JP3089986B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition for curing an unsaturated ester organic compound, an unsaturated polyester resin and an organic compound having a hydrosilyl group by an addition reaction in the presence of a hydrosilylation catalyst.

[0002]

2. Description of the Related Art It has long been known that the modification of an ester organic compound with an organosiloxane is effective for improving properties such as hydrophobicity, weather resistance and lubricity. For example, see JP-A-3-22.
No. 1 discloses that an organosiloxane having one hydrosilyl group in one molecule can be obtained in the presence of a hydrosilylation catalyst.
An organopolysiloxane-grafted polyester obtained by grafting to a side chain of a polyester having an average molecular weight of 500 to 5,000 via an alkylene group has been proposed. However, this organopolysiloxane-grafted polyester has poor compatibility between the organosiloxane and the polyester, resulting in a poor yield of the grafting reaction, and when added to polyester, has the above-mentioned hydrophobicity, weather resistance, lubricity, etc. Although the properties are improved, there is a problem that the properties inherent in polyester, such as mechanical strength and chemical resistance, may be impaired.

JP-A-5-279572 discloses an organopolysiloxane containing at least three hydrosilyl groups in a molecule and a polysiloxane-grafted polyester having an aliphatic unsaturated bond in the presence of a hydrosilylation catalyst. There has been proposed a curable composition comprising However, this curable composition gives an effective cured film to a polyester film or a polypropylene film, but has a drawback that the cured film is brittle and easily peeled off from a substrate to be applied because of a high ratio of a siloxane component.

Therefore, it is desired to develop a technique for modifying an ester organic compound with an organosiloxane without the above-mentioned problems.

[0005] The present invention has been made in view of the above circumstances,
A strong cured film that can maintain the original properties of polyester such as mechanical strength and chemical resistance, can improve the properties of polyester such as hydrophobicity, weather resistance and lubricity, and has excellent adhesion to the substrate. It is an object of the present invention to provide a curable composition giving the following.

[0006]

The present inventors have conducted intensive studies to achieve the above object, and as a result, (a) the following general formulas (I), (II), (III) and (IV) An organic compound having a molecular weight of 100 to 5000 and containing at least three hydrosilyl groups in one selected molecule;
(B) an unsaturated ester organic compound having a molecular weight of 100 to 5000 containing at least two alkenyl groups in one molecule, (c) an unsaturated polyester resin having a molecular weight of 10,000 or more, and (d) a hydrosilylation catalyst. Can improve the properties of the polyester such as hydrophobicity, weather resistance, lubricity, release properties, and printability without impairing the original properties of the polyester such as mechanical strength and chemical resistance. When adhered to a substrate such as a polyester film, it gives a strong cured film having excellent adhesion without peeling off from the substrate, and when added to a polyester resin or the like, has good compatibility and can bleed. It is also possible to impart properties such as surface slipperiness and hydrophobicity, and it has been found that a curable composition effective for modifying polyester resins and the like can be obtained. Leading to the completion of the.

[0007]

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Accordingly, the present invention provides the above (a), (b),
Provided is a curable composition containing (c) and (d) as essential components.

Hereinafter, the present invention will be described in more detail. The first essential component (component (a)) of the present invention is selected from the following general formulas (I), (II), (III) and (IV): An organic compound having three or more hydrosilyl groups (SiH groups) in one molecule. This organic compound has good compatibility with an ester-based organic compound, and as described above, has good cured product properties due to its compounding. Can be granted.

[0010]

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Here, in the formula, A represents a monovalent, and B represents a divalent silane or siloxane bond, and at least one, more preferably two or more, of the substituents directly bonded to the silicon atom of the silane or siloxane bond. A hydrogen atom, and when there is another substituent, the other substituent is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Groups, alkyl groups such as hexyl group, cyclohexyl group and octyl group, alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group, aryl groups such as phenyl group, tolyl group and xylyl group, benzyl group and phenylethyl group Aralkyl groups such as
Examples thereof include a trifluoropropyl group and a chloromethyl group in which part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms or the like.

[0012]

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As described above, the component (a) is composed of C, D,
It is necessary to have at least one bond of E, whereby the compatibility with the ester-based organic compound is improved, and the cured product can have excellent properties.

In this case, the bond of C, D and E preferably contains at least one group selected from the following formulas (1) to (11).

[0015]

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[0016]

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The substituted or unsubstituted monovalent hydrocarbon group represented by R ^{1 to} R ^{9 and} R ¹⁰ and R ¹¹ includes the above-mentioned A or B
And the alkoxy groups include those having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms.
Examples of the carbon ring and hetero ring in which ¹⁰ and R ¹¹ are bonded include the following.

