Organopolysiloxane compound and photocurable resin composition containing same

Abstract

Provided is a radical-polymerizable organopolysiloxane compound which is compatible with acrylic compounds and exhibits high photocurability, high anti-fouling properties, low viscosity and excellent workability.　The organopolysiloxane compound is represented by formula (1).　[Compound 1] (In formula (1), R1 moieties are each independently an alkyl group having 1-6 carbon atoms, 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). [Compound 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). R 3 is a group represented by formula (2), a is a number between 5 and 40, and b is a number between 0 and 5.

Description

Organopolysiloxane compound and photocurable resin composition containing same

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

[0002] One known method for imparting high water repellency, stain resistance, lubricity, etc. to photocurable resins is copolymerization with an organopolysiloxane containing a (meth)acryloyl group (Patent Document 1). However, many (meth)acryloyl group-containing organopolysiloxanes have low compatibility with photocurable resins, leading to problems such as separation when incorporated into photocurable resin compositions and cloudiness in the cured resin (Patent Document 2). Furthermore, many (meth)acryloyl group-containing organopolysiloxanes have low photocurability, leading to problems such as bleeding of unreacted organopolysiloxane from the cured resin over time (Patent Document 3). Furthermore, organopolysiloxanes with low photocurability are susceptible to curing inhibition by oxygen. One method for improving photocurability is the introduction of urea groups, but this increases viscosity and reduces workability (Patent Document 4). Therefore, an organopolysiloxane compound that solves these problems has been eagerly awaited.

[0003] JP 2022-138932 A JP 2013-23547 A JP 2005-36018 A JP 2020-152771 A

[0004] Therefore, an object of the present invention is to provide a radical-polymerizable organopolysiloxane compound that has high compatibility with photocurable resins such as acrylic compounds, high photocurability, and antifouling properties, and that has low viscosity and excellent workability, as well as a photocurable resin composition containing the same.

[0005] The present inventors have conducted extensive research to solve the above problems and have found that an organopolysiloxane compound having an acryloyl group connected via a specific linking group can achieve the above object, thereby completing the present invention.

[0006] [1] An organopolysiloxane compound represented by the following formula (1): (In formula (1), R 1 are each independently an alkyl group having 1 to 6 carbon atoms, and R 2 are each independently an alkyl group having 1 to 6 carbon atoms and a group represented by the following formula (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; 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, and the ratio of the number of groups represented by formula (2) to the total number of substituents in the organopolysiloxane compound represented by formula (1) is 4 to 15%. [2] R 1 [3] The organopolysiloxane compound according to [1], wherein a is a number from 5 to 40, b is 0, and R 2 [4] The organopolysiloxane compound according to [1] or [2], wherein all of R in formula (1) are groups represented by formula (2). 2 [5] The organopolysiloxane compound according to [1] or [2], wherein a is a number from 5 to 40, b is a number from 1 to 5, and R in formula (1) are all methyl groups. 2 The organopolysiloxane compound according to [1] or [2], wherein all of the groups represented by the formula (2) 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 polyhydric acrylic compound, and a photopolymerization initiator.

[0007] The organopolysiloxane compound of the present invention has excellent compatibility with photocurable resins such as acrylic compounds. Therefore, photocurable compositions containing the polysiloxane compound and the acrylic compound can be cured to have high transparency and excellent appearance. Furthermore, because the organopolysiloxane compound of the present invention has high photocurability, compositions containing the compound are less likely to bleed even when cured with low energy, and can also save energy and shorten the process when producing cured products. Furthermore, compositions containing the compound can be cured to have excellent antifouling properties. Furthermore, because the compound has low viscosity and excellent workability, compositions containing the compound also have good handleability. Therefore, the organopolysiloxane compound of the present invention and photocurable resin compositions containing the compound are suitable for paints, coating agents, inks, etc.

[0008] The organopolysiloxane compound synthesized in Example 1 1 1 is a H-NMR spectrum chart.

[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), has two or more acryloyl groups in one molecule, and readily reacts with radically polymerizable compounds. In the above formula (1), R 1 are independently alkyl groups having 1 to 6 carbon atoms, preferably methyl groups. 2 are independently selected from alkyl groups having 1 to 6 carbon atoms and groups represented by the following formula (2), and are preferably selected from methyl groups and groups represented by the following formula (2). 3 is a group represented by the following formula (2):

[0011] In formula (2), L 1 is an alkylene group having 3 to 8 carbon atoms, preferably an alkylene group having 3 to 4 carbon atoms, and more preferably an alkylene group having 3 carbon atoms. 2 is an alkylene group having 2 to 4 carbon atoms, preferably an alkylene group having 2 carbon atoms. n is a number from 9 to 12, preferably a number from 9 to 10.

[0012] In the above formula (1), a is a number from 5 to 40, preferably a number from 10 to 30, and more preferably a number from 15 to 35. b is a number from 0 to 5, and 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 2 When all of the groups are alkyl groups having 1 to 6 carbon atoms, b is a number from 2 to 5, and preferably a number from 2 to 4.

