Organopolysiloxane compound and photocurable resin composition containing the same

Abstract

To provide a radical-polymerizable organopolysiloxane compound or the like which is highly compatible with acrylic compounds and exhibits high photocurability and anti-fouling properties, as well as low viscosity and excellent workability.SOLUTION: The present invention provides an organopolysiloxane compound represented by formula (1). (In formula (1), R1 moieties are each independently an alkyl group having 1-6 carbon atoms, and R2 moieties are each independently a group selected from among an alkyl group having 1-6 carbon atoms and a group represented by formula (2). (In formula (2), L1 is an alkylene group having 3-8 carbon atoms, L2 is an alkylene group having 2-4 carbon atoms, and n is a number between 9 and 12).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an organopolysiloxane compound and a photocurable resin composition containing the same.

Background Art

[0002] As a method for imparting high water repellency, antifouling property, lubricity, etc. to a photocurable resin, a method of blending and copolymerizing an organopolysiloxane having a (meth)acryloyl group is known (Patent Document 1). However, many organopolysiloxanes having a (meth)acryloyl group have low compatibility with photocurable resins, and problems such as separation when blended in a photocurable resin composition or turbidity in the cured resin are likely to occur (Patent Document 2). In addition, many organopolysiloxanes having a (meth)acryloyl group have low photocurability, and problems such as unreacted organopolysiloxane bleeding out over time from the cured resin are likely to occur (Patent Document 3). Also, those with low photocurability are prone to inhibition of curing by oxygen. Although the introduction of a urea group is one of the techniques for improving photocurability, there is a concern that the viscosity will increase and the workability will deteriorate (Patent Document 4). Therefore, an organopolysiloxane compound that solves these problems has been urgently desired.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

[0004] Accordingly, an object of the present invention is to provide a radically polymerizable organopolysiloxane compound having high compatibility with a photocurable resin such as an acrylic compound, high photocurability, antifouling properties, low viscosity, and excellent workability, and a photocurable resin composition containing the same. [Means for Solving the Problems]

[0005] As a result of intensive studies to solve the above problems, the present inventors have found that an organopolysiloxane compound having an acryloyl group via a specific linking group can achieve the above object, and have completed the present invention. That is, the present invention is as follows.

[0006] [1] An organopolysiloxane compound represented by the following formula (1), [Chemical formula] (In formula (1), each R 1 is independently an alkyl group having 1 to 6 carbon atoms, each R 2 is independently an alkyl group having 1 to 6 carbon atoms and the following formula (2) [Chemical formula] (In formula (2), L 1 is an alkylene group having 3 to 8 carbon atoms, L 2 is an alkylene group having 2 to 4 carbon atoms, and n is a number from 9 to 12.) and is a group selected from the groups represented by, each R 3 is a group represented by formula (2), a is a number from 5 to 40, and b is a number from 0 to 5.) The organopolysiloxane compound represented by formula (1) has two or more groups represented by formula (2) in one molecule, An organopolysiloxane compound in which the proportion of the groups represented by the formula (2) is 4 to 15% with respect to the total number of substituents in the organopolysiloxane compound represented by the formula (1). [2] R 1 The organopolysiloxane compound according to [1], wherein all of are methyl groups. [3] a is a number from 5 to 40, b is 0, and all of R in the formula (1) 2 The organopolysiloxane compound according to [1] or [2], wherein all of are groups represented by the formula (2). [4] a is a number from 5 to 40, b is a number from 2 to 5, and all of R in the formula (1) 2 The organopolysiloxane compound according to [1] or [2], wherein all of are methyl groups. [5] a is a number from 5 to 40, b is a number from 1 to 5, and all of R in the formula (1) 2 The organopolysiloxane compound according to [1] or [2], wherein all of are groups represented by the formula (2). [6] A photocurable resin composition comprising the organopolysiloxane compound according to any one of [1] to [5], a polyvalent acrylic compound, and a photopolymerization initiator.

