JPH0379615A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent photo-setting properties free from smell, providing coating films with improved physical properties, comprising a polymer containing a (meth)acryloyl group at the side chain and constituting C-C bond in the main chain and a specific (meth)acrylate. CONSTITUTION:The objective composition using both (A) a polymer containing a (meth)acryloyl group at the side chain and constituting C-C bond in the main chain and (B) an acetoacetyl group-containing (meth)acrylate having both (meth) acryloyl group and acetoacetic ester group. An unsaturated urethane-based polymer prepared by reacting a polymer containing hydroxyl group at the side chain with isocyanatoethyl methacrylate may be cited as the component A. The component B is preferably obtained by reacting a (meth)acryloyl group- containing unsaturated alcohol with diketene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photocurable (hereinafter referred to as UV cure) resin composition useful in the fields of coatings, inks, and adhesives.

[Conventional technology and issues]

UV cure can cure paint films, ink, etc. in a short time, is energy saving, and greatly contributes to improving productivity, as well as tJl due to UV cure.
Because ryA is hard and has a beautiful appearance, it is used for wood painting,
It is well known that it is useful and heavily used in offset printing inks and various resists related to electronics.

However, there are still some unresolved problems, and solving these drawbacks will be useful in expanding the range of applications.

The main reason is that since UV curing is too rapid, stress relaxation of the coating film during curing is difficult to occur, and as a result, the adhesion between the substrate and the coating film is significantly impaired.

When monofunctional monomers are used, this disadvantage becomes less noticeable, but it is exacerbated, especially when difunctional or higher polyfunctional monomers are used for dilution.

Unfortunately, existing monofunctional Motsumar has problems such as having a strong odor, being irritating to the skin, being easily affected by oxygen even when UV cured, and furthermore, decreasing the hardness of the coating film. points are pointed out. These are fatal disadvantages, and the advantages of using -sensual motsuma, such as W! Improved adhesion, greater dilution ability,
The current situation is that these advantages are being negated.

The present invention improves the drawbacks of conventional monofunctional motsumers, and although it is a functional motsumah, the photocurable resin using this has almost no odor and is also excellent in UV curing.
The present invention provides a composition in which the physical properties of the cured coating film are significantly improved compared to those using conventional monofunctional motumer.

[Means to solve the problem]

That is, the present invention provides (1) a polymer having at least one (meth)acryloyl group side chain in one molecule and a carbon-carbon bond forming the main chain; Contains an acetoacetyl group that shares a (meth)acryloyl group and an acetoacetate group (meth)
The present invention provides a curable composition comprising an acrylate.

Acetoacetyl group-containing (meth)acrylates that share an acetoacetate group and a (meth)acryloyl group are
Almost eliminates the drawbacks of the functional monomers mentioned above,
It has good photocurability and dilutability into polymers or oligomers.

Acetoacetyl group-containing (meth)acrylates that share an acetoacetate group and a (meth)acryloyl group are
An unsaturated alcohol having a (meth)acryloyl group,
It is synthesized by acetylacetonation with diketene.

2-Hydroxyethyl methacrylate Diketene υ (2-acetoacetyl ethyl methacrylate) The methylene bond between the two carbonyls of acetoacetate is active and easily causes a hydrogen abstraction reaction, and as is well known, acetoacetate shows typical keto-enol tautomerism and may be related to keto-enol photocuring.

Although the reason is not clear, polymers having acetoacetate groups in their side chains become insoluble in solvents when heated.

The raw material unsaturated alcohol for synthesizing the acetoacetyl group-containing (meth)acrylate that shares an acetoacetate group and a (meth)acryloyl group in one molecule, which is a component of the curable composition of the present invention, is , for example, the following types:

2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyphenyl methacrylate, polyethylene glycol mono (obtained by adding two or more molecules of ethylene oxide to (meth)acrylic acid) meth)acrylate, polypropylene glycol mono<meth>acrylate obtained by similarly adding propylene oxide, and monomers having a terminal hydroxyl group obtained by adding caprolactone to an unsaturated alcohol having a (meth)acryloyl group.

Although primary hydroxyl groups of unsaturated alcohols are more easily converted into acetylacetonate, even secondary ones can be converted into acetylacetonate by selecting conditions.

The other component of the curable composition of the invention, 1
The following types of polymers having at least one (meth)acryloyl group side chain in the molecule and carbon-carbon bonds forming the main chain are synthesized and utilized.

(1) An unsaturated urethane-based polymer that has a (meth)acryloyl group in the polymer side chain via a urethane bond. ) An adduct of a diisocyanate and an unsaturated alcohol having a (meth)acryloyl group.

