Organopolysiloxane compounds, compositions containing the same, and cured products thereof

Abstract

The present invention provides: an organopolysiloxane compound which has high reactivity; and a composition containing the same.　The present invention specifically provides an organopolysiloxane compound which is represented by formula (1). (In formula (1), W represents a monovalent organopolysiloxane residue, L represents an alkylene group having 2 to 12 carbon atoms, each Z independently represents an oxygen atom or the like, b represents a number of 2 to 20, M represents a polyvalent organic group having a valence of (b + 1), and Xi represents one or more groups that are selected from among a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and a group represented by formula (3) (in formula (3), M, Z, L, W, b and Xi are the same as defined above, i represents a number of 1 to 5, provided that i begins with 1, and ai represents a number of 0 to b, provided that a5 is 0.)

Description

[Technical Field]

[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. [Background technology]

[0002] In recent years, with increasing demands for energy conservation and process shortening, photocurable resins that can cure quickly at room temperature have attracted attention, and are mainly made from radically polymerizable acrylic compounds. Such photocurable resins are used in paints, coatings, and inks, but sometimes properties such as high water repellency, stain resistance, and lubricity are required. A known method for imparting high water repellency, stain resistance, and lubricity to photocurable resins involves copolymerizing them with organopolysiloxanes having (meth)acryloyl groups (Patent Document 1). However, many organopolysiloxanes having a (meth)acryloyl group have low reactivity, which can easily lead to problems such as unreacted organopolysiloxanes bleeding from the cured resin over time (Patent Document 2). Therefore, there was a strong need for organopolysiloxane compounds that could solve this problem. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2022-138932 [Patent Document 2] Japanese Patent Publication No. 2005-36018 [Overview of the project] [Problems that the invention aims to solve]

[0004] Therefore, the present invention aims to provide a highly reactive radical polymerizable organopolysiloxane compound, a composition containing the same, and a cured product thereof. [Means for solving the problem]

[0005] The inventors of the present invention conducted extensive research to solve the above problems and, as a result, discovered that organopolysiloxane compounds having a specific acryloyl group can achieve the above objectives, thus completing the present invention. In other words, the present invention is as follows.

[0006] [1] An organopolysiloxane compound represented by the following formula (1). [ka] [In formula (1), W is given by the following equation (2) [ka] (In formula (2), R 1 and R 1' Each of these groups is independently selected from alkyl groups having 1 to 18 carbon atoms and aryl groups having 6 to 18 carbon atoms, and n is a number from 0 to 500. It is a base represented by, L is an alkylene group with 2 to 12 carbon atoms. Each Z independently represents an oxygen atom, a sulfur atom, or NR. 2 The group is shown by and the NR 2 R inside 2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. b is a number between 2 and 20. M is a b+1 valent polyvalent organic group, X i is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms (however, the alkyl group may have one or more selected from ether bonds, ester bonds, amide bonds, and hydroxyl groups) and the following formula (3) [ka] (In equation (3), M, Z, L, W, b and X iis the same as above, i is a number from 1 to 5, provided that i starts from 1, a i is a number from 0 to b, provided that a5 is 0.) is one or more groups selected from the groups represented by ] [2] X i is the group represented by formula (3). The organopolysiloxane compound according to [1]. [3] X i is the group represented by formula (3), and i is a number from 1 to 3. The organopolysiloxane compound according to [1] or [2]. [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)-valent polyvalent acrylic monomer. [7] A cured product of the composition according to any one of [4] to [6]. [Effects of the Invention]

[0007] The organopolysiloxane compound of the present invention has two or more acryloyl groups in sterically close positions within one molecule, has high photocurability and reactivity, and is less prone to bleeding when blended into a photocurable resin composition or the like and copolymerized. Furthermore, since it cures with less energy, energy saving and process shortening during the production of cured products are possible. The present invention is suitable for paints, coating agents, inks and the like. Brief Description of the Drawings

[0008] [Figure 1]This is the 1H-NMR spectral chart of the organopolysiloxane compound synthesized in Example 1. [Modes for carrying out the invention]

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

[0010] [Organopolysiloxane compounds] The organopolysiloxane compound of the present invention is represented by the following formula (1), and since it has two or more acryloyl groups in one molecule, it can react with radical polymerizable compounds. [ka]

[0011] In formula (1) above, W is a group represented by formula (2) below (a monovalent organopolysiloxane-containing group). [ka]