Advantages of the Invention

[0007] The organopolysiloxane compound of the present invention is excellent in compatibility with photocurable resins such as acrylic compounds. Therefore, a photocurable composition containing the polysiloxane compound and an acrylic compound can be a cured product with high transparency and excellent appearance. Further, since the organopolysiloxane compound of the present invention has high photocurability, a composition containing the compound can be cured with less energy and is less likely to bleed. Furthermore, energy saving and process shortening during the production of the cured product are also possible. In addition, a composition containing the compound can be a cured product with excellent antifouling properties. Also, since the compound has a low viscosity and excellent workability, a composition containing the compound also has good handleability. Therefore, the organopolysiloxane compound of the present invention and the photocurable resin composition containing the compound are suitable for paints, coating agents, inks, etc.

Brief Description of the Drawings

[0008]

Figure 1

Modes for Carrying Out the Invention

[0009] Hereinafter, the present invention will be described in more detail.

[0010] [Organopolysiloxane Compound] The organopolysiloxane compound of the present invention is represented by the following formula (1), has two or more acryloyl groups in one molecule, and is easily reactive with a radical polymerizable compound.

Chemical formula

[0011]

Chemical formula

[0012] In the above formula (1), a is a number from 5 to 40, preferably a number from 10 to 30, more preferably a number from 15 to 35. b is a number from 0 to 5, preferably a number from 0 to 4. However, since the organopolysiloxane compound represented by formula (1) has two or more groups represented by formula (2) in one molecule, R in formula (1) 2 When all of them are alkyl groups having 1 to 6 carbon atoms, b is a number from 2 to 5, preferably a number from 2 to 4.

[0013] The molecular weight of the organopolysiloxane compound represented by the above formula (1) is preferably from 1,500 to 6,000, more preferably from 2,000 to 5,500, and even more preferably from 2,500 to 5,000. The molecular weight referred to in this specification shall refer to the calculated molecular weight calculated from the structural formula.

[0014] The organopolysiloxane compound represented by the above formula (1) has two or more groups represented by the above formula (2) in one molecule, preferably 3 to 6, more preferably 4 to 5. However, the proportion of the number of groups represented by the above formula (2) is 4 to 15% with respect to the total number of substituents in the organopolysiloxane compound represented by the above formula (1), preferably 4 to 12%.

[0015] The organopolysiloxane compound represented by the above formula (1) of the present invention can be produced by a urethanization reaction between an organopolysiloxane having a polyoxyethylene with a hydroxy group at the terminal and an acrylic compound having an isocyanate group. Examples of the acrylic compound having an isocyanate group include 2-isocyanatoethyl acrylate and the like.

[0016] The above reaction may be carried out by adding a catalyst as necessary. For example, di-n-octyltin oxide, dibutyltin dilaurate, iron(III) acetylacetonate, bismuth(III) octylate, titanium(IV) 2-ethylhexoxide, 1,4-diazabicyclo[2.2.2]octane, 2,2'-dimorpholinodiethyl ether, triethylamine, etc. may be mentioned. Among them, iron(III) acetylacetonate, which has high activity and low toxicity, is preferred. These catalysts can be used alone or in combination of two or more.

[0017] In the above reaction, the reaction temperature is not particularly limited, but it is preferably 20 to 80°C, more preferably 50 to 70°C, for the purpose of preventing the polymerization of the acrylic group and promoting the reaction. In the above reaction, the reaction time is not particularly limited, but it is preferably 1 to 8 hours, more preferably 2 to 6 hours.

[0018] Also, the above reaction may be carried out by adding a solvent as necessary. The solvent preferably does not have a group capable of reacting with the isocyanate group. For example, hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.), ethers (diethyl ether, tetrahydrofuran, 1,4-dioxane, etc.), esters (ethyl acetate, butyl acetate), ketones (methyl ethyl ketone, methyl isobutyl ketone), etc. may be mentioned. Also, these solvents can be used alone or in combination of two or more.

[0019] Further, the above reaction may be carried out by adding a polymerization inhibitor as needed. Any polymerization inhibitor that has been conventionally used for acrylic compounds may be used. 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 an amount of 5 to 1,000 ppm, more preferably 20 to 500 ppm, based on the mass of the resulting compound is preferred.

[0020] [Photocurable resin composition] The organopolysiloxane compound of the present invention can provide a cured product having excellent antifouling properties when blended into a photocurable composition containing a polyvalent acrylic compound and a photopolymerization initiator.

[0021] Examples of the polyvalent acrylic compound include bifunctional 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.