(2) A polymer having an epoxy group in its side chain is reacted with (meth)acrylic acid. Polymers having an epoxy group in its side chain include the following: (a) The epoxy group is glycidyl methacrylate. The polymer obtained by polymerization or (meth)acrylic acid is added to two or more epoxy groups, and the ratio of carboxyl groups to epoxy groups is C00.
A vinyl monomer is copolymerized with an oligomer having an epoxy group and a (meth)acryloyl group in one molecule, which is reacted at l'l/epoxy of 0.5 or less, preferably 0.2 or less, to form an epoxy side chain. A method for producing a polymer having groups.

(3) A polymer having an acid anhydride group in its side chain is reacted with an unsaturated alcohol having a (meth)acryloyl group.

The polymers mentioned in (1), (2> and (3) above are:
All of them are obtained by polymerization reaction of corresponding monomers, and have a number average molecular weight of 5,000 or more.

This is because oligomer types with a molecular weight of 5,000 or less tend to be inferior to polymer types in coating film properties such as adhesion, resistance to bending, resistance to impact, etc.

Although there is no need to particularly limit the monomers constituting the polymers, examples of monomers having suitable functional groups for producing each of the above-mentioned polymers include the following types.

(a) As monomers having a hydroxyl group, the aforementioned unsaturated alcohol having a (meth)acryloyl group is generally used, but allyl alcohol can also be used.

(b) Glycidyl methacrylate is practically the only monomer having an epoxy group.

Further, as the epoxy resin, various commercially available resins can be used as they are.

(c) Maleic anhydride and itaconic anhydride are used as the monomer having an acid anhydride group.

Copolymerizable monomers may be used in combination with the monomers having these functional groups, such as the following types.

Styrene, vinyltoluene, chlorostyrene, methyl methacrylate, methacrylic esters, acrylic esters, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylpyrrolidone, butadiene, isoprene, monomers with functional groups and these There is no particular restriction on the ratio of the monomer to be copolymerized with the functional group monomer, but it is 1 mol% or more and 50 mol%
The following is suitable, and more preferably 3 mol% or more and 30 mol% or less.

Any existing method can be used as the polymerization method.

Commercially available diisocyanates can be used as they are as diisocyanates which react with polymers having hydroxyl groups in their side chains to form unsaturated incyanates to form polymers having (meth)acryloyl groups, but commercially available types can be used as they are. Types such as diisocyanate and inphorone diisocyanate, in which two isocyanate groups have different reactivity, are useful.

The ratio of the polymer having a (meth)acryloyl group in the side chain and the acetoacetyl group-containing (meth)acrylate sharing an acetoacetate group and a (meth)acryloyl group is 10% by weight or more and 90% by weight of the latter. (%) or less, more preferably from 20 weight (%) to 70 weight (%).

If the proportion of the acetoacetyl group-containing (meth)acrylate used is low, the viscosity of the mixed system tends to be too high, and if the proportion used is too high, the meaning of the combined use of the unsaturated polymer is lost.

You are free to use any other monomers, but
In such a case, if the proportion of acetoacetoyl monomer used is less than 5% by weight, it tends to be difficult to exhibit the characteristics.

It goes without saying that the UV-curable composition according to the present invention can be used in combination with reinforcing materials, fillers, colorants, mold release agents, thermoplastic polymers, etc., as necessary.

Next, the present invention will be explained in more detail with reference to Examples.

°In an autoclave, 650y (5 mol) of 2-hydroxyethyl methacrylate, 5g of dibutyltin dilaurate.
After charging 0.5 g of rose benzoquinone, N2 substitution was performed three times at 3.0-+0.2+kg/cm''.

Next, 462 g (5 ml) of digetene was added to the dropping funnel while stirring.
, 5 mol) was added dropwise to the autoclave under a pressure of about 5 kg/cw'' with N2.

While dropping, the temperature was raised due to heat generation, and the reaction was carried out at a reaction temperature of 60° C. for 3 hours.

After dropping, while reducing the pressure to 0.71 g 7 cm,
The reaction was completed by maintaining the temperature at 60°C for 1.5 minutes.

The generated 2-acetoacetylethyl methacrylate is
The purity was 95%, and it was a pale yellowish brown liquid.

