JPH0621137B2 - Polyester acrylate resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition which comprises a polyester (meth) acrylate and a specific reactive diluent and cures to form a polyester acrylate resin having excellent durability.

2. Description of the Related Art In recent years, many radiation-curable resin compositions have been developed and started to be used in paints, adhesives, pressure-sensitive adhesives, binders for magnetic tapes, etc. There is. As a polyester-based acrylate composition comprising a polyester (meth) acrylate and a polymerizable monomer, those having various compositions are known. In other words, by controlling the type and composition of the polyhydric alcohol and polybasic acid as raw materials, it is possible to make almost infinite combinations, the properties and physical properties of the cured product can be selected over a wide range, and the physical properties of the resin obtained Is also regarded as promising because it has performance comparable to urethane-modified acrylate resin.

Problems to be Solved by the Invention When polyester (meth) acrylate is used in paints and adhesives, it is essential to reduce the viscosity, and it does not adversely affect paint properties and adhesive properties, and polyester (meth)
Excellent compatibility with acrylates and additives, large dilution effect, low skin irritation, cured physical properties and curability (curing speed,
Reactive diluents that give excellent cure in terms of volume shrinkage, elastic modulus of cured skin, flexibility, adhesion, adhesion, durability, strength and elongation) are extremely important. From this point of view,
6-Hexanediol diacrylate is highly diluted and hardened, and although it has excellent weather resistance, hydrolysis resistance, and flexibility of hardened skin, and has a fast hardening speed, it is frequently used, but has a drawback that it has a large skin irritation (PII value 5. 5) It is quite limited in use. Further, recently, the number of applications requiring flexibility and flexibility has become extremely large, and the hydrolysis resistance and weather resistance of the cured film have been severely demanded, and improvement thereof is desired.

An object of the present invention is to provide a curable resin composition having a low viscosity, excellent workability and coating properties, and having little skin irritation. In addition, another object of the present invention is to have excellent hydrolysis resistance after curing, weather resistance, excellent strength, strong resistance and flexibility,
It is an object of the present invention to provide a composition which produces a polyester acrylate resin which is highly flexible and has excellent adhesion and adhesiveness.

Means for Solving the Problems According to the present invention, the above object is achieved by providing a polyester-based acrylate resin composition comprising a polyester (meth) acrylate and 1,9-nonanediol diacrylate.

The polyester (meth) acrylate used in the present invention can be produced, for example, from a polyhydric alcohol, a polycarboxylic acid and acrylic acid or methacrylic acid, has an ester bond in the polymer main chain, and has a polymer terminal. Is a polymer having an acryloyl group or a methacryloyl group. As a typical example thereof, the general formula (I) (Wherein R ₁ and R ′ ₁ are hydrogen or a methyl group, R ₂ is a polyester polyol residue, and l and m are integers of 1 to 3). .

The average molecular weight of the polyether polyol constituting the polyester (meth) acrylate used in the present invention is 2
A polyester polyol of 00 to 10,000 is preferable, but as the polyester polyol, one composed of a usual organic dibasic acid and a low molecular weight polyhydric alcohol can be used.
As the organic dibasic acid, adipic acid, succinic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, maleic acid and the like can be used. The low molecular weight polyhydric alcohols are 1,4-butanediol, 1,6-hexane glycol, 1,9-nonanediol, diethylene glycol, propylene glycol, trimethylolpropane, glycerin, 3-methyl-1,5-pentanediol, etc. Is used. Polyester polyols obtained by ring-opening polymerization such as ε-caprolactone and β-methyl-δ-valerolactone can also be used.
Among them, particularly preferable polyester polyols include those containing at least one group selected from the following formulas as a constituent component of the polyester polyol. By using the polyester polyol containing the constituents, a composition having further excellent hydrolysis resistance, weather resistance and flexibility is provided.

In the molecule Specific examples of the polyester polyol having 3 to 3 are methyl 3-methyl-1,5-pentanediol or a low molecular weight polyol mixture containing the same, adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, and terephthalate. It is a polyester polyol synthesized from dicarboxylic acids such as acid, isophthalic acid, maleic acid, and phthalic acid.

In the molecule Specifically, the polyester polyol having is a poly (β-methyl-δ-valerolactone) polyol or a polyol mixture containing the same, or β-methyl-δ
A block or random copolymer polyol obtained by ring-opening copolymerization of valerolactone as one component.

That is, a copolymer with another lactone, for example, ε-caprolactone and β-methyl-δ-valerolactone obtained by ring-opening copolymerization is randomly or block-wise in the molecule. This may be the case when using a group-introduced polyol or when using an adipate-based polyester polyol and a block polymer polyol composed of β-methyl-δ-valerolactone.

