JPH0733420B2 - Curable resin composition - Google Patents

Description

The present invention relates to a radical-curable resin composition useful in various fields such as lamination, casting, and adhesion, and a method for producing the same.

[Conventional technology and problems]

Conventionally, there are polyester resins, vinyl ester resins and the like as radical curable resins, and they have been used for a wide range of applications. However, these existing resins are not all-purpose, and it can be said that there will be applications in which it becomes difficult to meet with the development of fields of use and sophistication of requirements.

That is, all of the existing radical curable resins belong to oligomers having a molecular weight of several hundred to several thousand, and therefore, depending on the use, for example, a molding material or the like has an increased molecular weight (this may be called thickening). However, it is difficult to secure certain conditions.

In addition, when molding an artificial marble bathtub by casting, a balance between the toughness of the resin for preventing cracks, boiling whitening resistance, yellowing, and the like is required.

[Means for Solving the Problems]

That is, the present invention includes (1) an acid anhydride composed of 0.1 to 50 mol% of a radical-polymerizable unsaturated compound having an acid anhydride group, and 99.9 to 50 mol% of monomers which are radically copolymerized with the unsaturated compound. A polymer having a group and a molecular weight of 10,000 or more and 100,000 or less, and (2) one end of the molecule is a (meth) acryloyl group, the other end is a hydroxyl group, and 2 in one molecule. The present invention provides a curable resin composition which is used in combination with one or a polyester acrylate having two or more ester bonds.

In this case, the combination means that both components (1) and (2) may simply be mixed immediately before molding, or the acid anhydride group of (1) and the hydroxyl group of (2) may be previously reacted with each other. You can keep it.

The polymer having a molecular weight of 10,000 or more and 100,000 or less in (1) above is
It contains substantially one or more acid anhydride groups in the molecule. Here, the reason is substantially explained as follows, for example.

If we look at the copolymerized polymer of styrene and maleic anhydride, if the composition is 99 moles of styrene and 1 mole of maleic anhydride, this polymer is one acid anhydride if the molecular weight is 10,000 or more. It becomes a calculation having a group.

Similarly, if the molecular weight is 100,000, the molar ratio of maleic anhydride should be 0.1%.

From a practical point of view, the molecular weight of the polymer containing an acid anhydride group is preferably 10,000 or more and 100,000 or less. Therefore, the proportion of the unsaturated acid anhydride used is 0.1 mol% or more and 50 mol% or less, preferably 1 mol% or more 30 It is not more than mol%.

Among the radically polymerizable unsaturated compounds having an acid anhydride group, maleic anhydride is the most typical, and is most suitable for the purpose of the present invention. In addition to these, itaconic anhydride and the like can be used although the cost is high.

Monomers for radical copolymerization with these unsaturated acid anhydrides to form a polymer having an acid anhydride group,
If copolymerization is possible, there is no particular need to add any limitation. For example, there are the following types. Examples thereof include styrene, vinyltoluene, chlorostyrene, methyl methacrylate and methacrylic acid esters, acrylic acid esters, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, isobutylene, ethylene and the like. Further, it is of course possible to use these in combination.

The polymerization method is carried out by the existing methods, but the thermal polymerization method in an inert gas stream without using a catalyst is the most convenient. It is not necessary to complete the polymerization, and it is convenient to leave the monomer and use it as a monomer solution.

As one aspect of polymerization, for example, maleic anhydride is also added to a thermoplastic polymer by a grafting method, which is not necessarily unavailable, but it has a particular advantage as compared with the polymerization method. I don't think there is.

One component of the present invention is a polyester having a (meth) acryloyl group and a hydroxyl group. Such a polyester acrylate can be easily synthesized by a ring-opening addition reaction using (meth) acrylic acid or glycidyl methacrylate with an alkylene monoepoxide and a polybasic acid anhydride.

Another method is the ring-opening addition of caprolactone to unsaturated monoalcohols having a (meth) acryloyl group.

