Organopolysiloxane compound, composition containing same, and cured product thereof

Abstract

The present invention provides: an organopolysiloxane compound which has high reactivity; and a composition containing the same.　The organopolysiloxane compound is represented by formula (1). (In formula (1), W is a divalent organopolysiloxane residue, each L is independently an alkylene group having a carbon number of 2-12, each Xi is independently at least one type of group selected from alkylene groups having a carbon number of 1-18 and groups represented by formula (3) (in formula (3), W, each L, and each Xi are the same as defined above, each Z is independently an oxygen atom or the like, M is a polyvalent organic group having a valence of b+1, i is a number from 1 to 30 and i starts from 1, ai is a number from 0 to b, and b is a number from 1 to 20), and at least one Xi in formula (1) is a group represented by formula (3), b-ai being a number of 1 or greater.)

Description

Organopolysiloxane compound, composition containing same, and cured product thereof

[0001] The present invention relates to an organopolysiloxane compound having an acryloyl group, which is a radically polymerizable functional group, a composition containing the same, and a cured product thereof.

[0002] In recent years, with increasing demands for energy conservation and process shortening, photocurable resins that can be cured in a short time at room temperature have attracted attention, and radically polymerizable acrylic compounds are primarily used as raw materials. Such photocurable resins are used in paints, coatings, inks, etc., and are sometimes required to have properties such as high water repellency, antifouling properties, and lubricity. One known method for imparting high water repellency, antifouling properties, and lubricity to photocurable resins is to incorporate and copolymerize an organopolysiloxane having a (meth)acryloyl group (Patent Document 1). However, many organopolysiloxanes having a (meth)acryloyl group have low reactivity, which can lead to problems such as unreacted organopolysiloxane bleeding from the cured resin over time (Patent Document 2). Therefore, an organopolysiloxane compound that solves this problem has been eagerly awaited.

[0003] JP 2022-138932 A JP 2005-36018 A

[0004] Therefore, an object of the present invention is to provide a highly reactive radically polymerizable organopolysiloxane compound, a composition containing the same, and a cured product thereof.

[0005] As a result of extensive research aimed at solving the above problems, the present inventors have discovered that a specific organopolysiloxane compound having an acryloyl group can achieve the above object, and have thus completed the present invention.

[0006] [1] An organopolysiloxane compound represented by the following formula (1): [In formula (1), W is represented by the following formula (2)] (In formula (2), R 1are each independently a group selected from an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms, and n is a number from 0 to 1,000; each L is independently an alkylene group having 2 to 12 carbon atoms; X i are each independently an alkyl group having 1 to 18 carbon atoms (wherein the alkyl group may have one or more bonds selected from an ether bond, an ester bond, an amide bond, and a hydroxyl group), and a group represented by the following formula (3): (W, L and X in formula (3) i is the same as above, and each Z is independently an oxygen atom, a sulfur atom, or NR 2 and the NR 2 R in 2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M is a polyvalent organic group having a valence of (b+1), i is a number from 1 to 30, provided that i starts from 1, i is a number from 0 to b, and b is a number from 1 to 20. i At least one of the following is b-a i is a group represented by formula (3) in which X is a number of 1 or more.] [2] X i are groups represented by formula (3). [3] The organopolysiloxane compound according to [1] or [2], wherein b is a number from 1 to 5. [4] A composition comprising the organopolysiloxane compound according to any one of [1] to [3]. [5] The composition according to [4], further comprising one or more acrylic compounds other than the organopolysiloxane compound. [6] The composition according to [5], wherein the acrylic compound is a b+1 polyvalent acrylic monomer. [7] A cured product of the composition according to any one of [4] to [6].

[0007] The organopolysiloxane compound of the present invention has high photocurability and reactivity, and is less likely to bleed when copolymerized with a photocurable resin composition. Furthermore, because it cures with less energy, it is possible to save energy and shorten the process when producing a cured product. The present invention is suitable for paints, coatings, inks, etc.

[0008] The organopolysiloxane compound synthesized in Example 1 1 1 is a H-NMR spectrum chart, and 2 is a GPC chart of the organopolysiloxane compound synthesized in Example 1.

[0009] The present invention will be described in more detail below.

[0010] [Organopolysiloxane Compound] The organopolysiloxane compound of the present invention is represented by the following formula (1), and since it has an acryloyl group in one molecule, it easily reacts with a radically polymerizable compound.