[0012] In formula (2), R 1 R is a group independently selected from alkyl groups having 1 to 18 carbon atoms and aryl groups having 6 to 18 carbon atoms, preferably a methyl group or a phenyl group. 1 ' is a group independently selected from C1-C18 alkyl groups and C6-C18 aryl groups, preferably a methyl group, an n-butyl group, or a phenyl group, more preferably a methyl group or an n-butyl group. n is a number from 0 to 500, preferably a number from 3 to 200, more preferably a number from 8 to 60. Examples of groups represented by formula (2) above include those represented by formulas (4) to (8) below, but are not limited to those formulas below. [ka]

[0013] In formula (1) above, 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. In formula (1) above, Z is independently an oxygen atom, a sulfur atom, or NR. 2 The group is represented by , and is preferably an oxygen atom. 2 R inside 2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably a hydrogen atom. In formula (1) above, b is a number between 2 and 20, preferably a number between 2 and 10, and more preferably a number between 2 and 5. In formula (1) above, M is a b+1 valent polyvalent organic group (for example, a chain-like hydrocarbon group having 2 to 50 carbon atoms that may have ether and ester bonds), preferably a 3 to 6 valent polyvalent organic group, and more preferably a 3 to 6 valent aliphatic hydrocarbon group that may have ether, ester, and hydroxyl groups. Examples of the polyvalent organic group M mentioned above include, but are not limited to, the group represented by the following formula.

[0014] [ka]

[0015] In formula (1) above, Xi is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms (however, the alkyl group may have one or more selected from ether bonds, ester bonds, amide bonds, and hydroxyl groups), and a group represented by the following formula (3), preferably a group represented by the following formula (3). [ka]

[0016] In equation (3), M, Z, L, W, b and X i The same as in formula (1) above can be given. i is a number from 1 to 5, preferably from 1 to 3. However, i starts from 1. i a5 is a number between 0 and b, where a5 is 0. The above X i Examples include, but are not limited to, the base represented by the following formula. [ka] [ka] [ka] [ka]

[0017] [Method for producing organopolysiloxane compounds] The organopolysiloxane compound represented by formula (1) of the present invention can be produced, for example, by the following method. In other words, it can be produced by reacting an organopolysiloxane having a primary or secondary amino group at one end with a trifunctional (b+1 valent) acrylic compound via a Michael addition reaction as shown in the reaction formula (A) below. [ka]

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

[0019] Examples of the three- or more functional acrylic compounds mentioned above include 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 Michael addition reactivity with organopolysiloxanes having amino groups, 3 to 6 functional acrylic monomers are preferred.

[0020] In the above reaction, it is preferable to charge at least one equivalent of a trifunctional or more acrylic compound to the -NH- group of the organopolysiloxane. In this case, the reaction product is an organopolysiloxane compound represented by formula (1) above, which has two or more acryloyl groups in sterically close positions within the molecule, and exhibits 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 an organopolysiloxane having an amino group with a trifunctional or higher acrylic compound and heating it. 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]undeca-7-ene, etc.). These catalysts can be used individually or in combination of two or more.

[0022] In the above reaction, there are no particular restrictions on the reaction temperature, but it is preferably 20 to 100°C, and more preferably 50 to 80°C, for the purpose of preventing polymerization of the acrylic group and promoting the reaction. In the above reaction, there are no particular restrictions on the reaction time, but it is preferably 3 to 24 hours, and more preferably 6 to 18 hours.

[0023] Furthermore, the above reaction may be carried out with the addition of a solvent as needed. Adding a solvent can make the organopolysiloxane having an amino group more compatible with the trifunctional or higher acrylic compound, which can allow the Michael addition reaction to proceed more efficiently. The solvent is preferably one that does not have groups that can react with the amino group and the acrylic group, and examples include hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.) and ethers (diethyl ether, tetrahydrofuran, 1,4-dioxane, etc.). These solvents can also be used individually or in combination of two or more.

[0024] Furthermore, the above reaction may be carried out with the addition of a polymerization inhibitor as needed. Any polymerization inhibitor conventionally used for acrylic compounds may be used. Examples of polymerization inhibitors 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 individually or in combination of two or more. The amount of polymerization inhibitor is not particularly limited, but it is preferably 5 to 1,000 ppm relative to the mass of the resulting compound, and more preferably 20 to 500 ppm.