[0018]

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The component (a) is represented by the above formulas (I) to (I).
(IV) whose molecular weight is 10
It is required to be 0 to 5000, preferably 100 to 3000, whereby the unsaturated ester-based organic compound having a molecular weight of 100 to 5000 as the component (b) described later can be satisfactorily modified.

The component (a) preferably has 1 to 30, particularly preferably 4 to 30, silicon atoms in one molecule.
It is particularly preferable that the bond between A and B is as follows.

[0021]

Embedded image (However, R represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms. N is 1 to 3.)
Examples of such component (a) include the following.

[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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The amount of the component (a) is appropriately selected, but the mixing ratio of the components (a), (b) and (c) is based on the alkenyl group in the components (b) and (c) described below. a)
The molar ratio to the hydrosilyl group (SiH group) in the component is 0.1.
2-5 mol / mol, especially 0.4-2.5 mol / m
It is preferable to mix in an amount of ol. When the molar ratio is less than 0.2, curing may be insufficient and the cured product may have insufficient strength. On the other hand, when the molar ratio is greater than 5, cracks and voids may be formed in the cured product due to the remaining active hydrosilyl groups. May occur.

Next, the unsaturated ester organic compound as the component (b) has a molecular weight of at least two alkenyl groups in one molecule of from 100 to 5,000, preferably from 100 to 5,000.
000.

Here, examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group,
Examples thereof include a butenyl group, an acryl group, and a methacryl group, and a vinyl group and an allyl group are particularly preferable.

The unsaturated ester organic compound is an unsaturated ester compound which can be synthesized by subjecting an unsaturated monohydric alcohol or allyl halide to a polycarboxylic acid or a derivative thereof by a transesterification reaction or a condensation reaction. An unsaturated ester compound which can be synthesized by performing a polycondensation reaction between a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol is used.

In this case, the unsaturated monohydric alcohol used as a raw material of the former unsaturated ester compound includes:
For example, those having preferably 2 to 10 carbon atoms, such as vinyl alcohol, allyl alcohol, and methallyl alcohol, are exemplified. As the allyl halide, for example, allyl chloride is exemplified. Further, as the polycarboxylic acid or its derivative, specifically, phthalic acid, phthalic anhydride, isophthalic acid and the like, and derivatives thereof are preferably used.

Examples of the polycarboxylic acid used as a raw material for the latter unsaturated ester compound include phthalic acid, isophthalic acid, adipic acid, sebacic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, and oxalic acid. , Malonic acid, succinic acid, saturated polycarboxylic acids such as cyclopentanedicarboxylic acid, allyloxyisophthalic acid, allyloxyterephthalic acid, allylmalonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid,
Unsaturated polycarboxylic acids such as mesaconic acid, itaconic acid, and tetrahydrophthalic acid, and derivatives thereof. Furthermore,
Examples of polyhydric alcohols include ethylene glycol,
Glycols such as propylene glycol, butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin monoallyl ether, trimethylolpropane monoallyl ether, and pentaeristol monoallyl Those containing an alkenyl group such as ether and pentaerythritol diallyl ether are exemplified. In addition, various unsaturated ester compounds are synthesized by variously combining the above-mentioned saturated polycarboxylic acids or derivatives thereof, unsaturated polycarboxylic acids or derivatives thereof, glycols, polyhydric alcohols containing an alkenyl group, and the like. However, in the present invention, it is preferable to use a saturated polycarboxylic acid, an unsaturated polycarboxylic acid or a derivative thereof and a glycol as raw materials from the viewpoint of cured physical properties.

A known method for producing the unsaturated ester-based organic compound may be employed. For example, as a method for producing an unsaturated ester compound by polycondensation, a conventionally known polyvalent carboxylic acid and polyhydric alcohol may be used. , A transesterification reaction of a polycarboxylic acid ester and a polyhydric alcohol, a dehydrochlorination condensation of a polycarboxylic acid halide and a polyhydric alcohol in the presence of a base, and the like.

The component (c) of the present invention has a weight average molecular weight of 1
It is an unsaturated polyester resin of 0000 or more, preferably 10,000 to 50,000.

As the unsaturated polyester resin, conventionally known resins can be used. For example, a method in which the monomer component described in the above-mentioned component (b) is peroxide-polymerized, heated and polymerized using radiation or ultraviolet rays. A method obtained by a known method such as a method described above can be used. In this case, the unsaturated polyester resin is preferably a polymer that is soluble in the monomer of component (b) or an organic solvent (for example, ketones).