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

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

[0015] The organopolysiloxane compound of the present invention represented by the above formula (1) can be produced by a urethane reaction between an organopolysiloxane having a polyoxyethylene group terminated in a hydroxy group and an acrylic compound having an isocyanate group, such as 2-isocyanatoethyl acrylate.

[0016] The above reaction may be carried out in the presence of a catalyst, if necessary. Examples of such catalysts include di-n-octyltin oxide, dibutyltin dilaurate, iron(III) acetylacetonate, bismuth(III) octoate, titanium(IV) 2-ethylhexyloxide, 1,4-diazabicyclo[2.2.2]octane, 2,2'-dimorpholinodiethyl ether, and triethylamine. Among these, iron(III) acetylacetonate is preferred because of its high activity and low toxicity. These catalysts may be used alone or in combination of two or more.

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

[0018] The reaction may be carried out in the presence of a solvent, if necessary. The solvent preferably does not have a group reactive with an isocyanate group, and examples thereof include hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.), ethers (diethyl ether, tetrahydrofuran, 1,4-dioxane, etc.), esters (ethyl acetate, butyl acetate), and ketones (methyl ethyl ketone, methyl isobutyl ketone). These solvents may be used alone or in combination of two or more.

[0019] 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.

[0020] [Photocurable Resin Composition] The organopolysiloxane compound of the present invention can be blended into a photocurable composition containing a polyacrylic compound and a photopolymerization initiator to provide a cured product with excellent antifouling properties.

[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 polyacrylic 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 per 100 parts by mass of the polyacrylic compound, since the effect of adding the organopolysiloxane compound of the present invention to the photocurable resin composition can be fully obtained within this range.

[0023] Examples of photopolymerization initiators include 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-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 130, manufactured by IGM Resins), and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Omnirad 140, manufactured by IGM Resins). Examples of photopolymerization initiators include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (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), and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO manufactured by IGM Resins). 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 photopolymerization initiator is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the organopolysiloxane compound and 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 suitable additives include polymerization inhibitors, solvents, photosensitizers, leveling agents, slip agents, antifoaming agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive agents, inorganic fillers, pigments, and dyes. The optional components are incorporated into the photocurable resin composition of the present invention to the extent that they do not impair the effects of the present invention. The content of the organopolysiloxane compound represented by formula (1) in the photocurable resin composition of the present invention 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 formula (1), a polyacrylic compound, a photopolymerization initiator, and the various additives described above, if necessary. The mixing method and the equipment used for mixing are not particularly limited, and known methods and equipment may be used. The order in which the components are mixed is also not particularly limited; all components may be mixed at once, or the components may be added and mixed sequentially in any order. Because the organopolysiloxane compound of the present invention has excellent compatibility with photocurable resins such as acrylic compounds, photocurable compositions containing the compound and the acrylic compound can produce cured products with high transparency and excellent appearance. Furthermore, because the organopolysiloxane compound of the present invention has high photocurability, compositions containing the compound are less likely to bleed even when cured with low energy, and furthermore, energy savings and process shortening are possible when producing cured products. Furthermore, the organopolysiloxane compound of the present invention has low viscosity and excellent workability, and therefore compositions containing the compound also have good handleability. Furthermore, compositions containing the organopolysiloxane compounds of the present invention can give cured products with excellent antifouling properties.

[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 kinematic viscosity is a value measured at 25°C using a Cannon-Fenske viscometer in accordance with JIS Z 8803:2011.

[0028] Example 1 200 g of 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 in a reaction vessel, and 25.4 g of 2-isocyanatoethyl acrylate was added dropwise at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (1-1) (Figure 1 shows the organopolysiloxane compound synthesized in Example 1). 1 1 H-NMR spectrum chart).

[0029] The obtained organopolysiloxane compound 1 Chemical shift of H-NMR spectrum (measurement equipment: AVANCE 400 manufactured by Bruker, solvent: CDCl3)

[0030] Example 2 A reaction vessel was charged with 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, and 25.4 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (1-2).

[0031] Example 3 200 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 in a reaction vessel, and 31.9 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (1-3).

[0032] Example 4 A reaction vessel was charged with 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, and 45.4 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (1-4).

[0033] Comparative Example 1 A reaction vessel was charged with 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, and 32.3 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (4).

[0034] Comparative Example 2 A reaction vessel was charged with 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, and 27.7 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (5).

[0035] Comparative Example 3 A reaction vessel was charged with 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, and 23.7 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (6).

[0036] Comparative Example 4 A reaction vessel was charged with 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, and 15.9 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (7).

[0037] Comparative Example 5 A reaction vessel was charged with 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, and 9.32 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (8).

[0038] Comparative Example 6 A reaction vessel was charged with 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, to which 7.5 g of acrylic acid chloride was added dropwise over 30 minutes at 50° C., and the mixture was allowed to react with stirring for an additional 4 hours at 60° C. The resulting mixture was filtered, and the toluene, triethylamine, and excess acrylic acid chloride were distilled off under reduced pressure to obtain an organopolysiloxane represented by the following formula (9).

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

[0040] Comparative Example 8 A reaction vessel was charged with 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, and 34.8 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (11).

[0041] Comparative Example 9 A reaction vessel was charged with 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, and 15.0 g of 2-isocyanatoethyl acrylate was added dropwise thereto at 50°C over 30 minutes. The mixture was then stirred at 60°C for a further 4 hours to allow the reaction to proceed, yielding an organopolysiloxane represented by the following formula (12).

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

[0043] [Evaluation of Compatibility with Acrylic Monomers] 5 g of each of the organopolysiloxanes of Examples 1 to 4 and Comparative Examples 1 to 10 above was mixed with 5 g of each of the three acrylic monomers listed in Table 2, and the resulting mixture was visually observed 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 cloudy but homogeneous. ×: The mixture is separated into two phases.

[0044] [Evaluation of Transparency of Cured Products] A composition liquid was prepared by adding 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 and 0.05 g of Omnirad TPO, both manufactured by IGM Resins, as photopolymerization initiators. The composition liquid was applied to a PMMA substrate using a No. 4 bar coater. Using a UV curing device (MUVBA manufactured by ITEC Systems), the cured product was cured with light at a wavelength of 365 nm and an intensity of 140 mW / cm. 2 The coating film was irradiated with ultraviolet light of 1000 kJ / cm 2 for 10 seconds in a nitrogen atmosphere to cure. The cured product was visually observed and its transparency was evaluated according to the following criteria. [Evaluation criteria] ○: No turbidity. ×: Turbidity present. -: No evaluation due to separation of the composition liquid.

[0045] [Evaluation of Photocurability] 0.020 g of Omnirad 1173 (manufactured by IGM Resins) was added as a photopolymerization initiator to 10 g of each of the organopolysiloxanes obtained in Examples 1 to 4 and Comparative Examples 1 to 10 to prepare a liquid composition. The gel point (the time at which storage modulus (G') = loss modulus (G")) of the resulting liquid composition was measured under the following conditions using a viscoelasticity measuring device (TA Instruments' DHR2 (Discovery Hybrid Rheometer)) to evaluate photocurability. Note that the organopolysiloxane of Comparative Example 3 was solid and therefore could not be measured. The gel point of a liquid composition in which 0.020 g of Omnirad 1173 was added to 10 g of trimethylolpropane triacrylate was also measured under the same conditions, and the gel point was found to be 28.9 seconds. The results of the other Examples and Comparative Examples are shown in Table 2. [Conditions for measuring gel point] UV light source: OmniCure SERIES 2000 (Excelitas Technologies) UV irradiance: 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 Stain Resistance] Cured products were prepared using the organopolysiloxanes obtained in Examples 1 to 4 and Comparative Examples 1 to 10 in the same manner as in [Evaluation of Transparency of Cured Products] above. After UV irradiation and leaving to stand at 25°C for 24 hours, a mark was drawn with an oil-based marker, and after leaving to stand for a further 4 hours at 25°C, the mark was rubbed with a Kimwipe and visually inspected to evaluate stain resistance according to the following criteria. The results are shown in Table 2. [Evaluation Criteria] ○: No mark left. ×: Mark left. −: No evaluation due to separation of the composition liquid.

[0047]

[0048] The results in Table 2 demonstrate that the organopolysiloxane compounds of the present invention have excellent compatibility with acrylic compounds compared to the organopolysiloxanes of Comparative Examples 1 and 2, which have short polyoxyethylene chains (n ​​in formula (2) is less than 9), the organopolysiloxane of Comparative Example 5, which has a low ratio of the number of groups represented by formula (2) to the total number of substituents, and the organopolysiloxanes of Comparative Examples 8 to 10, which do not have a group represented by formula (2).

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

[0050] Furthermore, it was found that the organopolysiloxane compounds of the present invention have excellent antifouling properties compared to the organopolysiloxane of Comparative Example 7, which does not have a group represented by formula (2), has polyoxyethylene groups in the side chains, and has acryloyl groups at both ends.

[0051] Furthermore, compared to the organopolysiloxane of Comparative Example 3, which has a long polyoxyethylene chain (n in formula (2) is greater than 12), and the organopolysiloxane of Comparative Example 4, which has a group represented by formula (2) but has a high molecular weight because the value of b in formula (1) is greater than 5, the organopolysiloxane of the present invention has a kinematic viscosity of 3,000 mm 2 It was found that it was easy to handle and had excellent workability at 0.05 wt. / s or less.

[0052] From the above, it can be seen that the organopolysiloxane compounds of the present invention are superior to the acrylic-modified organopolysiloxanes of the comparative examples in all aspects: compatibility with acrylic compounds, photocurability, antifouling properties, and workability. They are therefore useful as additives to photocurable resin compositions, photocurable silicone elastomers, coating agents, and the like.

Claims

1. An organopolysiloxane compound represented by the following formula (1): (In formula (1), R 1 are each independently an alkyl group having 1 to 6 carbon atoms; R 2 each independently represents an alkyl group having 1 to 6 carbon atoms and a group represented by the following formula (2): (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; 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, and the ratio of the number of groups represented by formula (2) to the number of all substituents in the organopolysiloxane compound represented by formula (1) is 4 to 15%.

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

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

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

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

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

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