[0025] [Compositions containing organopolysiloxane compounds] 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. Furthermore, the reaction described above for producing the organopolysiloxane compound may result in the presence of unreacted trifunctional or higher (b+1 valent) acrylic compounds (e.g., polyvalent acrylic monomers) in the reaction product. That is, the reaction may yield a mixture of the organopolysiloxane compound of the present invention represented by formula (1) and unreacted trifunctional or higher (b+1 valent) acrylic compounds. Therefore, as an example of a method for preparing the composition of the present invention, one method is to obtain the reaction product obtained in the above reaction as the composition of the present invention, which contains an organopolysiloxane compound represented by formula (1) and a trifunctional (b+1 valent) acrylic compound. In this case, the trifunctional (b+1 valent) acrylic compound included in the composition of the present invention can be any of the various acrylic compounds exemplified as trifunctional (b+1 valent) acrylic compounds shown in reaction formula (A) above, and 3- to 6-functional acrylic monomers are preferred. Alternatively, the composition of the present invention may be prepared by using a mixture of the organopolysiloxane compound represented by formula (1) obtained in the above reaction and an unreacted trifunctional or more (b+1 valent) acrylic compound, either as is or purified by conventional methods, and separately adding one or more acrylic compounds, preferably b+1 valent polyhydric acrylic monomers, more preferably tri- to hexafunctional acrylic monomers. [Cured product] A cured product of the present invention can be obtained by curing the above-described composition of the present invention. Curing proceeds by radical polymerization of the above-described composition with heat or light using conventional methods, thereby obtaining a cured product. [Examples]

[0026] The present invention will be specifically described 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 dispersion (weight-average molecular weight / number-average molecular weight) are polystyrene-converted values ​​obtained by GPC (gel permeation chromatography) measurement using tetrahydrofuran as the developing solvent under the conditions shown below. [Measurement conditions] Developing solvent: tetrahydrofuran Flow rate: 0.6mL / min Detector: Differential refractive index detector (RI) Column: TSK Guardcolumn SuperH-H TSKgel SuperHM-N(6.0mmI.D.×15cm×1) TSKgel SuperH2500(6.0mmI.D.×15cm×1) (All manufactured by Tosoh Corporation) Column temperature: 40℃ Sample injection volume: 50 μL (0.3 wt% tetrahydrofuran solution)

[0027] [Example 1] In a reaction vessel, 5.93 g of trimethylolpropane triacrylate, 4.37 g of toluene, and 0.005 g of 2,6-di-tert-butyl-p-cresol were added and stirred. A solution consisting of 8.57 g of organopolysiloxane having an amino group at one end as shown in formula (8-1) and 5.61 g of toluene was added dropwise at 60°C for 1 hour to prepare a mixed solution. The resulting mixed solution was stirred further at 60°C for 12 hours, after which toluene was removed from the mixed solution under reduced pressure to obtain a liquid. 14.5 g of hexane was added to the obtained liquid to make a solution, then 29.0 g of methanol was added and washed, and the hexane phase was recovered by liquid-liquid separation. Hexane was then removed from the hexane phase under reduced pressure to obtain 8.3 g of liquid. [ka]

[0028] [Table 1] [Table 2]

[0029] From the above results, the obtained liquid was a mixture of organopolysiloxane and trimethylolpropane triacrylate represented by the following formulas (1-1), (1-2), and (1-3). [ka]

[0030] [Example 2] In a reaction vessel, 5.93 g of trimethylolpropane triacrylate, 4.07 g of toluene, and 0.006 g of 2,6-di-tert-butyl-p-cresol were added and stirred. A solution consisting of 12.4 g of organopolysiloxane having an amino group at one end as shown in formula (8-2) and 8.80 g of toluene was added dropwise at 60°C for 1 hour to prepare a mixed solution. The resulting mixed solution was stirred further at 60°C for 12 hours, after which toluene was removed from the mixed solution under reduced pressure to obtain a liquid. 18.3 g of hexane was added to the obtained liquid to make a solution, then 36.6 g of methanol was added and washed, and the hexane phase was recovered by liquid-liquid separation. Hexane was then removed from the hexane phase under reduced pressure to obtain 11.9 g of liquid. [ka] [Table 3] [Table 4] From the above results, the obtained liquid was a mixture of organopolysiloxane represented by the following formulas (1-4), (1-5), and (1-6) and trimethylolpropane triacrylate. [ka]

[0031] [Example 3] In a reaction vessel, 11.6 g of dipentaerythritol hexaacrylate, 13.4 g of toluene, and 0.006 g of 2,6-di-tert-butyl-p-cresol were added and stirred. 8.57 g of organopolysiloxane having an amino group at one end, as shown in formula (8-1), was added dropwise at 60°C for 1 hour to prepare a mixed solution. The resulting mixed solution was further stirred at 60°C for 12 hours, and then toluene was removed from the mixed solution under reduced pressure to obtain 14.3 g of liquid. [Table 5] [Table 6]

