JPH04154823A - Active energy ray-curable unsaturated polyester, its production and resin composition containing the same - Google Patents

Abstract

PURPOSE:To obtain the title flexible polymer excellent in curability by reaction of an alpha,beta-unsaturated dicarboxylic acid, alpha,omega-((hydrogenated)polybutadiene glycol, acid anhydride and unsaturated monoglycidyl compound in a specified order. CONSTITUTION:Firstly, a reaction is made, in the presence of an excess of an alcohol, between (A) an alpha,beta-unsaturated dicarboxylic acid (anhydride) (pref. fumaric acid) and (B) an alpha,omega-(hydrogenated)polybutadiene glycol, and, if needed, (C) a polyhydric alcohol and/or polybasic acid, and the resultant reaction product is allowed to react with (D) an acid anhydride (pref. maleic anhydride). Then the reaction product thus obtained is made to react with (E) an unsaturated monoglycidyl compound [pref. glycidyl (meth)acrylate], thus obtaining the objective polymer modified with both the components B and E.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a new and useful active energy ray-curable unsaturated polyester, a method for producing the same, and a resin composition containing the same. More specifically, an unsaturated polyester modified with (hydrogenated) polybutadiene glycol and an unsaturated monoglycidyl compound, which has excellent curability and cutting properties, and a method for producing the same; , relates to a resin composition containing the same.

(Conventional technology) Recently, due to social needs, productivity is high, and
Demand for high-performance paints is increasing.

Such a paint should (1) be fast curing;
Active energy ray-curable resins are used because of their advantages such as (2) low energy costs and (3) non-pollution due to solvent-free use.

For example, in wood painting, unsaturated polyester made by reacting a polyhydric alcohol component and/or a polybasic acid component is desirable for its luster and texture, and in order to give a beautiful finish, it is cured with active energy rays. It is widely used in the field of wood coatings.

(Problems to be Solved by the Invention) In general, although the cured product of polybutadiene unsaturated polyester resin compositions has excellent flexibility, flexibility, and water resistance, it is difficult to cure with active energy rays. In some cases, it has the disadvantage of slow curing.

(Means for Solving the Problems) However, as a result of intensive research to solve the above problems, the present inventors have completed the present invention.

That is, the present invention provides, on the one hand, a specific unsaturated polyester modified with (hydrogenated) polybutadiene glycol and modified with an unsaturated monoglycidyl compound, and on the other hand, The following describes a method for producing such a specific unsaturated monoglycidyl compound-modified/polybutadiene-modified unsaturated polyester, and thirdly, a method for producing such a specific unsaturated monoglycidyl compound-modified/polybutadiene-modified unsaturated polyester and the polymerizable monomer. The object of the present invention is to provide a resin composition comprising a polyamide and a polyester as an essential film-forming component.

That is, α,β-unsaturated dicarboxylic acid or its anhydride, α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol, acid anhydride, and unsaturated monoglycidyl compound, respectively, First, α,β-unsaturated dicarboxylic acid or its anhydride, α,ω-polybutadiene glycol and/or α,ω- Hydrogenated polybutadiene glycol is essential, and a polyhydric alcohol and/or a polybasic acid is also used, the reaction is carried out in an excess of this polyhydric alcohol, and then an acid anhydride is reacted. Alternatively, firstly, α , ω-polybutadiene glycol and/or α.

ω-hydrogenated polybuttadiene glycol and acid anhydride are used as essential ingredients, and a polyhydric alcohol or a polybasic acid is also used, and the reaction is carried out in an excess of this polybasic acid. By reacting the reaction product with an unsaturated monoglycidyl compound, we can produce the desired product with excellent active energy ray curability (hydrogenation).
An unsaturated polyester modified with polybutadiene glycol and an unsaturated monoglycidyl compound, a method for producing the same, and a resin composition using the polybutadiene-modified and unsaturated monoglycidyl compound-modified unsaturated polyester thus obtained. This is what we provide.

Here, first of all, among the above-mentioned α,β-unsaturated dicarboxylic acids or anhydrides thereof, only the most representative examples are maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid. such as acids.