X1 LJ- (meth)acryloyl via a urethane bond in the side chain
Styrene 1042.2-
Hydroxyethyl methacrylate 26g, ethyl acrylate 75y, acrylic acid 5g, methyl ethyl ketone 19
0 g, azobisisobutyronitrile 2 g, and t-butyl mercaptan 0.5 g, and heated at 70 to 75°C in a nitrogen stream.
After polymerization for 8 hours, 1 g of azobisisobutyronitrile was further added, and the polymerization was further carried out for 12 hours, resulting in a 6-polymerization rate of about 92 (%). Polymerization was stopped by adding 0.1y of hydroquinone.

The temperature was lowered to 60°C, 30 g of incyanatoethyl methacrylate and 0.6 g of dibutyltin dilaurate were added in a stream of dry air, and the mixture was reacted at 60°C for 5 hours. As a result of infrared analysis, free isocyanate groups completely disappeared. This was confirmed.

210 g of 2-acetoacetoylethyl methacrylate was added to the polymer obtained above, and methyl 1-methylketone was eluted under reduced pressure at 65 to 70°C, and finally 10 To
Volatile matter was removed by reducing the pressure to rr.

A pale yellow, viscous polymer (2-acetoacetoylethyl methacrylate solution) (A) having a methacryloyl group in the side chain via a urethane bond was obtained.

Sarachiku Earthwork 1 100 parts by weight of polymer (A) (the weight is omitted below) and Merck Co., Ltd. "Darocure #1173°゛3" as a photoinitiator
The mixture was coated on a Bonderite steel plate to a thickness of 50 μm, and after degassing, the mixture was passed through a 10 cm distance under an ultraviolet lamp with an output of 2 KW at a speed of 11 I/min.

Curing occurred in one pass.

The resulting coating film had a hardness of 2H and an adhesion of 100/100 according to a cross-cut test.

``Ban'' U tip ttX length 12.5cm, width 2.5cm, thickness 3mm steel plate #6
Polish well with 00 sand vapor, wash with 1,1,1-trichloroethane, and add 50 parts of polymer (A) to 1.3 cm of the end.
A mixture of 50 parts benzoyl peroxide, 1 part dimethylaniline, and 0.1 part was coated, overlapped, and left overnight at room temperature.

Adhesive strength by tensile shear is 151 to 219 kg/a
s” was shown.

208 g of styrene was charged into a separable flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, and the temperature was 120 to 120. At 125° C., a mixture of 30 g of molten maleic anhydride and 2 g of lauryl mercaptan was added dropwise in a nitrogen gas stream over 4 hours.

When the temperature was kept at the same temperature for 1.5 hours after the completion of the dropwise addition, no coloring was observed in the dimethylaniline or triphenylphosphine test, and free maleic anhydride appeared to have disappeared.

Add 0.1g of hydroquinone to stop polymerization, and lower the temperature to 8.
Lower the temperature to 0°C and add 52 g of 2-hydroxyethyl acrylate.
, 1 g of triethylamine was added and the mixture was reacted for 5 hours. As a result of infrared analysis, it was found that 90% or more of the acid anhydride groups had reacted.

The polymer solids content was approximately 52%.

Then 2-acetoacetoylethyl acrylate 110
In addition, a polymer (mixed monomer solution of styrene and 2-acetoacetoylethyl acrylate) (B) having an acryloyl group in the side chain via an ester bond is pale yellow,
It was obtained with a viscosity of 9.1 voids.

Toyofu lid 1: 100 parts of polymer (B), 10 ppm of silicone antifoaming agent
, 1 part of Erosil, and 0.3 part of cobalt naphthenate were roll-kneaded to make a homogeneous solution, and then 1 part of methyl ethyl ketone peroxide was added. After gelation, it rapidly generated heat in about 14 minutes, and the maximum exothermic temperature was The temperature reached 158°C.

The bending strength of the FRP plate obtained by laminating #450 glass mats to a thickness of 3 cypresses was excellent at 22.9 kfI/mw2 (glass content 28.1%).

In a 21 separable flask equipped with a stirrer, reflux condenser, thermometer, and gas inlet tube, 380 g of bisphenol A diglycidyl ether with an epoxy equivalent of 187 as an epoxy resin, 22 g of methacrylic acid, 0.8 g of trimethylbenzylammonium chloride, and 0 hydroquinone were added.
．． 02g was charged and heated at 130-135°C for 1 hour in a stream of air.

The acid value became virtually zero.