By using the above polyester polyol having a C6 group having a methyl branch in the molecule, the resulting composition is excellent in hydrolysis resistance, solvent resistance, and flexibility, and at the same time, is a pigment. The dispersibility becomes particularly good. The above structure of polyester has excellent pigment dispersibility because the odd carbons are linearly arranged, and also has a methyl branch,
It becomes amorphous, has good low-temperature flexibility, and has excellent adhesion to the substrate.

Polyester polyols having
It is derived from 9-nonanediol or azelaic acid. By using the polyester containing the group having 9 carbon atoms in the molecule, the low temperature characteristics of the obtained composition,
Flexibility, flexibility, solvent resistance, hydrolysis resistance, etc. are excellent overall, and at the same time pigment dispersibility is excellent.

In the present invention, a polyester (meth) acrylate and a polymerizable monomer 1,9-nonanediol diacrylate are mixed and used to obtain a polyester acrylate resin composition. Polyester (meth) acrylate and 1,9-
The mixing ratio with nonanediol diacrylate is 95: 5
It is 5:95, preferably 90:10 to 30:70 (weight ratio).

The 1,9-nonanediol diacrylate used in the present invention has a PII value of 2.0 showing skin irritation, which is extremely lower than the PII value of 5.5 of 1,6-hexanediol diacrylate. , Is advantageous in handling. In addition, 1,9-nonanediol diacrylate is
Regarding curing speed, volume shrinkage, low temperature characteristics, flexibility, etc.
Not inferior to 1,6-hexanediol diacrylate and 1,3-neopentyl glycol diacrylate. The compatibility with the polyester (meth) acrylate is also very good. For these reasons, the polyester-based acrylate resin composition of the present invention has a low viscosity and provides a film having excellent adhesion, adhesiveness and flexibility. The reactive diluent in the present invention is 1,
Although 9-nonanediol diacrylate is essential, even if a polyfunctional acrylate such as trimethylolpropane triacrylate or pentaerythritol triacrylate or a monofunctional acrylate such as dicyclopentadienyl acrylate or 2-ethylhexyl acrylate is used together. Not to mention good things. Further, other known reactive diluents can be used in combination within the range of not impairing the effects of the present invention. In addition, polyester (meth) acrylate or 1,9
-The synthesis method of nonanediol diacrylate is not particularly limited, but the following method is exemplified.

(1) Dehydrochlorination reaction of acrylic acid or methacrylic acid chloride with polyester polyol (or 1,9-nonanediol) (2) Direct reaction of acrylic acid or methacrylic acid with polyester polyol (or 1,9-nonanediol) Dehydration reaction (3) Transesterification reaction of lower alkyl ester of acrylic acid or methacrylic acid with polyester polyol (or 1,9-nonanediol) (4) Polyester (meth) acrylate derivative (or 1,
Dehydrochlorination reaction of 9-nonanediol monoacrylate) with an acid chloride of acrylic acid or methacrylic acid The polyester (meth) acrylate of the present invention or 1,9-
Nonanediol diacrylate is (1), (2), (3) or (4)
Can be synthesized by any of the above methods. In order to further improve the adhesion and the adhesive performance of the composition thus obtained, the general formula (II) (In the formula, R ₃ is hydrogen or a methyl group, R ₄ is a divalent organic group,
q is 1 or 2, r is 1 or 2, and q + r = 3). Examples of the phosphorus-containing (meth) acrylate include mono [2- (meth) acrylate ethyl] phosphate, mono [2- (meth) acrylatepropyl] phosphate, di [2- (meth) acrylateethyl] phosphate, and phosphoric acid. The [2-
(Meth) acrylate propyl] and the like. The addition amount of the phosphorus-containing (meth) acrylate is preferably 50% by weight or less of the total resin.

Further, in order to prevent radical polymerization of the produced polyester (meth) acrylate, a radical polymerization inhibitor of about 0.001 to 0.05% by weight can be added to the system. Examples of such inhibitors include hydroquinone,
Hydroquinone monomethyl ether etc. can be mentioned.

As a means for curing the composition of the present invention, for example, electron beam curing, ultraviolet curing, heat curing or any other known means can be adopted.

When the composition of the present invention is cured by ultraviolet rays, a photoinitiator as shown below is added. Specific examples thereof include benzophenone, p-methoxybenzophenone, acetophenone, propiophenone, xanthone, benzoin, benzoin ethyl ether, anthraquinone, and naphthoquinone, and the amount thereof is a polyester (meth) acrylate contained in the composition. To about 0.1 to 15% by weight. At that time, a photoactivator such as methylamine, diethanolamine, N-methyldiethanolamine or tributylamine may be added.

When the composition of the present invention is cured by heat, hydrogen peroxide, benzoyl peroxide, cumene peroxide, t-butyl hydroperoxide, azobisbutyronitrile, etc., which are known as radical polymerization initiators, are used. Can be used.

In the case of irradiating with an electron beam for curing, addition of a photoinitiator, a radical polymerization initiator or the like is not particularly required.