A transesterification reaction of the (meth) acrylic acid esters with the polybasic acid methyl ester or glycol can be used, but the cost tends to be disadvantageous.

Examples of the type of monoepoxide used in the present invention include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide, phenyl glycidyl ether, allyl glycidyl ether, and butyl glycidyl ether.

As the acid anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, anhydrous Het acids or mixed acids thereof are also used.

For the ring-opening addition reaction, a Lewis base, a phosphine compound, a quaternary ammonium salt, a quaternary phosphonium salt,
A catalyst such as an alkali metal alcoholate is required.
The reaction is usually carried out by adding a polymerization inhibitor in the presence of air.

The use ratio of the polymer having an acid anhydride group and the unsaturated polyester acrylate is selected according to the purpose,
Polymer is 99-10% by weight (weight is omitted below) 1-90% unsaturated polyester acrylate, preferably 95%
It is in the range of -30% and 5-70%. When both components are mixed and molded, the curing is carried out by radical polymerization of the (meth) acryloyl group of the unsaturated polyester and copolymerization with the monomer, and acid anhydride group in the polymer and hydroxyl of the unsaturated polyester. It is performed by a competitive reaction with an addition reaction.

Therefore, in this case, it is necessary to use a radical generating catalyst as a curing catalyst and a catalyst for ring-opening addition reaction of an acid anhydride group and a hydroxyl group (for example, a Lewis base or an alkali metal alcoholate).

The resin composition according to the present invention is mild in heat generation during curing and hardly cracks, and the cured resin is hard but has elongation and exhibits toughness.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to further correct the drawbacks caused by the restriction of the molecular weight of the existing resin, and at the same time, it can be advantageously applied to an application requiring compatibility of flexibility and strength, for example, a copper clad laminate.

The curable composition according to the present invention can, of course, be used in combination with a filler, a reinforcing material, a coloring agent, a defoaming agent, a release agent, polymers, etc., if necessary.

Next, the present invention will be described in more detail with reference to examples. In the examples, "parts" means "parts by weight" unless otherwise specified.

Example 1 Synthesis of Styrene-Maleic Anhydride Copolymer (A) 967 g of styrene was weighed in a 2 separable flask equipped with a stirrer, a heating dropping funnel, a reflux condenser, and a thermometer with a gas introduction tube, and nitrogen gas was added. 69 g of molten maleic anhydride was added dropwise at 120 ° C. to 125 ° C. in an air stream over 4 hours. During this period, 2.5 g of lauryl mercaptan was added every hour by 2.5 g.

After the dropping of maleic anhydride was completed, the temperature was kept at the same temperature for 1 hour, and it was confirmed that free maleic anhydride had disappeared with dimethylaniline tellate, and 0.1 g of hydroquinone was added to terminate the polymerization. The number average molecular weight is about 38,000, the polymerization rate reaches about 52%, the molar ratio of styrene and maleic anhydride in the copolymer is about 85:15, and the Hazen color number is 2
A styrene-maleic anhydride copolymer (A) having 0 and a viscosity of 11.4 poise was obtained.

Production of polyester acrylate (B) A stainless steel reaction vessel equipped with a stirrer, thermometer, gas inlet, and reflux condenser was charged with 740 parts phthalic anhydride, 430 parts methacrylic acid, 0.3 parts hydroquinone, and 5 parts triphenylphosphine. Then, the temperature was raised to 130 ° C., 630 parts of propylene oxide was injected under pressure for 1 hour, and the reaction was continued for 1 hour until the acid value became 2 or less, so 760 parts of styrene was added,
Polyester acrylate (B) was obtained. Hazen color number
The viscosity was 450 and the viscosity was 3.4 poise.