[0011] In the above formula (1), W is a group (divalent organopolysiloxane-containing group) represented by the following formula (2).

[0012] In formula (2), R 1 are independently a group selected from an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms, preferably a methyl group or a phenyl group, and more preferably a methyl group. n is a number from 0 to 1,000, preferably a number from 3 to 500, and more preferably a number from 5 to 200. Examples of the group represented by formula (2) above include groups represented by formulas (4) to (7) below, but are not limited to these formulas.

[0013] In the above formula (1), L is an alkylene group having 2 to 12 carbon atoms, preferably an alkylene group having 3 to 8 carbon atoms, and more preferably an alkylene group having 3 to 4 carbon atoms. i are independently a group selected from an alkyl group having 1 to 18 carbon atoms (wherein the alkyl group may have one or more bonds selected from an ether bond, an ester bond, an amide bond, and a hydroxyl group) and a group represented by the following formula (3), and preferably a group represented by the following formula (3):

[0014] In formula (3), W, L and X i The Z's are the same as those in the formula (1). Each Z is independently an oxygen atom, a sulfur atom, or NR 2and preferably an oxygen atom. 2 R in 2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably a hydrogen atom. M is a polyvalent organic group having a valence of (b+1), preferably a polyvalent organic group having a valence of 2 to 6, more preferably a divalent to hexavalent aliphatic hydrocarbon group which may have an ether bond and a hydroxyl group. i is a number from 1 to 30, preferably a number from 1 to 20, more preferably a number from 1 to 10. However, i starts from 1. a i is an integer from 0 to b, and a 10 is preferably 0. b is a number from 1 to 20, preferably a number from 1 to 5. Examples of the polyvalent organic group M include groups represented by the following formulas, but are not limited to these formulas:

[0015] Above X i Examples of the group include, but are not limited to, groups represented by the following formulas:

[0016] The number average molecular weight (Mn) of the organopolysiloxane compound represented by formula (1) above is preferably 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 2,000 to 20,000, and i in formula (3) is a number from 1 to 30 that satisfies the number average molecular weight (Mn). The number average molecular weight (Mn) referred to in this specification refers to the number average molecular weight measured by GPC under the following conditions using polystyrene as the standard. [Measurement conditions] Developing solvent: tetrahydrofuran Flow rate: 0.6 mL / min Detector: differential refractive index detector (RI) Column: TSK Guard column Super H-H TSKgel Super HM-N (6.0 mm I.D. × 15 cm × 1) TSKgel Super H2500 (6.0 mm I.D. × 15 cm × 1) (all manufactured by Tosoh Corporation) Column temperature: 40°C Sample injection volume: 50 μL (tetrahydrofuran solution with a concentration of 0.3 wt%)

[0017] [Method for Producing Organopolysiloxane Compound] The organopolysiloxane compound of the present invention represented by the above formula (1) can be produced, for example, by the following method: That is, it can be produced by a Michael addition reaction between an organopolysiloxane having primary amino groups or secondary amino groups at both ends and a bifunctional or higher functional acrylic compound, as shown in the following reaction formula (A).

[0018] In the above reaction formula (A), W, L, Z, M, b and X i The X's are the same as those in formula (1) above. Each X is independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms (wherein the alkyl group may have one or more bonds selected from an ether bond, an ester bond, an amide bond, and a hydroxyl group). When X is a hydrogen atom, i.e., when the organopolysiloxane has a primary amino group, two equivalents of acrylic groups react with -NH2, and X in the reaction product is i is a group represented by the above formula (3).

[0019] Examples of the di- or higher functional acrylic compound include difunctional acrylic monomers such as 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and tripropylene glycol diacrylate; trifunctional acrylic monomers such as trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, glycerin triacrylate, and pentaerythritol triacrylate; tetrafunctional acrylic monomers such as pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, and ditrimethylolpropane tetraacrylate; pentafunctional acrylic monomers such as dipentaerythritol pentaacrylate; hexafunctional acrylic monomers such as dipentaerythritol hexaacrylate; and oligomeric acrylic compounds such as urethane acrylate, polyester acrylate, and epoxy acrylate. From the viewpoint of the reactivity of the organopolysiloxane represented by formula (1) obtained by the Michael addition reaction, di- to hexafunctional acrylic monomers are preferred.