Regardless of which of these curing methods is adopted, the polyester-based acrylate resin composition obtained by the production method of the present invention is tough, which has not been obtained so far, and has excellent hydrolysis resistance, weather resistance, A cured product having flexibility, adhesion and adhesiveness is provided. Further, the internal strain due to the volume shrinkage during curing is small, and it is particularly useful as an adhesive.

In addition to the above-mentioned compounding agents, usual additives and fillers can be added to the composition of the present invention within the range that does not impair the object of the present invention, depending on the purpose of use.

To further describe specific applications, the polyester-based acrylate resin composition of the present invention is useful for paints, coating agents, adhesives, inks, sealing agents and the like.

Examples In order to more specifically describe the present invention, the following examples are given,
A comparative example will be given. In the examples, “part” means “part by weight”. The performance of the cured coating film was determined by the following method.

(i) Adhesion: x / 10 of the number of 100 test pieces adhered by the method of peeling cellophane tape.
It is indicated by 0.

(ii) Flexibility: A strip-shaped test piece having a width of 5 mm and a length of 10 cm was evaluated along the outer circumference of a cylinder having a diameter of 2 cm by observing whether or not the folded coating film was cracked.

(iii) Water resistance: After the test piece was immersed in pure water at 40 ° C. for 240 hours, the appearance and adhesion of the outer coating layer (method according to (i) above) were evaluated.

(iv) Weather resistance: The test piece was held in a Sunshear weatherometer for 600 hours to evaluate the appearance and adhesion of the outer coating layer (method according to (i) above).

Example 1 3-Methyl-1,5-pentanediol (920.0 g) and adipic acid (876 g) (diol / acid molar ratio: 1.3 / 1) were condensed water at a temperature of about 210 ° C. while passing N ₂ gas under normal pressure. Esterification was carried out while distilling. When the acid value of the polyester became 0.3 or less, the degree of vacuum was gradually raised by a vacuum pump to complete the reaction. Thus, a polyester polyol having a hydroxyl value of 56 and an acid value of 0.1 (hereinafter referred to as polyester
(a) is obtained. This polyester (a) was liquid at room temperature and had a molecular weight of about 2,000. To 500 g of this polyester polyol, 36 parts of acrylic acid and 0.4 part of hydroquinone monomethyl ether were added, and esterification was performed at 180 ° C. to obtain a polyester acrylate. 1,9-
100 parts of nonanediol diacrylate and diphosphoric acid [2
-Methacrylate ethyl] 50 parts was added to obtain a polyester acrylate resin composition.

Obtained polyester-based acrylate resin composition 100
A coating composition was prepared by adding 3 parts of benzoin ethyl ether to 1 part. This was coated on an aluminum plate with a 75 micron applicator and irradiated with a high pressure mercury lamp with an output of 80 W / cm. The coating film became tack-free by irradiating twice at a speed of 6 m / min, and was completely cured by irradiating four times. A coating film irradiated 6 times was used for the measurement of physical properties.

Examples 2 to 7 Polyester-based acrylate resin compositions having the compositions shown in Table 1 were obtained in the same manner as in Example 1 with the same molar ratio.

Comparative Examples 1 to 3 Polyester-based acrylate resin compositions having the compositions shown in Table 1 were obtained by the same method with the same molar ratio as in Example 1.

In Examples 2 to 5, adipic acid / isophthalic acid =
1/1 (molar ratio), azelaic acid / isophthalic acid = 1 /
1 (molar ratio), 3-methyl-1,5-pentanediol /
The ratio of 1,9-nonanediol is 1/1 (molar ratio).

As described above, the resin composition of the present invention has flexibility, film physical properties,
It is industrially useful in that it gives a cured product having excellent adhesion, water resistance, and weather resistance, and has little skin irritation.

Claims (4)

[Claims] 1. A polyester (meth) acrylate and 1,
A polyester acrylate resin composition comprising 9-nonanediol diacrylate. 2. A polyester (meth) acrylate having the general formula (I) (In the formula, R ₁ and R ′ ₁ are hydrogen or a methyl group, and R ₂ is A polyester polyol residue having at least one group selected from the above as a constituent component, and l and m each represent an integer of 1 to 3. ] The polyester-based acrylate resin composition of Claim 1 which is a polyester (meth) acrylate represented by these. 3. A polyester (meth) acrylate, 1,
9-nonanediol diacrylate and general formula (II) (In the formula, R ₃ is hydrogen or a methyl group, R ₄ is a divalent organic group, q is 1 or 2, r is 1 or 2, and q + r =
It is 3. ) A polyester-based acrylate resin composition comprising an acrylate represented by: 4. A polyester (meth) acrylate having the general formula (I) (In the formula, R ₁ and R ′ ₁ are hydrogen or a methyl group, and R ₂ is A polyester polyol residue having at least one group selected from the above as a constituent component, and l and m each represent an integer of 1 to 3. ] The polyester-based acrylate resin composition of Claim 3 which is a polyester (meth) acrylate represented by these.