Synthesis and physical properties of curable resin (I) In a one-separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 500 parts of styrene-maleic anhydride copolymer (A) prepared as described above, polyester acrylate ( B) 230 parts, triphenylphosphine 3
And 0.3 part of hydroquinone were reacted at 100 ° C. for 5 hours in the presence of a styrene monomer. As a result of infrared analysis, it was estimated that about 80% of the acid anhydride groups had disappeared. To this, styrene
270 parts were added to obtain the desired resin (I). The Gardner color number was 3 and the viscosity was 19.3 poise.

To 100 parts of Resin (I), 2 parts of Kayaku Nouri Co. # 328EM and 0.5 part of cobalt naphthenate were added and cured, and further 120 ° C 2
Post-curing was performed for an hour.

Table 1 shows the physical properties of the obtained test piece.

Example 2 Synthesis of Polymer (C) Having Acid Anhydride Group In a one-separable flask equipped with a stirrer, a reflux condenser, a gas introduction tube, and a thermometer, 250 g of styrene and 20 g of methacrylonitrile were charged, and the mixture was heated to 130- 135 ° C
Then, 30 g of molten maleic anhydride was added dropwise over about 3 hours.

At the end of the dropwise addition, the viscosity increased and stirring became somewhat difficult, so 52 g of styrene was added, the temperature was lowered to 120 ° C., and polymerization was continued for another 2 hours. It was observed that the maleic anhydride had disappeared.

As a result of gas chromatographic analysis, the residual amount of methacrylonitrile was estimated to be 0.3% or less.

Hydroquinone (0.1 g) and styrene (104 g) were added, and a polymer (C) having an acid anhydride group was obtained with a Hazen color number of 150 and a viscosity of 9.1 poise.

Synthesis of unsaturated polyester-acrylate (D) In a one-separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 72 parts of acrylic acid, 165 parts of methyltetrahydrophthalic anhydride, 114 parts of allyl glycidyl ether,
Phenylglycidyl ether 180 parts, sodium methylate 2.5 parts (solid content), triphenylphosphite 2.5
And hydroquinone (0.3 parts) were charged and reacted at 100 to 110 ° C for 4 hours, and the acid value reached 10.1, so it was stopped.
Unsaturated polyester-acrylate (D)
Got The Hazen color number was 200 and the viscosity was 3.2 poise.

Synthesis of curable resin (II) and coating film physical properties 250 parts of polymer (C) having an acid anhydride obtained as described above, polyester-acrylate (D) 100
Parts, sodium methylate 1 part, copper naphthenate 2ppm,
The reaction was carried out at 90 to 100 ° C for 5 hours. As a result of infrared analysis, it was estimated that about 80% of the acid anhydride groups were ring-opened and added.

50 g of styrene was added, and Resin (II) was obtained with a Hazen color number of 350 and a viscosity of 10.7 poise.

100 parts of resin (II), # 328EM on the bonderite copper plate 1.
A mixture containing 5 parts, 0.5 part of cobalt naphthenate and 0.2 part of acetoacetoylmorpholine was coated to a thickness of 50 μm.

After about 1 hour, it was dried to the touch, and after 6 hours, it became possible to polish.

The cured coating film had a pencil hardness of 2H and had a beautiful glossy film after polishing.

〔The invention's effect〕

Since the curable resin of the present invention is configured as described above, at the same time as correcting the defects of the existing resin, the heat generated during curing is gentle, and the cured resin is hard but has elongation and exhibits toughness,
Since it is possible to achieve a good balance between flexibility and strength, it can be applied to a wide range of fields.

Claims (1)

[Claims] (1) 0.1-50 mol% of a radical-polymerizable unsaturated compound having an acid anhydride group, and monomers 99.9 radical-copolymerizable with this unsaturated compound
A polymer having an acid anhydride group composed of ˜50 mol% and having a molecular weight of 10,000 or more and 100,000 or less, and (2) one end of the molecule is a (meth) acryloyl group and the other end is A curable resin composition, which is used in combination with a polyester acrylate having a hydroxyl group and having two or more ester bonds in one molecule.