[0022] The blending ratio of the above polyvalent acrylic compound and the organopolysiloxane compound of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass of the organopolysiloxane compound with respect to 100 parts by mass of the polyvalent acrylic compound. Within this range, it is preferable because the effect of adding the organopolysiloxane compound of the present invention to the photocurable resin composition can be sufficiently obtained.

[0023] Examples of the photopolymerization initiator include 2,2 - diethoxyacetophenone, 2,2 - dimethoxy - 1,2 - diphenylethane - 1 - one (Omnirad 651 manufactured by IGM Resins), 1 - hydroxy - cyclohexyl - phenyl - ketone (Omnirad 184 manufactured by IGM Resins), 2 - hydroxy - 2 - methyl - 1 - phenyl - propan - 1 - one (Omnirad 1173 manufactured by IGM Resins), 2 - hydroxy - 1 - {4 - [4 - (2 - hydroxy - 2 - methyl - propionyl) - benzyl] - phenyl} - 2 - methyl - propan - 1 - one (Omnirad 127 manufactured by IGM Resins), 2 - methyl - 1 - [4 - (methylthio)phenyl] - 2 - morpholinopropan - 1 - one (Omnirad 907 manufactured by IGM Resins), 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinophenyl) - 1 - butanone (Omnirad 369 manufactured by IGM Resins), bis(2,4,6 - trimethylbenzoyl) - phenylphosphine oxide (Omnirad 819 manufactured by IGM Resins), 2,4,6 - trimethylbenzoyl - diphenyl - phosphine oxide (Omnirad TPO manufactured by IGM Resins), etc. These photopolymerization initiators can be used alone or in combination of two or more.

[0024] In the photocurable resin composition of the present invention, the blending ratio of the above photopolymerization initiator is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass in total of the organopolysiloxane compound and the acrylic compound in the resin composition.

[0025] The photocurable resin composition of the present invention may contain additives as optional components. The additives are not particularly limited, but additives such as polymerization inhibitors, solvents, photosensitizers, leveling agents, slip agents, defoaming agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive agents, inorganic fillers, pigments, dyes, etc. are preferably used. However, the optional components are blended into the photocurable resin composition of the present invention within a range that does not impair the effects of the present invention. In the photocurable resin composition of the present invention, the content of the organopolysiloxane compound represented by the formula (1) is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 7.5% by mass, and even more preferably 0.2 to 5.0% by mass.

[0026] The photocurable resin composition of the present invention can be produced by mixing the organopolysiloxane compound represented by the formula (1), a polyvalent acrylic compound, a photopolymerization initiator, and the various additives added as necessary. The mixing method and the apparatus used for mixing are not particularly limited, and known methods and apparatuses may be used. Also, the order of mixing the respective components is not particularly limited, and all the components may be mixed at once, or the respective components may be sequentially added and mixed in an arbitrary order. Since the organopolysiloxane compound of the present invention is excellent in compatibility with photocurable resins such as acrylic compounds, a photocurable composition containing the compound and an acrylic compound can be a cured product with high transparency and excellent appearance. Further, since the organopolysiloxane compound of the present invention has high photocurability, a composition containing the compound can be cured with less energy and is less likely to bleed. Furthermore, it is possible to save energy and shorten the process when producing a cured product. Also, since the organopolysiloxane compound of the present invention has a low viscosity and excellent workability, a composition containing the compound is also a composition with good handleability. Furthermore, a composition containing the organopolysiloxane compound of the present invention can be a cured product with excellent antifouling properties.

Examples

[0027] Hereinafter, examples and comparative examples will be shown to specifically describe the present invention. However, the present invention is not limited to the following examples. In the following examples, the kinematic viscosity is the value measured at 25 °C using a Cannon-Fenske viscometer in accordance with JIS Z 8803:2011.