[0020] The reaction is preferably carried out by adding at least one equivalent of a difunctional or higher functional acrylic compound to the —NH— of the organopolysiloxane, in which case the reaction product is an organopolysiloxane compound represented by formula (1) above, which has excellent photocurability and reactivity.

[0021] The above reaction proceeds without a catalyst, and the organopolysiloxane compound represented by formula (1) can be produced simply by mixing and heating an organopolysiloxane having amino groups with a difunctional or higher acrylic compound. However, an acid catalyst or a base catalyst may be added as needed. Examples of acid catalysts include AlCl3 and MgCl2. Examples of base catalysts include non-nucleophilic tertiary amines (N,N,N',N'-tetramethyl-1,8-naphthalenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, etc.). These catalysts can be used alone or in combination of two or more.

[0022] In the above reaction, the reaction temperature is not particularly limited, but for the purpose of preventing polymerization of the acrylic group and promoting the reaction, it is preferably 20 to 100° C., and more preferably 50 to 80° C. In the above reaction, the reaction time is not particularly limited, but it is preferably 3 to 24 hours, and more preferably 6 to 18 hours.

[0023] The reaction is preferably carried out in the presence of a solvent. Addition of a solvent facilitates compatibility between the amino group-containing organopolysiloxane and the difunctional or higher functional acrylic compound, which is preferable because it allows the Michael addition reaction to proceed efficiently. The solvent is preferably one that does not have a group reactive with the amino group or the acrylic group, and examples thereof include hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.) and ethers (diethyl ether, tetrahydrofuran, 1,4-dioxane, etc.). These solvents can be used alone or in combination of two or more.

[0024] Furthermore, the above reaction may be carried out with the addition of a polymerization inhibitor, if necessary. The polymerization inhibitor may be any one that has been conventionally used for acrylic compounds. Examples of the polymerization inhibitor include phenolic polymerization inhibitors such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, 2-tert-butylhydroquinone, 4-methoxyphenol, and 2,6-di-tert-butyl-p-cresol. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor is not particularly limited, but is preferably 5 to 1,000 ppm, more preferably 20 to 500 ppm, based on the mass of the resulting compound.

[0025] [Composition Containing Organopolysiloxane Compound] The composition of the present invention contains the organopolysiloxane compound of the present invention described above. In addition to the organopolysiloxane compound of the present invention described above, the composition of the present invention may also contain one or more acrylic compounds other than the organopolysiloxane compound of the present invention. Because the organopolysiloxane compound of the present invention has high photocurability and reactivity, a composition containing this compound can be cured with little energy.

[0026] Furthermore, in the reaction for synthesizing the organopolysiloxane compound of the present invention, unreacted difunctional or higher (b+1) acrylic compounds (e.g., polyfunctional acrylic monomers) may remain in the reaction product. This unreacted acrylic compound may be removed by solvent extraction or the like, or may be used as a copolymerizable monomer in the composition of the present invention. That is, the composition of the present invention may be obtained as the reaction product obtained in the above reaction, comprising an organopolysiloxane compound represented by formula (1) above and a difunctional or higher (b+1) acrylic compound. In this case, examples of the difunctional or higher (b+1) acrylic compound contained in the composition of the present invention include the various acrylic compounds exemplified as the difunctional or higher (b+1) acrylic compound represented by reaction formula (A) above, with di- to hexafunctional acrylic monomers being preferred. Alternatively, the composition of the present invention may be prepared by purifying a mixture of the organopolysiloxane compound represented by formula (1) obtained by the above reaction and an unreacted difunctional or higher (b+1) acrylic compound using a conventional method, followed by adding one or more acrylic compounds, preferably a b+1 polyvalent acrylic monomer, more preferably a di- to hexafunctional acrylic monomer. Alternatively, the composition of the present invention may be prepared by using a mixture of the organopolysiloxane compound represented by formula (1) obtained by the above reaction and an unreacted trifunctional or higher (b+1) acrylic compound as is, or by purifying the mixture using a conventional method, followed by adding one or more acrylic compounds, preferably a b+1 polyvalent acrylic monomer, more preferably a tri- to hexafunctional acrylic monomer. [Cured Product] The cured product of the present invention can be obtained by curing the composition of the present invention. Curing proceeds by radical polymerization of the composition using heat or light using a conventional method, resulting in a cured product.