Next, to exemplify only particularly representative α,ω-polybutadiene glycols, rPB
These include various [Nfsso PBGJ grades made by Nippon Soda Co., Ltd., including G-700J and the like.

On the other hand, if we only exemplify particularly representative α,ω-hydrogenated polybutadiene glycols,
Examples include HPBGJ grade manufactured by Shin Nippon Chemical Co., Ltd.

Further, among the above polyhydric alcohols that may be used as necessary, only particularly representative ones are exemplified.
Examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexanediol.

In addition, among the polybasic acids that may be used as necessary, only representative examples include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or adipic acid. etc.

Next, among the acid anhydrides mentioned above, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are mentioned to exemplify only the most representative ones. .

Further, among the unsaturated monoglycidyl compounds mentioned above, to exemplify only the most representative ones, glycidyl acrylate, glycidyl methacrylate, etc. of unsaturated basic acids such as acrylic acid or methacrylic acid. or glycidyl ethers of unsaturated alcohols such as allyl alcohol or methallyl alcohol, such as allyl glycidyl ether or methallyl glycidyl ether.

Here, the above-mentioned α,β-unsaturated dicarboxylic acid or its anhydride, polybasic acid used as necessary (referred to as the first component), α,ω-polybutadiene glycol and/or α,ω - The reaction between the hydrogenated polybutadiene glycol and the optionally used polyhydric alcohol (second component) is carried out at a molar ratio of second component/first component of 1.0 to 1.5. It is preferable to carry out the reaction in an excess of alcohol, and then react with an acid anhydride (which is used as the third component).

As such α,β-unsaturated dicarboxylic acid, it is particularly desirable to use fumaric acid, and its ratio, that is, the ratio occupied by the above-mentioned first component, is preferably within the range of 80 to 100 mol%.

In addition, the acid value after the reaction of acid anhydride is 50 to 150.
It is appropriate to fall within the following range.

On the other hand, in the reaction of α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol with an acid anhydride, the molar ratio of third component/first component is 1.
It is carried out under an acid excess of 0 to 1.5.

Among these acid anhydrides, it is preferable to use maleic anhydride, and the acid value after the reaction of the acid anhydride is 50 to 50.
A range of 100 is appropriate.

The above reaction can be carried out, for example, in an inert gas atmosphere for 1
It is carried out at a temperature of about 00 to 250°C.

Furthermore, an unsaturated monoglycidyl compound (referred to as the fourth component) has an epoxy group of 0.4 to 1 per equivalent of the acid group.
．． It is preferable to carry out the reaction in such a proportion that the amount becomes 0 equivalent.

As such unsaturated monoglycidyl compounds, it is particularly desirable to use glycidyl acrylate or glycidyl methacrylate.

This reaction is carried out, for example, in an air atmosphere at a temperature of about 90 to 110°C.

The unsaturated polyester of the present invention or the unsaturated polyester obtained by the method of the present invention has: - a polymerizable monomer having one or more polymerizable unsaturated double bonds in the molecule; body, and if necessary,
An active energy ray-curable resin composition can be prepared by also mixing a photoinitiator.

As such polymerizable monomers, any known and commonly used monomers can be used, but among them, only representative examples include styrene, α-methylstyrene, vinyltoluene, and chlorine. Aromatic vinyl monomers such as styrene; acrylic acid or methacrylic acid or their alkyl esters; or acrylonitrile, vinyl acetate, allyl acetate, triallylisocyanurate, acrylamide, diaseptone acrylamide, β-hydroxy ( meth)acrylate or diallyl phthalate.

The ratio of the polymerizable monomers to be mixed is not particularly limited, but from the viewpoint of curability, viscosity, flexibility, etc., the ratio of unsaturated polyester modified with polybutadiene and unsaturated monoglycidyl compound is preferably 50 parts by weight
A range of 100 parts by weight is suitable.

As the polymerizable monomer, it is desirable to use styrene from the viewpoint of curability, viscosity, cost, etc.; It is preferable to use more than one species in combination.

Examples of the polymerizable monomer used with styrene include the various polymerizable monomers listed above.

Among them, particularly representative ones include alkyl (meth)acrylates represented by methyl methacrylate, β-hydroxy (meth)acrylates, (meth)acrylonitrile, and (meth)acrylamides.

Furthermore, as the photoinitiator, any known and commonly used photoinitiator can be used, but among them, particularly representative ones include benzoin, benzoin methyl ether, benzophenone, benzyl dimethyl ketul, and 1- Examples include hydroxycyclohexylphenyl ketone.

Furthermore, depending on the purpose, the active energy ray-curable resin composition of the present invention may be used with other commonly used vinyl ester resins, vinyl urethane resins, polyisocyanate compounds, polyepoxide acrylic resins, alkyd resins, urea resins, etc. Resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyesters or saturated polyethers, cellulose derivatives such as nitrocellulose or cellulose acetate butyrate, linseed oil, Tung oil, soybean oil,
fats and oils such as castor oil or epoxidized parts,
Natural or synthetic polymeric substances, various fillers such as calcium carbonate, talc, mica, clay, silica paratha, colloidal silica, asbestos powder, aluminum hydroxide, zinc stearate, titanium white zinc white, red iron or azo pigments, It is also possible to add polymerization inhibitors such as pigments, hydroquinone, benzoquinone, toluhydroquinone, and paratertiary-butylcatechol.

The active energy ray-curable resin composition of the present invention thus obtained is extremely useful and can be applied to coating various substrates.

(Example) Next, the present invention will be explained by reference examples, examples, and comparative examples.
Although the layers will be described in detail, the present invention is not limited to these examples.

In the following, all parts and percentages are based on weight unless otherwise specified.

Reference example 1 (Preparation example of polybutadiene-modified unsaturated polyester) 232 g (2 mol) of fumaric acid and rPBG-700
α,ω-polybutadiene glycol manufactured by JC Nippon Soda Co., Ltd.; 2.100 g (3
mol) was subjected to heating dehydration condensation at 170° C. under an inert gas atmosphere to obtain Intermediate-1 having an acid value of 30 in solid content.

Next, 147 g (1.5 mol) of maleic anhydride was added thereto, and the mixture was reacted by heating at 120° C. under an inert gas atmosphere to obtain Intermediate-2 with an acid value of 65 in solid content.

Thereafter, this intermediate-2 was cooled to 80°C and made into an air atmosphere, and the 184.6 of glycidyl methacrylate was
g (1.3 mol), 664°6 g of styrene, 0.26 g of hydroquinone, and 7.7 g of triphenylphosphine were added, and the reaction was heated at 80°C until the Gardner viscosity at 25°C (the same applies hereafter) was determined by Z2 ZS. ,
In addition, a polybutadiene-modified and unsaturated monoglycidyl compound-modified unsaturated polyester having an acid value of 7 was obtained.

Hereinafter, this will be abbreviated as compound (A-1).

Reference Example 2 (Preparation example of polybutadiene-modified unsaturated polyester resin for comparison) 232 g (2 mol) of fumaric acid, 1,260 g (1.8 mol) of "PBG-700", 85. 6 g (0.4 mol) and 0.16 g of hydroquinone were added and subjected to dehydration condensation under heating at 170° C. under an inert gas atmosphere to obtain a compound with an acid value of 15 in solid content.

The compound thus obtained was then diluted with styrene monomer to obtain a control polybutadiene-modified unsaturated polyester having a solid content of 70% and a viscosity of -W. Hereinafter, this will be abbreviated as compound (A'-1).

Reference Example 3 (Preparation example of unsaturated polyester resin for comparison) 117.6 g (1.2 mol) of maleic anhydride, 118.4 g (0.8 mol) of phthalic anhydride, 116 g (1.1 mol) of diethylene glycol mol), = 76 g (1,0 mol) of 16-propylene glycol and 0.04 g of hydroquinone were added and subjected to dehydration condensation under heating at 220°C under an inert gas atmosphere to obtain a compound with an acid value of 20 in solid content. .

The compound thus obtained was then diluted with styrene monomer to obtain a control unsaturated polyester resin having a solid content of 70% and a viscosity of -W. Hereinafter, this will be abbreviated as compound (A'-2).

Example 1 and Comparative Examples 1 and 2 First, as Example 1, a polymerizable monomer was added to the polybutadiene-modified/unsaturated monoglycidyl compound-modified unsaturated polyester (A-1) obtained in Reference Example 1. glycidyl methacrylate (hereinafter abbreviated as GMA), and further benzyl dimethyl ketal (hereinafter abbreviated as B
It is abbreviated as DK. ) were also blended in the following proportions.

Example 1 Modified unsaturated polyester resin (A-1) 85 parts GMA 15 parts BDK
Comparative Examples 1 and 2 were also blended in the same manner as the 3 parts.

Comparative Example l Modified unsaturated polyester resin (A"-1) 100 parts BDK 3 parts Comparative Example 2 Unmodified unsaturated polyester resin (A'-2) 100 parts BDK 3 parts About each resin composition thus obtained A curability test using ultraviolet rays as active energy rays and a tensile test were conducted on the cured coating film.The results are shown in Table 1.

Curability Test The coating was applied to a tin plate using a 6 mil applicator and irradiated with ultraviolet light. Curability is evaluated based on the amount of ultraviolet irradiation (mJ/C
m”).

The breaking strength, breaking elongation, and initial elastic modulus were measured using a Tensilon tensile test.

Flexibility test: Apply to 5 pccl board with 6 mil applicator,
Irradiated with ultraviolet light. This was used as a test piece, and JIS K-
A flexibility test was conducted in accordance with 5400.

As described above, the active energy ray-curable resin composition of the present invention has high elongation at break without impairing curability.
It is known that it provides a coating film with excellent flexibility.

(Effects of the Invention) As described above, the polybutadiene-modified and unsaturated monoglycidyl compound-modified unsaturated polyesters and active energy ray-curable resin compositions of the present invention obtained in this manner can be obtained by: It is extremely useful because it cures quickly and the cured product has excellent flexibility.

Agent Patent Attorney Katsutoshi Takahashi Procedural Amendment 1, Case Description 1990 Patent Application No. 279221 2, Title of Invention Active energy ray-curable unsaturated polyester, manufacturing method thereof, and resin composition containing the same Representative Shigeru Kawamura Kuni 5, in the “Claims” column of the specification subject to amendment.

(2) The description from page 7, line 14 to page 8, line 1 is corrected as follows.

“Alternatively, alcohols and/or polybasic acids can also be used and reacted in an excess of alcohol and then an acid anhydride, or first α.

ω-polybutadiene glycol and/or α, ω-
1. α, ω-, ω-tadiene glycol and/or α, An active energy ray-curable unsaturated polyester modified with ω-hydrogenated polyptadiene glycol and modified with an unsaturated monoglycidyl compound.

2. The active energy ray-curable unsaturated polyester described above is first treated with α,β-unsaturated dicarboxylic acid or its anhydride, α,ω-,ω-tadiene glycol and/or α,ω-hydrogenated polyester. Polyptadiene glycol is used as an essential component, and if necessary, a polyhydric alcohol and/or a polybasic acid is also used, and the reaction is carried out in an excess of alcohol, and then an acid anhydride is reacted, or, The above-mentioned α, ω-, ω-tadiene glycol and/or α, ω-hydrogenated polybutadiene glycol are reacted with an acid anhydride in an acidic excess, and then an unsaturated monoglycidyl compound is further formed. according to claim 1, which is modified with α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol, which is obtained by reacting the polybutadiene glycol, and is modified with an unsaturated monoglycidyl compound. unsaturated polyester.

3. α,β-unsaturated dicarboxylic acid or its anhydride and α,ω-polybutadiene glycol and/or α,ω-hydrogenated polyptadiene glycol are essential components, and further, if necessary, Polyhydric alcohols and/or polybasic acids are also used, reacted in excess of alcohol and then acid anhydride, or α,ω-polybutadiene glycol and/or α,ω-hydrogenation as described above. A method for producing an active energy ray-curable unsaturated polyester, which comprises reacting polyptadiene glycol and an acid anhydride under excessive acid conditions, and then further reacting an unsaturated monoglycidyl compound. .

4゜ An active energy ray-curable unsaturated polyester modified with α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol and modified with an unsaturated monoglycidyl compound, and a polymerizable An active energy ray-curable resin composition comprising a monomer as an essential film-forming component.

5. α,β-unsaturated dicarboxylic acid or its anhydride and α,ω-polybutadiene glycol and/or α,ω-hydrogenated polyptadiene glycol are essential components, and further, if necessary, Polyhydric alcohols and/or polybasic acids may also be used and reacted in an excess of alcohol and then an acid anhydride, or alternatively the α, ω Z- monovoliptadiene glycol and/or α, ω - α, ω-polybutadiene glycol and/or α obtained by reacting hydrogenated polyptadiene glycol and acid anhydride in excess acid, and then further reacting with an unsaturated monoglycidyl compound, An active energy ray-curable unsaturated polyester modified with ω-hydrogenated polyptadiene glycol and an unsaturated monoglycidyl compound and an essential film-forming component on a polymerizable monomer. An active energy ray-curable resin composition.

6. The resin composition according to claim 4 or 5, wherein the polymerizable monomer is styrene and another polymerizable unsaturated monomer other than styrene. "that's all

Claims (1)

[Claims] 1. Active energy ray-curable unsaturated polyester modified with α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol and modified with an unsaturated monoglycidyl compound . 2. The active energy ray-curable unsaturated polyester described above is first treated with α,β-unsaturated dicarboxylic acid or its anhydride, α,ω-polybutadiene glycol and/or
Alternatively, α,ω-hydrogenated polybutadiene glycol is used as an essential component, and if necessary, a polyhydric alcohol and/or a polybasic acid is also used, the reaction is carried out in an excess of this polyhydric alcohol, and then acid anhydride is used. Alternatively, the above-described α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol and acid anhydride are reacted in an excess of a polybasic acid, and then further Claim 1, wherein the polybutadiene glycol is modified with α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol obtained by making an unsaturated monoglycidyl compound, and is modified with an unsaturated monoglycidyl compound. Unsaturated polyester as described. 3. α,β-unsaturated dicarboxylic acid or its anhydride;
α,ω-polybutadiene glycol and/or α,
ω-Hydrogenated polybutadiene glycol is used as an essential component, and if necessary, a polyhydric alcohol and/or a polybasic acid is used to react in excess of this polyhydric alcohol, and then an acid anhydride is reacted. Alternatively, the α,ω-polybutadiene glycol and/or
Or active energy ray curing, characterized by reacting α,ω-hydrogenated polybutadiene glycol and acid anhydride in an excess of polybasic acid, and then further reacting with an unsaturated monoglycidyl compound. Method for producing polyester unsaturated polyester. 4. Active energy ray-curable unsaturated polyester modified with α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol and modified with an unsaturated monoglycidyl compound, and polymerizable monomer An active energy ray-curable resin composition in which the body is an essential film-forming component. 5, α,β-ethylenically unsaturated dicarboxylic acid or its anhydride, α,ω-polybutadiene glycol and/or
Alternatively, α,ω-hydrogenated polybutadiene glycol is used as an essential component, and if necessary, a polyhydric alcohol and/or a polybasic acid is also used, the reaction is carried out in an excess of this polyhydric alcohol, and then acid anhydride is used. Alternatively, the above-described α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol and acid anhydride are reacted in an excess of a polybasic acid, and then further Active energy ray-curable unsaturated monoglycidyl compound modified with α,ω-polybutadiene glycol and/or α,ω-hydrogenated polybutadiene glycol and modified with an unsaturated monoglycidyl compound. An active energy ray-curable resin composition containing a saturated polyester and a polymerizable monomer as essential film-forming components. 6. The resin composition according to claim 4 or 5, wherein the polymerizable monomer is styrene and another polymerizable unsaturated monomer other than styrene.