[0028] [Example 1] Into a reaction vessel, 200 g of an organopolysiloxane represented by the following formula (3-1), 0.034 g of 2,6-di-tert-butyl-p-cresol, and 0.011 g of iron(III) acetylacetonate were placed. Thereto, 25.4 g of 2-isocyanatoethyl acrylate was added dropwise at 50 °C over 30 minutes, and further stirred at 60 °C for 4 hours to cause a reaction, obtaining an organopolysiloxane represented by the following formula (1-1) (FIG. 1 is the 1 1H-NMR spectrum chart of the organopolysiloxane compound synthesized in Example 1). [Chemical formula]

[0029] The 1 chemical shift of the 1H-NMR spectrum of the obtained organopolysiloxane compound (Measuring device: AVANCE400 manufactured by Bruker, solvent CDCl3) [Table 1]

[0030] [Example 2] Into a reaction vessel, 224 g of an organopolysiloxane represented by the following formula (3-2), 0.037 g of 2,6-di-tert-butyl-p-cresol, and 0.012 g of iron(III) acetylacetonate were placed. Thereto, 25.4 g of 2-isocyanatoethyl acrylate was added dropwise at 50 °C over 30 minutes, and further stirred at 60 °C for 4 hours to cause a reaction, obtaining an organopolysiloxane represented by the following formula (1-2). [Chemical formula]

[0031] [Example 3] Into a reaction vessel, 200 g of an organopolysiloxane represented by the following formula (3-3), 0.035 g of 2,6-di-tert-butyl-p-cresol, and 0.017 g of iron(III) acetylacetonate were placed. Thereto, 31.9 g of 2-isocyanatoethyl acrylate was added dropwise at 50°C over 30 minutes, and the mixture was further stirred at 60°C for 4 hours to cause a reaction, obtaining an organopolysiloxane represented by the following formula (1-3). [Chemical formula]

[0032] [Example 4] Into a reaction vessel, 225 g of an organopolysiloxane represented by the following formula (3-4), 0.045 g of 2,6-di-tert-butyl-p-cresol, and 0.027 g of iron(III) acetylacetonate were placed. Thereto, 45.4 g of 2-isocyanatoethyl acrylate was added dropwise at 50°C over 30 minutes, and the mixture was further stirred at 60°C for 4 hours to cause a reaction, obtaining an organopolysiloxane represented by the following formula (1-4). [Chemical formula]

[0033] [Comparative Example 1] Into a reaction vessel, 200 g of an organopolysiloxane represented by the following formula (3-5), 0.035 g of 2,6-di-tert-butyl-p-cresol, and 0.018 g of iron(III) acetylacetonate were placed. Thereto, 32.3 g of 2-isocyanatoethyl acrylate was added dropwise at 50°C over 30 minutes, and the mixture was further stirred at 60°C for 4 hours to cause a reaction, obtaining an organopolysiloxane represented by the following formula (4). [Chemical formula]

[0034] [Comparative Example 2] Into a reaction vessel, 200 g of an organopolysiloxane represented by the following formula (3-6), 0.035 g of 2,6-di-tert-butyl-p-cresol, and 0.018 g of iron(III) acetylacetonate were placed. Thereto, 27.7 g of 2-isocyanatoethyl acrylate was added dropwise at 50 °C over 30 minutes, and the mixture was further stirred at 60 °C for 4 hours to effect reaction, thereby obtaining an organopolysiloxane represented by the following formula (5). [Chemical formula]

[0035] [Comparative Example 3] Into a reaction vessel, 200 g of an organopolysiloxane represented by the following formula (3-7), 0.033 g of 2,6-di-tert-butyl-p-cresol, and 0.017 g of iron(III) acetylacetonate were placed. Thereto, 23.7 g of 2-isocyanatoethyl acrylate was added dropwise at 50 °C over 30 minutes, and the mixture was further stirred at 60 °C for 4 hours to effect reaction, thereby obtaining an organopolysiloxane represented by the following formula (6). [Chemical formula]

[0036] [Comparative Example 4] Into a reaction vessel, 200 g of an organopolysiloxane represented by the following formula (3-8), 0.032 g of 2,6-di-tert-butyl-p-cresol, and 0.016 g of iron(III) acetylacetonate were placed. Thereto, 15.9 g of 2-isocyanatoethyl acrylate was added dropwise at 50 °C over 30 minutes, and the mixture was further stirred at 60 °C for 4 hours to effect reaction, thereby obtaining an organopolysiloxane represented by the following formula (7). [Chemical formula]

[0037] [Comparative Example 5] Into a reaction vessel, 230 g of an organopolysiloxane represented by the following formula (3-9), 0.036 g of 2,6-di-tert-butyl-p-cresol, and 0.018 g of iron(III) acetylacetonate were placed, and 9.32 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was further stirred at 60°C for 4 hours to cause a reaction, and an organopolysiloxane represented by the following formula (8) was obtained.