[0032] From the above results, the obtained liquid was a mixture of organopolysiloxane represented by the following formulas (1-7), (1-8), (1-9), and (1-10) and dipentaerythritol hexaacrylate. [ka] [ka] [ka] [ka]

[0033] [Comparative Example 1] A monoacrylic-modified organopolysiloxane represented by the following formula (9). [ka]

[0034] [Comparative Example 2] A polyfunctional acrylic-modified organopolysiloxane represented by the following formula (10). [ka]

[0035] [Comparative Example 3] Trimethylolpropane triacrylate

[0036] [Comparative Example 4] Dipentaerythritol hexaacrylate

[0037] [Evaluation of UV curability] To prepare a compositional solution, 0.020 g of Omnirad 1173 from IGM Resins, a photopolymerization initiator, was added to 10 g each of the compositions of the above examples or the compounds of the above comparative examples. The gelation point (the time at which the storage modulus (G') = loss modulus (G)) of the compositional solution was measured using a viscoelasticity analyzer (DHR2 (Discovery Hybrid Rheometer) from TA Instruments) under the following conditions, and the UV curability was evaluated.

[0038] [Measurement conditions for the gelation point] UV light source: OmniCure SERIES 2000 (Excelitas Technologies) UV illuminance: 10mW / cm 2 Viscoelasticity measuring device: DHR2 (Discovery Hybrid Rheometer) (TA Instruments) Measurement mode: Compression Initial torque: 10.0 μN·m Distortion: 10.0% Frequency: 25.0Hz Sample film thickness: 200 μm

[0039] [Table 7]

[0040] [Breed evaluation] To each of the above examples or comparative examples, 0.5 g of the organopolysiloxane compound was prepared by adding 10 g of trimethylolpropane triacrylate and 0.1 g of Omnirad 1173 from IGM Resins, a photopolymerization initiator. This solution was then coated onto a polycarbonate substrate using a bar coater No. 4. A UV curing device (MUVBA from ITEC Systems) was used at a wavelength of 365 nm and an intensity of 140 mW / cm². 2 The above coating film was cured by irradiating it with UV light in a nitrogen atmosphere at room temperature for 2 seconds, and the presence or absence of bleeding was evaluated by touch. The results are shown in Table 8. [Table 8]

[0041] The results in Table 7 show that the organopolysiloxane compounds of the present invention have a faster gelation point and higher UV curability than conventional acrylic-modified organopolysiloxanes. Surprisingly, the organopolysiloxane compounds of the present invention, obtained by Michael addition of an organopolysiloxane having a primary amino group to a polyfunctional acrylic compound, showed higher UV curability than the polyfunctional acrylic compound used as a raw material. Furthermore, the results in Table 8 show that the organopolysiloxane compounds of the present invention react even with low UV irradiation doses and are less prone to bleeding due to their high UV curability. The organopolysiloxane compounds of the present invention are useful as additives in UV-curable resin compositions and as UV-curable silicone elastomers.

Claims

1. An organopolysiloxane compound represented by the following formula (1). 【Chemistry 1】 [In formula (1), W is given by the following formula (2) 【Chemistry 2】 (In formula (2), R 1 and R 1' Each of these groups is independently selected from alkyl groups having 1 to 18 carbon atoms and aryl groups having 6 to 18 carbon atoms, and n is a number from 0 to 500. It is a base represented by, L is an alkylene group having 2 to 12 carbon atoms. Z can be an oxygen atom, a sulfur atom, or NR, each independently. 2 The group is represented by and the NR 2 R inside 2 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. b is a number between 2 and 20. M is a b+1 valent polyvalent organic group, X i is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms (however, the alkyl group may have one or more selected from ether bonds, ester bonds, amide bonds, and hydroxyl groups) and the following formula (3) 【Transformation 3】 (In equation (3), M, Z, L, W, and b are the same as above, X i+1 is defined in the same way as X i in equation (1), i is a number from 1 to 5, where i starts from 1, and a i is a number from 0 to b, where a 5 (It is 0.) It is one or more groups selected from the groups represented by [the formula shown].

2. X i is a group represented by formula (3), the organopolysiloxane compound according to claim 1.

3. X i The organopolysiloxane compound according to claim 1, wherein is a group represented by formula (3), and i is a number from 1 to 3.

4. A composition comprising the organopolysiloxane compound described in claim 1.

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

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

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

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