As the hydrosilylation catalyst of the component (d), those usually used can be used, and examples thereof include compounds containing platinum, palladium, rhodium, ruthenium, cobalt, nickel and the like. Platinum olefin complexes, complexes of chloroplatinic acid and vinyl siloxane, and the like are preferably used because of their high catalytic effect and little side reactions.

The amount of the hydrosilylation catalyst to be added can be a catalytic amount, which is usually 0.1 to 10% based on the total amount of the above components (a), (b) and (c). 2000 ppm, preferably 1 to 200 ppm
Is the amount used.

Further, when it is necessary to adjust the curing time in order to put the curable composition of the present invention to practical use, a vinyl group-containing organopolysiloxane such as vinylcyclotetrasiloxane may be used as a control agent. , Triallyl isocyanurate, alkyl maleate, acetylene alcohols or their silanes, modified siloxanes, hydroperoxides, tetramethylethylenediamine, benzotriazole or mixtures thereof can be added. The amount of the control agent added is 0.1% of the whole composition.
-10% by weight is desirable.

The curable composition of the present invention can be blended with a polyester resin such as polyethylene terephthalate or polybutylene terephthalate, a polyester copolymer, or the like, and used for modifying these resins. Can be used to form a cured film on resin films and molded products, etc., thereby giving the resin, film, molded products, etc. the properties inherent in polyester, as well as hydrophobicity, weather resistance, lubricity, etc. Can be.

When the curable composition of the present invention is applied, the curable composition may be used in the form of an aromatic hydrocarbon such as toluene, xylene or benzene, an ether such as diethyl ether or tetrahydrofuran, or a carboxylic acid ester such as ethyl acetate or butyl acetate. Can be used by dissolving in an organic solvent such as Further, the curable composition of the present invention can be rapidly cured by heating, and the curing can be usually performed at 60 to 150 ° C. for about 5 to 60 minutes.

[0041]

The curable composition of the present invention has a mechanical strength,
In addition to maintaining good properties inherent in polyester such as chemical resistance, it also gives a strong cured film with excellent properties such as hydrophobicity, weather resistance, lubricity, and excellent adhesion to the substrate,
It can be suitably used for modifying polyester resins, films and molded products.

[0042]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. All parts in each example are parts by weight.

Example 1 A four-necked one-liter flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a reflux condenser with a distilling tube was charged with 290.4 parts of isophthalic acid and 58.7 parts of glycerin monoallyl ether. Parts, 174.7 parts of neopentyl glycol and 35 parts of xylene. While flowing nitrogen gas, the temperature was gradually raised to 230 ° C. While maintaining this temperature and removing water generated by the condensation reaction from the distilling tube, the acid value was measured by sampling periodically. When the acid value becomes 5 or less, low-boiling substances are distilled off under reduced pressure, and allyl groups are contained in the side chain, and the amount of allyl groups is 2.4%.
0 parts were synthesized. This polyester (A) was a pale yellow solid at room temperature, and had a carbinol group content of 1.6%.

Further, 600 parts of diallyl phthalate, 3 parts of water, 13.2 parts of benzoyl peroxide were placed in a reaction vessel equipped with a stirrer.
Parts, 100 parts of dimethylbenzyl alcohol, and 10
After heating to 0 ° C. for polymerization for 7 hours, the mixture was cooled to room temperature. The reaction solution was allowed to stand until it was separated into a bottom organic layer and an upper aqueous layer, and the bottom organic layer was separated. When 400 parts of isopropanol was added to this organic layer and stirred vigorously, a white solid was formed, which was filtered and dried to obtain a polyester (B) having a weight average molecular weight of 12,000 and a vinyl group content of 10%.

Next, 50 parts of the polyester (A) and the polyester (B) were placed in a dry reaction vessel equipped with a stirrer.
50 parts and 3 parts of a compound having the following structure were added to tetrahydrofuran 2
After dissolving in 00 parts, 0.2 part of an isopropyl alcohol solution of chloroplatinic acid (platinum concentration: 0.4%) was added, and an addition reaction was carried out while heating and refluxing.

[0046]

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When the IR spectrum was measured at the time when the reaction was carried out for 4 hours, the absorption of the olefin near 1640 cm ^-1 had completely disappeared, and the reaction was terminated at this time. After completion of the reaction, the mixture was concentrated under reduced pressure to obtain a light yellow solid curable composition.