[0027] 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. In the following examples, the number average molecular weight and dispersity (weight average molecular weight / number average molecular weight) are polystyrene-equivalent values ​​determined by GPC (gel permeation chromatography) measurement using tetrahydrofuran as the developing solvent under the following conditions. [Measurement conditions] Developing solvent: tetrahydrofuran Flow rate: 0.6 mL / min Detector: differential refractive index detector (RI) Column: TSK Guard column Super H-H TSKgel Super HM-N (6.0 mm I.D. × 15 cm × 1) TSKgel Super H2500 (6.0 mm I.D. × 15 cm × 1) (all manufactured by Tosoh Corporation) Column temperature: 40°C Sample injection volume: 50 μL (tetrahydrofuran solution with a concentration of 0.3 wt %)

[0028] Example 1 70.5 g of an organopolysiloxane having amino groups at both ends, represented by the following formula (8-1), 31.4 g of 1,6-hexanediol diacrylate, 67.9 g of toluene, and 0.031 g of 2,6-di-tert-butyl-p-cresol were placed in a reaction vessel and stirred at 70°C for 20 hours to prepare a mixed solution. The toluene was then removed from the mixed solution by distillation under reduced pressure, yielding a liquid. 86.0 g of methanol was added to the resulting liquid for washing, and the liquids were separated to recover the organopolysiloxane phase. After performing the same washing procedure a total of three times, the remaining methanol was removed by distillation under reduced pressure, yielding 46.3 g of a liquid (FIGS. 1 and 2).

[0029]

[0030]

[0031] From the above results, the obtained liquid was an organopolysiloxane represented by the following formula (1-1). (In the formula, a i is 0 or 1. i is a number from 1 to 8, starting from 1.

[0032] Example 2 A reaction vessel was charged with 57.8 g of an organopolysiloxane having amino groups at both ends, represented by the following formula (8-2), 38.2 g of tripropylene glycol diacrylate, 64.0 g of toluene, and 0.029 g of 2,6-di-tert-butyl-p-cresol, and the mixture was stirred at 70° C. for 20 hours to prepare a mixed solution. Thereafter, the toluene was distilled off under reduced pressure from the mixed solution, yielding 91.7 g of a liquid product.

[0033] From the above results, the obtained liquid was a mixture of organopolysiloxane represented by the following formula (1-2) and tripropylene glycol diacrylate. (In the formula, a i is 0 or 1. i is a number from 1 to 8, starting from 1.

[0034] Example 3 A reaction vessel was charged with 52.1 g of the organopolysiloxane having amino groups at both ends, represented by the above formula (8-2), 35.0 g of trimethylolpropane triacrylate, 58.1 g of toluene, and 0.026 g of 2,6-di-tert-butyl-p-cresol, and the mixture was stirred at 70° C. for 20 hours to prepare a mixed solution. Thereafter, the toluene was distilled off from the mixed solution under reduced pressure, yielding 80.6 g of a liquid product.

[0035] From the above results, the obtained liquid was a mixture of organopolysiloxane represented by the following formula (1-3) and trimethylolpropane triacrylate. (In the formula, a i is 0, 1, or 2. i is a number from 1 to 10, starting from 1.

[0036] Example 4 A reaction vessel was charged with 3.98 g of the organopolysiloxane having amino groups at both ends, represented by the above formula (8-2), 11.6 g of dipentaerythritol hexaacrylate, 10.4 g of toluene, and 0.005 g of 2,6-di-tert-butyl-p-cresol, and the mixture was stirred at 70° C. for 20 hours to prepare a mixed solution. Thereafter, the toluene was distilled off from the mixed solution under reduced pressure, yielding 12.2 g of a liquid product.

[0037] From the above results, the obtained liquid was a mixture of organopolysiloxane represented by the following formula (1-4) and dipentaerythritol hexaacrylate. (In the formula, a i is 0, 1, or 2. i is a number from 1 to 8, starting from 1.