Chemical formula

[0038] [Comparative Example 6] Into a reaction vessel, 90 g of an organopolysiloxane represented by the following formula (3-10), 75 g of toluene, 10.5 g of triethylamine, and 0.040 g of 2,6-di-tert-butyl-p-cresol were placed, and 7.5 g of acryloyl chloride was added dropwise thereto at 50°C over 30 minutes. The mixture was further stirred at 60°C for 4 hours to cause a reaction. The resulting mixture was filtered, and toluene, triethylamine, and the excess amount of acryloyl chloride were distilled off under reduced pressure to obtain an organopolysiloxane represented by the following formula (9).

Chemical formula

[0039] [Comparative Example 7] An organopolysiloxane represented by the following formula (10).

Chemical formula

[0040] [Comparative Example 8] Into a reaction vessel, 280 g of an organopolysiloxane represented by the following formula (3-11), 0.048 g of 2,6-di-tert-butyl-p-cresol, and 0.024 g of iron(III) acetylacetonate were placed, and 34.8 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was further stirred at 60°C for 4 hours to cause a reaction, and an organopolysiloxane represented by the following formula (11) was obtained. [Chemical formula]

[0041] [Comparative Example 9] Into a reaction vessel, 100 g of an organopolysiloxane represented by the following formula (3-12), 0.017 g of 2,6-di-tert-butyl-p-cresol, and 0.008 g of iron(III) acetylacetonate were placed. Then, 15.0 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes, and the mixture was further stirred at 60°C for 4 hours to cause a reaction, thereby obtaining an organopolysiloxane represented by the following formula (12). [Chemical formula]

[0042] [Comparative Example 10] An organopolysiloxane represented by the following formula (13). [Chemical formula]

[0043] [Evaluation of Compatibility with Acrylic Monomers] 5 g of the organopolysiloxanes of Examples 1 to 4 and Comparative Examples 1 to 10 above were mixed with 5 g of each of the three acrylic monomers described in Table 2, and the resulting mixture was observed visually to evaluate the solubility according to the following criteria. The results are shown in Table 1. [Evaluation Criteria] ○: The mixture is transparent. △: The mixture is turbid but homogeneous. ×: The mixture is separated into two phases.

[0044] [Evaluation of Transparency of Cured Product] 0.2 g of each of the organopolysiloxanes obtained in Examples 1 to 4 and Comparative Examples 1 to 10, 5.0 g of dipentaerythritol hexaacrylate, 5.0 g of 1,6 - hexanediol diacrylate, and 0.05 g of Omnirad 1173 of IGM Resins and 0.05 g of Omnirad TPO as a photopolymerization initiator were added to prepare a composition liquid. The composition liquid was applied to a PMMA substrate using a bar coater No. 4. Using a UV curing device (MUVBA of Aitech System), ultraviolet rays with a wavelength of 365 nm and an intensity of 140 mW / cm 2 were irradiated onto the coated film for 10 seconds in a nitrogen atmosphere to cure it. The cured product was visually observed, and the transparency was evaluated according to the following criteria. [Evaluation Criteria] ○: No turbidity. ×: There is turbidity. -: Evaluation not possible due to separation of the composition liquid.

[0045] [Evaluation of Photocurability] A composition liquid was prepared by adding 0.020 g of Omnirad 1173 of IGM Resins as a photopolymerization initiator to 10 g of each of the organopolysiloxanes obtained in Examples 1 to 4 and Comparative Examples 1 to 10. For the obtained composition liquid, using a viscoelasticity measuring device (DHR2 (Discovery Hybrid Rheometer) of TA Instruments), the gelation point (the time when the storage modulus (G') = the loss modulus (G'')) of the composition liquid was measured under the following conditions to evaluate the photocurability. Note that the organopolysiloxane of Comparative Example 3 was solid and could not be measured. Also, the gelation point of a composition liquid prepared by adding 0.020 g of Omnirad 1173 to 10 g of trimethylolpropane triacrylate was measured under the same conditions, and the gelation point was 28.9 seconds. The results of other examples and comparative examples are shown in Table 2. [Measurement Conditions for Gelation 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

[0046] [Evaluation of antifouling property] Regarding the organopolysiloxanes obtained in Examples 1 to 4 and Comparative Examples 1 to 10 above, cured products were prepared in the same manner as in the above [Evaluation of transparency of cured products]. After being left standing at 25°C for 24 hours after ultraviolet irradiation, they were drawn with an oil-based magic marker, and after being left standing at 25°C for another 4 hours, the magic marker marks were wiped with a Kimwipe and visually observed to evaluate the antifouling property according to the following criteria. The results are shown in Table 2. [Evaluation criteria] ○: No magic marker marks remain. ×: Magic marker marks remain. -: No evaluation due to separation of the composition liquid.