The above curable composition 5 was added to 100 parts of a polyethylene terephthalate resin using a lab plast kneader.
When the mixture was added and mixed at 220 ° C. for 15 minutes, the compatibility was good, no bleeding occurred, and the surface slipperiness and hydrophobicity were significantly improved.

Further, the obtained curable composition is uniformly dissolved in butyl acetate, and this solution is coated on a 50-μm-thick polyester film so as to have a thickness of 25 μm. I baked it for a minute. The obtained cured film adhered well to the polyester film. Further, a peeling test was performed at room temperature at a peeling speed of 200 mm / min, and the peeling force was measured.
0 g / 25 mm, and the interface fracture rate was 100%. Also, when the peel resistance with a commercially available cellophane adhesive tape was measured, it showed a value of 5 to 10 g / 2 cm, showing good releasability. In addition, when letters were written on the cured film with oil-based magic, good printability was exhibited.

Comparative Example 1 Polyester (A) having an allyl group on the side chain and having a molecular weight of 3647 was obtained in the same manner as in Example 1.
When an addition reaction was carried out using 50 parts, 50 parts of the polyester (B), and 3 parts of an organosiloxane compound having the following structure, a curable composition was obtained as a pale yellow transparent solid.

[0051]

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When this curable composition was added to and mixed with polyethylene terephthalate under the same conditions as in Example 1,
Poor compatibility and bleed.

A solution obtained by uniformly dissolving the obtained curable composition in butyl acetate is applied on a 50-μm-thick polyester film so as to have a thickness of 25 μm, and is applied at 150 ° C. for 10 minutes. Baked. The resulting cured film was brittle and easily broken.

Example 2 Propylene glycol 1 was placed in a reaction vessel equipped with a partial condenser for releasing water out of the system.
58 parts were added, the mixture was stirred while passing nitrogen gas at 30 ml / min, and heating was started. When the temperature reached 80 ° C., 98 parts of maleic anhydride and 140 parts of phthalic anhydride were added. After about 2 hours, formed water distilled at 170 ° C. After 5 hours, when the generated water disappeared, the partial condenser was heated and the nitrogen gas was increased to 150 ml / min. Heating was stopped when the acid value reached 40 in 16 hours, and the mixture was cooled to room temperature.
0 polyester (C) was obtained.

Next, 25 parts of the polyester (C) and the polyester (B) were placed in a dry reaction vessel equipped with a stirrer.
50 parts and 3 parts of a compound having the following structure were added to tetrahydrofuran 2
After dissolving in 00 parts, 0.2 part of an isopropyl alcohol solution of chloroplatinic acid (platinum concentration: 0.4%) was added, and an addition reaction was carried out while heating and refluxing.

[0056]

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When the IR spectrum was measured at the time when the reaction was carried out for 4 hours, the absorption of the olefin near 1640 cm ^-1 had completely disappeared, and the reaction was terminated at this time. After completion of the reaction, the mixture was concentrated under reduced pressure to obtain a curable composition as a pale yellow transparent solid. When this curable composition was added to polyethylene terephthalate, it had good compatibility, did not bleed, and markedly improved surface slipperiness and hydrophobicity.

A solution obtained by uniformly dissolving the obtained curable composition in butyl acetate is applied on a 50-μm-thick polyester film so as to have a thickness of 25 μm, and is applied at 150 ° C. for 10 minutes. Baked. The obtained cured film adhered well to the polyester film. Further, a peeling test was performed at room temperature at a peeling speed of 200 mm / min, and the peeling force was measured.
0 g / 25 mm, and the interface fracture rate was 100%. Also, when the peel resistance was measured with a commercial cellophane tape,
It showed a value of 5-10 grams / 2 cm, indicating good releasability. In addition, when letters were written on the cured film with oil-based magic, good printability was exhibited.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 67/06-67/07 C08L 83/05

Claims (2)

(57) [Claims] (1) The following general formulas (I), (II),
(III) and (IV), having a molecular weight of 100 to 50 containing at least three hydrosilyl groups in the molecule.
(B) an unsaturated ester organic compound having a molecular weight of 100 to 5,000 containing at least two alkenyl groups in the molecule, (c) an unsaturated polyester resin having a molecular weight of 10,000 or more, (d) hydrosilylation A curable composition containing a catalyst as an essential component. Embedded image 2. The bond of C, D, and E is represented by the following formula (1):
The composition according to claim 1, comprising at least one group selected from (11). Embedded image Embedded image