Styrene 1020y was added to this, polymerization was carried out at 130-135°C in a nitrogen stream until the reaction rate reached approximately 38%, the temperature was lowered to 110°C, 0.79% of hydroquinone was added, and 65t of methacrylic acid was added. , add 2.2 g of trimethylbenzylammonium chloride, and heat to 105-110°C.
After 6 hours of reaction, the acid value was 14.7. A mixed polymer of a vinyl ester oligomer and a polymer having a vinyl ester bond in the side chain was obtained.

t This mixed polymer was divided into two parts, and 50 parts of 2-acetoacetylethyl methacrylate as the polymer (C) and 30 parts of styrene as the polymer (D) were added per 100 parts of the mixed polymer.

The viscosity was between 5 and 7 voids in all cases.

Toyotoshi 1: 100 parts each of polymer (C) and polymer (D), 30 parts of #325 glass flakes, 2 parts of silane coupling agent -174, Erosil OJB part, silicone antifoaming agent 1099m, naphthenic acid Add 1 part of cobalt,
After mixing thoroughly, add 1 part of #328E from Kayaku Nouri Co., Ltd.
．． 5 parts were added and each coated on a Bonderite steel plate to a thickness of 100 μm.

Polymer (C) gels for about 15 minutes, and polymer (D) gels for about 15 minutes.
) was about 35 minutes.

After leaving it in a constant temperature bath at 40°C overnight, the coating film was subjected to a Dolly test using an Elcometer, and the tensile adhesive strength of the coating film using polymer (C) was 55 to 70 kg/c.
1 Coating film using polymer CD> 35-40 kg/
A large difference with am' was observed.

Methyl methacrylate (90%) was added to a separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a gas inlet tube.
y, 128 t of isobutyl methacrylate, 29 g of 2-hydroxypropyl methacrylate, 1.3 g of lauryl mercaptan, 203 g of methyl ethyl ketone, and 2.5 g of azobisisobutyronitrile were charged and polymerized for 6 hours in a nitrogen stream at 70 to 75°C, and then further Add 1.5 l of azobisisobutyronitrile and react for 12 hours. The zero polymerization rate when 0.129% of hydroquinone was added to stop the polymerization was approximately 9.
It was 4 (%).

As an unsaturated isocyanate, 90 g of a reaction product of 174 g (1 mol) of 2,4-)lylene diisocyanate and 169y (1,3 mol) of 2-hydroxyethyl methacrylate, 1 g of dibutyltin dilaurate, and 130 g of methyl ethyl ketone were added. After reacting at 60 to 65° C. for 3 hours, infrared analysis confirmed that free incyanato groups disappeared.

I t 80 g of 2-acetoacetoylethyl acrylate was added and a polymer (meth)acryloyl group-containing polymer (mixed solution of methyl ethyl ketone and 2-acetoacetoylethyl acrylate) (E) was obtained as a pale yellow liquid through urethane bonds. .

Aidome 1 100 parts of polymer (E) and # on 35μ thick electrolytic copper foil
A photocurable resin containing 2 parts of 1173 was coated to a thickness of 50 μm, and methyl ethyl ketone was evaporated in a constant temperature bath, initially at 40° C. and then at 80° C.

The resulting coating film was non-adhesive.

A desired shape that does not transmit light was placed on the coating film, and 10 cIl of ultraviolet light was passed through it at a speed of 50 cm/min under an ultraviolet irradiation device with an output of 2 kW.

When immersed in methyl ethyl ketone, the uncured portion is eluted,
The photocured portion remained on the copper foil, forming a pattern.

〔Effect of the invention〕

Since the present invention uses a composition having the above-mentioned structure, it is possible to obtain a cured resin that has a fast curing speed, high hardness, and little internal distortion.

Claims (1)

[Scope of Claims] 1. (1) A polymer having at least one (meth)acryloyl group side chain in one molecule and in which the bond constituting the main chain is carbon-carbon, and (2) 1 Contains an acetoacetyl group (meth) that shares a (meth)acryloyl group and an acetoacetate group in the molecule
A curable composition comprising an acrylate. 2. A polymer having at least one (meth)acryloyl group side chain in one molecule and a carbon-carbon bond constituting the main chain has a (meth)acryloyl group via a urethane bond. A curable composition according to claim 1, characterized in that: 3. Polymers having at least one (meth)acryloyl group side chain in one molecule and carbon-carbon bonds constituting the main chain can be used to form secondary molecules through ring-opening of epoxy groups via ester bonds. The curable composition according to claim 1, which is a polymer having a (meth)acryloyl group having a structure having a hydroxyl group. 4. A polymer that has at least one (meth)acryloyl group side chain in one molecule, and the bond that constitutes the main chain is carbon-carbon, has a (meth)acryloyl group via an ester bond A curable composition according to claim 1, characterized in that: