a-1
-, 1) does not in any way preclude a method in which an organic diyn 7anate and a hydroxyl group-containing polymerizable monomer are subjected to a direct reaction.

Typical organic diisocyanates include tolylene diisocyanate, xylylene diisocyanate, 4,
Aromatic f6 diisocyanates such as 4'-diphenylmethane diisocyanate; inphorone diisocyanate, 4,4
Alicyclic diisocyanates such as '-dicyclohexylmethane diisocyanate; furthermore, aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2',4-)limethylhexamethylene diisocyanate; polymerizable monomers having hydroxyl groups include At least one double bond and one hydroxyl group
It is best to use low-molecular-weight compounds that contain 100% acetate, and typical examples include β-hydroxyethyl (meth)-acrylate and β-hydroxypropyl (meth)-acrylate.
Addition reaction products of (meth)acrylic acid with hydroxyalkyl (meth)acrylates such as acrylate, β-hydroxylauryl (meth)acrylate, or butyl glycidyl ether, phenyl glycidyl ether, persatic acid lycidyl ester, etc. Things like that.

Although the reaction between NCO groups and OH groups proceeds without a catalyst, for example, tertiary amines such as triethylamine; organometallic compounds such as dibutyltin silaurylate and dibutyltin diacetate; or tin chlorides, etc. Conventional catalysts may be used.

On the other hand, in order to obtain the latter resin of the polymerizable prepolymer (AI), the polyester polyol (a-1-1)
A preferred method is to esterify one hydroxyl group with (meth)acrylic acid or the like to introduce a double bond into the terminal or side chain.

Generally, the esterification is carried out in the presence of such a double bond, and also in the presence of an ester agent.

Typical examples of such esterification catalysts include 1)-) sulfonic acids such as luenesulfonic acid, methanesulfonic acid, and fluorinated methanesulfonic acid, and titanium compounds such as tetraisopropyl titanate; As the inhibitor, phenothiazine or nitrobenzene can be used.

As a result of such an esterification reaction, slight dispersion (meta)
Acrylic acid and esterification catalyst remain, but these can be completely removed much more easily by neutralizing them with an alkaline substance such as caustic soda and then washing with water, so one method is to remove them by such means. Yes, it is. However, in the present invention, since these residual substances do not pose any problem, it is of course possible to use a polymerizable polymer obtained by omitting the washing step.

The above polymerizable polymer ((conversion) is about 1100
It has a number average molecular weight of ~900 units and has a molecular weight of 1 per molecule.
0.6 to 2.511 per 000! , especially 1 to 1 per molecule
This polymerizable prepolymer (
If A) contains a crystalline part and a non-crystalline part in its molecule in an appropriate ratio, the features of the present invention will be fully exhibited, and furthermore, resins such as the above-mentioned resin (a-1) The polymerizable prepolymer into which urethane bonds have been introduced provides a hard and flexible film.

These polymerizable prepolymers (A) generally have a low Vi degree.

Since it is impossible to paint it by itself, it is recommended to use a diluent to lower the viscosity. As such diluent, known and commonly used diluents such as acetone, methyl ethyl ketone, toluene, xylene, methanol, ethanol, and Although it is possible to obtain a low viscosity composition by using an organic solvent with a large diluting effect such as banol, cellosolve, ethyl acetate or butyl acetate, if the composition becomes bulky, the final method according to the present invention is A single or two or more types of low-molecular compounds that have one or more monomorphic double bonds per molecule and have a boiling point of 200°C or higher, known as reactive diluents, without any disadvantages. It is preferable to use a mixed system of these polymerization-reactive diluents, and among these polymerization-reactive diluents, at least one yuzu contains hydroxyl groups.
It is essential that the diluent is functional or more polyfunctional, and the amount of such hydroxyl group-containing diluent used must be at least 10 it% of the total polymerization-reactive diluent (Bl). It takes.

Thus, the present invention is characterized by the combination of the polymerizable greborimer (a structural factor based on Al) and the hydroxyl-containing-functional or higher-functionality diluent, which constitutes the composition of the present invention ( Maximum metal adhesion with very good curability and flexibility, which cannot be predicted from a composition lacking either A) or (Bl). It is something that can be demonstrated.

Typical examples of the hydroxyl group-containing functional or polyfunctional reactive diluent B) in the present invention include R.