[0038] Comparative Example 1 A bifunctional acrylic-modified organopolysiloxane represented by the following formula (9): Comparative Example 2 A polyfunctional acrylic-modified organopolysiloxane represented by the following formula (10): [Comparative Example 3] 1,6-hexanediol diacrylate [Comparative Example 4] Tripropylene glycol diacrylate [Comparative Example 5] Trimethylolpropane triacrylate [Comparative Example 6] Dipentaerythritol hexaacrylate

[0039] [Evaluation of UV Curability] A liquid composition was prepared by adding 0.020 g of a photopolymerization initiator, Omnirad 1173, manufactured by IGM Resins, to 10 g of each of the compositions of the above Examples or the compounds of the above Comparative Examples. The gel point (the time at which storage modulus (G') = loss modulus (G")) of the liquid composition was measured under the following conditions using a viscoelasticity measuring device (DHR2 (Discovery Hybrid Rheometer) manufactured by TA Instruments), and UV curability was evaluated. The results are shown in Table 9.

[0040] [Conditions for measuring gel point] UV light source: OmniCure SERIES 2000 (Excelitas Technologies) UV illuminance: 10 mW / cm 2 Viscoelasticity measuring device: DHR2 (Discovery Hybrid Rheometer) (TA Instruments) Measurement mode: compression Initial torque: 10.0 μN·m Strain: 10.0% Frequency: 25.0 Hz Sample film thickness: 200 μm

[0041]

[0042] [Evaluation of Bleeding] A composition solution was prepared by adding 10 g of trimethylolpropane triacrylate and 0.1 g of a photopolymerization initiator, Omnirad 1173, manufactured by IGM Resins, to 0.5 g of each of the compositions of the above Examples or the organopolysiloxane compound of the above Comparative Examples, and the composition was applied to a polycarbonate substrate using a bar coater No. 4. Using a UV curing device (MUVBA manufactured by ITEC Systems), the composition was cured with light at a wavelength of 365 nm and an intensity of 140 mW / cm. 2 The coating film was cured by irradiating it with UV light of 1000 kJ / 2000 kJ / 2000 kJ for 2 seconds in a nitrogen atmosphere, and the presence or absence of bleeding was evaluated by touch. The results are shown in Table 10.

[0043] The results in Table 9 demonstrate that the organopolysiloxane compound of the present invention has a faster gel point and higher UV curability than conventional acrylic-modified organopolysiloxanes. Surprisingly, the organopolysiloxane compound of the present invention, in which an organopolysiloxane compound having a primary amino group is subjected to Michael addition to a polyfunctional acrylic compound, exhibits higher UV curability than the polyfunctional acrylic compound used as the raw material. The results in Table 10 demonstrate that the organopolysiloxane compound of the present invention is less susceptible to bleeding due to its high UV curability. The organopolysiloxane compound of the present invention is useful as an additive in UV-curable resin compositions, UV-curable silicone elastomers, coating agents, etc.

Claims

1. An organopolysiloxane compound represented by the following formula (1): 【Chemistry 1】 [In formula (1), W is expressed by the following formula (2): 【Chemistry 2】 (In formula (2), R 1 are each independently a group selected from an alkyl group having 1 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms, and n is a number from 0 to 1,000. is a group represented by Each L is independently an alkylene group having 2 to 12 carbon atoms; X i are each independently an alkyl group having 1 to 18 carbon atoms (wherein the alkyl group may have one or more bonds selected from an ether bond, an ester bond, an amide bond, and a hydroxyl group), and a group represented by the following formula (3): 【Transformation 3】 In formula (3), W and L are the same as defined above, X i+1 is defined the same as X i in formula (1), and each Z is independently an oxygen atom, a sulfur atom, or NR 2 and the NR 2 R in 2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, M is a polyvalent organic group having a valence of b+1, i is a number from 1 to 30, provided that i starts from 1, i is a number from 0 to b, and b is a number from 1 to 20.) and However, X in formula (1) i At least one of the following is b-a i is a group represented by formula (3) in which

2. X i The organopolysiloxane compound according to claim 1, wherein all of the following are groups represented by formula (3):

3. 3. The organopolysiloxane compound according to claim 2, wherein b is a number from 1 to 5.

4. A composition comprising the organopolysiloxane compound of claim 1.

5. The composition of claim 4 further comprising one or more acrylic compounds other than the organopolysiloxane compound.

6. 6. The composition according to claim 5, wherein the acrylic compound is a b+1 polyvalent acrylic monomer.

7. A cured product of the composition according to claim 4.

Images