[0047]

Table 2

[0048] From the results in Table 2, compared with the organopolysiloxanes of Comparative Examples 1 and 2 in which the polyoxyethylene chain is short (n in Formula (2) is less than 9), the organopolysiloxane of Comparative Example 5 in which the ratio of the number of groups represented by Formula (2) to the total number of substituents is small, and the organopolysiloxanes of Comparative Examples 8 to 10 that do not have the group represented by Formula (2), the organopolysiloxane compound of the present invention was found to be excellent in compatibility with the acrylic compound.

[0049] In addition, the gelation point of trimethylolpropane triacrylate, which is known as an acrylic monomer with high photocurability, is 28.9 seconds. It was found that the organopolysiloxane compound of the present invention has a gelation point more than twice as fast as that of trimethylolpropane triacrylate. Furthermore, compared with the organopolysiloxanes of Comparative Examples 1 and 2 in which the polyoxyethylene chain is short (n in formula (2) is less than 9), and the organopolysiloxanes of Comparative Examples 6 to 10 that do not have the group represented by formula (2), the organopolysiloxane compound of the present invention was found to have very high photocurability.

[0050] In addition, compared with the organopolysiloxane of Comparative Example 7 that does not have the group represented by formula (2), has a polyoxyethylene group in the side chain, and has acryloyl groups at both ends, the organopolysiloxane compound of the present invention was found to be excellent in antifouling properties.

[0051] Furthermore, compared with the organopolysiloxane of Comparative Example 3 in which the polyoxyethylene chain is long (n in formula (2) is more than 12) and the organopolysiloxane of Comparative Example 4 in which the molecular weight of the one having the group represented by formula (2) is large, the organopolysiloxane of the present invention has a kinematic viscosity of 3,000 mm 2 / s or less, is easy to handle, and was found to be excellent in workability.

[0052] From the above, the organopolysiloxane compound of the present invention is superior to the acrylic-modified organopolysiloxanes of the comparative examples in all of the compatibility with acrylic compounds, photocurability, antifouling properties, and workability, and is useful as an additive to photocurable resin compositions and the like, and as a photocurable silicone elastomer, coating agent, etc.

Claims

1. An organopolysiloxane compound represented by the following formula (1), 【Chemical 1】 (In formula (1), R 1 is each independently an alkyl group having 1 to 6 carbon atoms, R 2 are each independently an alkyl group having 1 to 6 carbon atoms and the following formula (2) [Chemical 2] (In formula (2), L 1 is an alkylene group having 3 to 8 carbon atoms, and L 2 is an alkylene group having 2 to 4 carbon atoms, and n is a number from 9 to 12.) is a group selected from the groups represented by, R 3 is a group represented by formula (2), a is a number from 5 to 40, and b is a number from 0 to 5.) The organopolysiloxane compound represented by the formula (1) has two or more groups represented by the formula (2) in one molecule, An organopolysiloxane compound in which the proportion of the number of groups represented by the formula (2) is 4 to 15% with respect to the total number of substituents in the organopolysiloxane compound represented by the formula (1).

2. R 1 The organopolysiloxane compound according to claim 1, wherein all of them are methyl groups.

3. a is a number from 5 to 40, b is 0, and all of R in formula (1) 2 are groups represented by formula (2). The organopolysiloxane compound according to claim 1.

4. a is a number from 5 to 40, b is a number from 2 to 5, and R in formula (1) 2 The organopolysiloxane compound according to claim 1, wherein all of them are methyl groups.

5. a is a number from 5 to 40, b is a number from 1 to 5, and all of R in formula (1) 2 are groups represented by formula (2). The organopolysiloxane compound according to claim 1.

6. A photocurable resin composition comprising the organopolysiloxane compound according to any one of Claims 1 to 5, a polyvalent acrylic compound, and a photopolymerization initiator.

Images