(I) Hydroxyethyl (meth) as shown by the general formula CH, = C-C-0-R, -OH1
Including hydroxyargyl (meth)acrylates such as acrylate, hydroxypropyl (meth)acrylate, and hydrobodipyl (meth)acrylate.

(However, R1 in the formula is as described above.) or a hydroxyl group-containing functional diluent such as trimethylolpropane diacrylate, pentaerythritol triacrylate, etc. Contains a polyfunctional diluent. Thus, the composition of the present invention is a polymerizable prepolymer of each of the above-mentioned (meth)acryloyl group-containing polyester urethane resin (&-1) and/or (meth)acryloyl group-containing polyester resin (a-2). , and especially the polymerizable dilution jllillB
It is characterized by containing 10M or more of the above-mentioned hydroxyl group-containing-functionality or higher polyfunctional diluent in 1.

The violet of these hydroxyl group-containing diluents is less than 10 kJ1% i
Sufficient metal adhesion cannot be obtained on the base.

On the other hand, other typical polymerization-reactive diluents that are compatible with the above-mentioned hydroxyl group-containing diluents include phenoxyethyl acrylate, ethyl diethylene glycol, tetrahydrofurfuryl acrylate, hexanediol diacrylate, and neopentyl. There are common reactive diluents such as glycol diacrylate, hydroxybivalyl nonopentyl glycol diacrylate, polyethylene glycol diacrylate or trimethylolpropanedryacrylate, etc., which can be used as one or a mixture of more than one. However, the above-mentioned hydroxyl group-containing diluents can also be used alone or in combination of a plurality of them.

The thus obtained polymerizable resin composition of the present invention is polymerized and cured by exposure to UV radiation, such as ultraviolet rays, X-rays, R-rays, or electron beams. Curing can also be accelerated by conventional photosensitizers such as benzoin or its alkyl ethers, benzophenone, anthraquinone, polynuclear quinones, disulfides or pencils. Further, it is appropriate to use the above-mentioned sensitizers such as benzophenone in an amount of 0.1 to 10 parts per 100 parts of the monomer resin composition.

The so-called clear paint, which is made by adding only the sensitizer to the polymerizable resin composition of the present invention, has excellent curing properties and is effective against materials such as steel, untreated steel, aluminum, copper, and brass. It also shows excellent adhesion.

Even in white enamels made by kneading Sarabanko with a pigment such as titanium white, the balance between metal adhesion and hardenability, which is a feature of the composition of the present invention, is never lost, and the composition of the present invention It is used as a paint for each shaft.

Next, the present invention will be specifically explained with reference to Examples, and in the following, "part" means "first part".

Synthesis Example 1 (Preparation Example of Polymerizable Prepolymer (A)) 50 parts of dimer acid, 150 parts of ethylene oxide adduct of bisphenol A, and 55 parts of isophthalic acid were mixed at a temperature of 220°C using a conventional esterification apparatus. The esterification reaction was carried out to an acid value of 5 to obtain a polyester polyol, and the reaction product was then cooled and dissolved and diluted with 200 parts of trimethylolpropane triacrylate. Thereafter, the active double bond and active isocyanate obtained by an addition reaction between 2 moles of inphorone diisocyanate (IPDI) prepared in advance and 1 mole of β-hydroxyethyl acrylate (β-HgA) are then added. 160 seconds of precursors having one each were added, and the reaction was continued at a reaction temperature of 70° C. until NGO% reached 0.5 to obtain a polymerizable acryloyl group-containing polyester urethane resin. Hereinafter, this will be abbreviated as prepolymer (A-1).

Synthesis Example 2 (same as above) 250 parts of the polyester polyol obtained in Synthesis Example 1 was dispersed in 20 parts of 1 Lactol Spirit (manufactured by Amsco Chemical Company, USA), processed with 30 parts of 98% acrylic acid, and further processed. The esterification reaction was carried out at 95°C with the addition of 80 ppm of phenothiazine, 25 ppm of nitrobenzene and 13 parts of methanesulfone to give an acid value of 5.2.
When the temperature reached 1 mHj 1%, the solvent was removed by vacuum distillation at 65°C. Next, this was diluted with 150 parts of trimethylolpropane triacrylate to obtain an acryloyl group-containing polyester resin. Hereinafter, this will be abbreviated as prepolymer (A-2).

Synthesis Example 3 (same as above) Phthalic anhydride 24 was added to this using a conventional esterification apparatus.
．． 5 parts and 17.2 parts of neopentyl glycol to 11
When the acid value reached 220 after the reaction at 0°C, 145.8 parts of dimer acid and 117.5 parts of [-Epicron 850J (epoxy resin manufactured by Inu Nippon Ink Chemical Industry ■) were added, and the reaction was carried out at a temperature of 150°C. The esterification reaction was carried out until the acid value reached 6 to obtain a polyester polyol. After cooling the esterification reaction product, it was dissolved and diluted in 270 parts of trimethylolpropane triacrylate. Next, the same precursor as used in Synthesis Example 1 was added to this bath solution.
Add 130 parts of J.

The reaction was continued at a reaction temperature of 70° C. until N00% reached 0.6 to obtain an acryloyl group-containing polyester urethane resin. Hereinafter, this will be abbreviated as prepolymer (A-, 5).

Synthesis Example 4 (same as above) Acid value 5.0 obtained by esterification in the same manner as Synthesis Example 1 except that 20 parts of dimer acid, 150 parts of ethylene oxide adduct of bisphenol A, and 9615 parts of inphthal were used. After cooling the polyester polyol, it was mixed with trimethylolpropane triacrylate 18
Then, 130 parts of the same precursor 'jt as used in Synthesis Example 1 was added, and the mixture was reacted at 70°C until N00% became 03 to obtain an acryloyl group-containing polyester urethane acrylate. Below, this is a prepolymer (
It is abbreviated as A-4).

Synthesis Example 5 (same as above) #*5 obtained by esterification in the same manner as in Synthesis Example 1, except that 2205.0 parts of dimer, 6 parts of Ia71kelRjO, and 495 parts of #yohyobentyl glycol were used. After cooling the polyester polyol, dilute it with 207 parts of trimethylolpropane triacrylate and add 135 parts of the same precursor as used in Synthesis Example 1 to give an NGO% of 0.03 at 70"C. An acryloyl group-containing polyester urethane resin was obtained.Hereinafter, this will be abbreviated as prepolymer (A-5).

Various polymerizable diluents were combined with each prepolymer obtained in each of the above synthesis examples, and a photoinitiator [Irga Cure+184J (Ciba Co., Ltd., West Germany) was added.
A coating obtained by adding 5 PHR of (manufactured by Geigy) to the coating was applied to an untreated mild steel plate, and immediately irradiated with a high-pressure mercury lamp to obtain a cured coating.

The results are summarized in Table 1.

(tf) Requirements for various test methods Hardenability: Output 80 W/ax manufactured by Iwasaki Electric ■
The film was cured using a single ultraviolet lamp with a line speed of 1011 I/min, and the film was closed in 11 passes.

At that time, a dry-to-touch test was conducted for each pass, and the number of cycles until dry to the touch was reached was indicated.

Hardness: The coating film after one bath was tested in accordance with JIS K-5400, Section 6.14 using the same procedure as for curability.

Adhesion...Approximately 1 coat of paint on each material with a record needle
Make 100 goblets at intervals of 111, cover the goblets thus obtained with cellophane tape and apply it with your foot, and instantly peel off the cellophane tape with great force to remove the goblins on the paint film that remained without being peeled off. I counted the number of eyes.

MEK Rubbing - Soak absorbent cotton in enough methyl ethyl ketone, use this cotton to rub with your index finger, and rub as described above.
This one round trip operation was counted as one time, and the number of times the remaining paint film was checked was displayed.

However, for the one that still remains after 200 attempts,
No further testing was performed, and after 1'200 cycles, the product was judged as passing.

Claims (1)

[Claims] ((meth)acryloyl group-containing polyester resin (a-1> and/or (meth)acryloyl group obtained using polyester polyol (a-1-1) containing 9 to yoMIIk% of Al dimer acid residues as a starting material) Group-containing polyester urethane resin (a-2) and (B1
The polymerization-reactive diluent is an essential component, and the former resin component is 20% by weight or more, and the latter diluent (81 components are 50% by weight).
A composition comprising m
1. A polymerizable resin composition in which 10% by weight or more of the reactive diluent (1) is a hydroxyl group-containing-functional or higher polyfunctional reactive diluent.